@article {42471, title = {1,4-Dipolar cycloaddition in organic synthesis: a facile route to isoquinoline fused heterocycles}, journal = {Arkivoc}, volume = {2005}, year = {2005}, month = {JAN}, pages = {178-188}, type = {Article}, abstract = {

The three component condensation reactions involving isoquinoline, dimethyl acetylenedicarboxylate and carbonyl dipolarophiles such as o- and p-benzoquinones and Nsubstituted isatins constitute a one-pot synthesis of a variety of [1,3]oxazino isoquinoline derivatives via 1,4-dipolar cycloaddition.

}, author = {Nair, Vijay and Sreekanth, Anakkalil R. and Abhilash, N. and Biju, Akkattu T. and Varma, Luxmi and Viji, Sreemathi and Mathew, Saumini} } @article { ISI:000231556400005, title = {2,5-dioxido-1,4-benzoquinonediimine (H2L2-), a hydrogen-bonding noninnocent bridging ligand related to aminated topaquinone: different oxidation state distributions in complexes [{(bpy)(2)Ru}(2)(mu-H2L)](n) (n=0,+,2+,3+,4+) and [{(acac)(2)Ru}(2)(mu-H2L)]}, journal = {Chemistry - a European Journal}, volume = {11}, number = {17}, year = {2005}, month = {AUG}, pages = {4901-4911}, publisher = {WILEY-V C H VERLAG GMBH}, type = {Article}, address = {PO BOX 10 11 61, D-69451 WEINHEIM, GERMANY}, abstract = {

{The symmetrically dinuclear title compounds were isolated as diamagnetic [(bpy)(2)Ru(mu-H2L)Ru(bpy)(2)]- (ClO4)(2) (1-(ClO4)(2)) and as paramagnetic [(acac)(2)Ru(mu-H2L)Ru(acac)(2)] (2) complexes (bpy = 2,2{\textquoteright}-bipyridine; acac(-) -

}, keywords = {bridging ligands, Density functional calculations, EPR spectroscopy, N, O ligands, ruthenium}, issn = {0947-6539}, doi = {10.1002/chem.2005.00202}, author = {Kar, S. and Sarkar, B. and Ghumaan, Sandeep and Janardanan, D. and van Slageren, J. and Fiedler, Jan and Puranik, Vedavati G. and Sunoj, R. B. and Kaim, Wolfgang and Lahiri, Goutam Kumar} } @article { ISI:000234202200037, title = {3-Aminopropyltriethoxysilyl functionalized Na-Al-MCM-41 solid base catalyst for selective preparation of 2-phenylpropionitrile from phenylacetonitrile}, journal = {Applied Catalysis A-General}, volume = {292}, year = {2005}, month = {SEP}, pages = {344-353}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Various solid base catalysts have been prepared by ion exchange of zeolites and Na-Al-MCM-41 and by organosilane grafting over mesoporous materials. Base catalysts thus synthesized were studied in the selective monomethylation of phenylacetonitrile (PAN) to 2-phenylpropionitrile (2-PPN) using dimethylcarbonate (DMC) as an alkylating agent in a Parr autoclave at a temperature ranging between 443 and 473 K and at autogenously developed pressure. NH2-Na-Al-MCM-41 (30) showed a high activity, and the optimum loading of 3-aminopropyltriethoxysilyl (3-APTES) was found to be 1.35 mmol g(-1), being consistent with the structural characterization. Co-condensation of 3-APTES, tetraethylorthosilicate (TEOS) and sodiumaluminate in the presence of surfactant provides a material with uniformly distributed basic sites responsible for high activity in the selective monomethylation of phenylacetonitrile. (c) 2005 Elsevier B.V. All rights reserved.

}, keywords = {2-phenylpropionitrile, base catalysis, dimethylcarbonate, monomethylation, NH2-Na-Al-MCM-41, phenylacetonitrile}, issn = {0926-860X}, doi = {10.1016/j.apcata.2005.06.013}, author = {Venkatesan, C. and Chidambaram, M. and Singh, A. P.} } @article { ISI:000228699400021, title = {Benzylation of benzene and other aromatics by benzyl chloride over mesoporous AlSBA-15 catalysts}, journal = {Microporous and Mesoporous Materials}, volume = {80}, number = {1-3}, year = {2005}, month = {MAY}, pages = {195-203}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Aluminum-containing mesoporous molecular sieves AISBA-15 with different n(Si)/n(Al), ratios and AIMCM-41 have been synthesized hydrothermally and characterized in detail by physicochemical methods, viz. XRD, N(2) adsorption and (27)Al NMR spectroscopy. The low angle XRD and N2 adsorption measurements reveal that the structural order of SBA-15 was retained after the incorporation of Al. The increase of the unit cell parameter with increasing aluminum content and (27)Al MAS NMR spectroscopy confirm the incorporation of aluminum in the framework. Benzylation of benzene and substituted benzenes reaction employing benzyl chloride as the alkylating agent over AISBA-15 and AIMCM-41 have been investigated. The influence of various reaction parameters such as reaction temperature, reactant feed ratio and catalyst amount affecting the activity and selectivity of AISBA-15, have been studied. Among the mesoporous catalysts studied, AISBA-15(45), where the number in parentheses indicates the molar nsilnA, ratio, shows both high conversion and high selectivity for the benzylation of benzene. The activity of this catalyst for the benzylation of different aromatic compounds is in the following order: benzene \> toluene \> p-xylene \> mesitylene \> anisole. Kinetics of the benzene benzylation over different catalysts have also been investigated. (c) 2005 Elsevier Inc. All rights reserved.

}, keywords = {Alkylation, AlSBA-15, Benzylation, SBA-15}, issn = {1387-1811}, doi = {10.1016/j.micromeso.2004.12.012}, author = {Vinu, A. and Sawant, D. P. and Ariga, Katsuhiko and Hartmann, Martin and Halligudi, Shivappa B.} } @article { ISI:000229592000044, title = {Copper- and ligand-free sonogashira reaction catalyzed by Pd(0) nanoparticles at ambient conditions under ultrasound irradiation}, journal = {Journal of Organic Chemistry}, volume = {70}, number = {12}, year = {2005}, month = {JUN}, pages = {4869-4872}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The Sonogashira reaction proceeds at ambient temperature (30 degrees C) in acetone or room-temperature ionic liquid, 1,3-di-n-butylimidazolium tetrafluoroborate ([bbim]BF4), as solvent under ultrasound irradiation to give enhanced reaction rates, excellent chemoselectivity, and high yields in the absence of a copper cocatalyst and a phosphine ligand. TEM analysis showed the formation of stable, crystalline, and polydispersed Pd(0) nanoparticles as catalyst for the reaction.

}, issn = {0022-3263}, doi = {10.1021/jo0503815}, author = {Gholap, Atul R. and Venkatesan, K. and Pasricha, R. and Daniel, Thomas and Lahoti, Rajgopal J. and Srinivasan, K. V.} } @article { ISI:000232743700020, title = {Direct synthesis of well-ordered and unusually reactive FeSBA-15 mesoporous molecular sieves}, journal = {Chemistry of Materials}, volume = {17}, number = {21}, year = {2005}, month = {OCT}, pages = {5339-5345}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Large-pore hexagonal SBA-15 molecular sieves partially substituted with iron(III) have been synthesized for the first time in highly acidic media. The degree of iron(III) incorporation into SBA-15 can easily be controlled by a simple adjustment of the molar ratio of water and hydrochloric acid. All the materials have been characterized by XRD, N-2 adsorption, UV-Vis DRS, ESR, and XANES spectroscopy. The characterization of the FeSBA-15 materials by UV-Vis DRS, ESR, and XANES spectroscopies suggests that the iron atoms are highly dispersed and mostly occupy isolated tetrahedral sites. XANES studies revealed that the proportion of tetrahedrally coordinated Fe atoms decreases with decreasing n(Si)/n(Fc) ratios. Benzylation of benzene (or substituted benzenes) using benzyl chloride as the alkylating agent over FeSBA-15 with different n(Si)/n(Fe) ratios was investigated as was the same reaction using AISBA-15 as catalyst. The influence of parameters such as reaction temperature, reactant feed ratio, and the presence of electron-donating substituents on the activity and selectivity of AISBA-15 was studied. Under optimized reaction conditions, the FeSBA-15 catalyst showed a superior catalytic performance in the benzylation of benzene and other aromatics using benzyl chloride, with a clean conversion of benzyl chloride to the monoalkylated product (100\% selectivity) with a very high rate constant when compared to other mesoporous materials such as AISBA-15 and FeHMS. Interestingly, use of FeSBA-15(21) resulted in quantitative conversion of benzyl chloride with a high rate constant of 2420.5 x 10(-4) min(-1) under the optimized reaction conditions.

}, issn = {0897-4756}, doi = {10.1021/cm050883z}, author = {Vinu, A. and Sawant, D. P. and Ariga, Katsuhiko and Hossain, K. Z. and Halligudi, Shivappa B. and Hartmann, Martin and Nomura, M.} } @article { ISI:000230122900010, title = {Effect of RuO2 in the shape selectivity of submicron-sized SnO2 structures}, journal = {Journal of Physical Chemistry B}, volume = {109}, number = {25}, year = {2005}, month = {JUN}, pages = {12297-12303}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Several dissimilar types of tin oxide microstructures including bipyramids, cubes, and wires synthesized effectively by means of a simple approach were investigated using X-ray diffraction (XRD), thermogravimetry/ differential thermometric analysis (TG-DTA), and X-ray photoelectron spectroscopy (XPS). A possible growth mechanism is proposed using the results of these studies. The texture coefficient values of all the structures, indexed to a tetragonal lattice, exhibit amazing variation in the preferred orientation with respect to their shapes. Although XPS data indicate that wires and cubes have a strong SnO2 type signal, bipyramids interestingly exhibit both SnO and SnO2 signals and a correlation of the binding energy helps in understanding the growth kinetics of such submicron structures. The. results suggest that the bipyramids are formed because of the vapor-solid process (VS) while wires and cubes are formed by the vapor-liquid-solid (VLS) progression.

}, issn = {1520-6106}, doi = {10.1021/jp044677a}, author = {Ramgir, N. S. and Mulla, Imtiaz S. and Vijayamohanan, K. P.} } @article { ISI:000227026100019, title = {Electrochemical studies of poly (3,4-ethylenedioxythiophene) PEDOT/VS2 nanocomposite as a cathode material for rechargeable lithium batteries}, journal = {Electrochemistry Communications}, volume = {7}, number = {2}, year = {2005}, month = {FEB}, pages = {213-218}, publisher = {ELSEVIER SCIENCE INC}, type = {Article}, address = {360 PARK AVE SOUTH, NEW YORK, NY 10010-1710 USA}, abstract = {

Here, we demonstrate the electrochemical characterization of a new type of layered poly (3,4-ethylenedioxythiophene) PEDOT/ VS2 nanocomposite. It has been prepared via flocculation of delaminated VS2 with subsequent in situ oxidative polymerization of 3,4-ethylenedioxythiophene (EDOT) with VS2 as a host material in the presence of an external oxidizing agent. The interlayer spacing Of VS2 expands from 5.71 to 14.01 A and this interlayer separation is consistent with the existence of a monolayer of PEDOT in the VS2 framework. X-ray diffraction, XPS and TEM studies have been;shown the change in interlayer separation is consistent with the existence of two phases of organic and inorganic species in the nanocomposites corresponding to the intercalation of PEDOT in the VS2 framework. The application potential of the nanocomposite as a cathode material for rechargeable lithium batteries is also demonstrated by the electrochemical intercalation of lithium into the PEDOT/VS2 nanocomposite, where a significant enhancement in the discharge capacity is observed (similar to130 mAh/g) compared to that (80 mAh/g) for pristine VS2. (C) 2004 Published by Elsevier B.V.

}, keywords = {layered nanocomposite, lithium batteries, polythiophene, vanadium disulfide}, issn = {1388-2481}, doi = {10.1016/j.elecom.2004.12.013}, author = {Murugan, A. Vadivel and Gopinath, Chinnakonda S. and Vijayamohanan, K.} } @article { ISI:000231714000001, title = {Electronic spectra and ionization potentials of halogen oxides using the fock space coupled-cluster method}, journal = {Collection of Czechoslovac Chemical Communications}, volume = {70}, number = {7}, year = {2005}, month = {JAN}, pages = {851-863}, publisher = {INST ORGANIC CHEM AND BIOCHEM}, type = {Article}, address = {ACAD SCI CZECH REPUBLIC, FLEMINGOVO NAM 2, PRAGUE 6 166 10, CZECH REPUBLIC}, abstract = {

The ionization potentials and excitation energies of halogen monoxides and dihalogen oxides are studied using fully size-extensive Fock space version of multi-reference coupled-cluster theory. The low-lying excited states of ClO-, FO-, Cl2O and F2O are obtained along with the ionization spectra of Cl2O and F2O. The adiabatic electron affinity of ClO, FO and the vertical detachment energy of ClO- and FO- are also presented.

}, issn = {0010-0765}, doi = {10.1135/cccc20050851}, author = {Vaval, N and Manohar, Prashant Uday and Pal, S} } @article { ISI:000233825900101, title = {Enhancement of double-layer capacitance behavior and its electrical conductivity in layered poly (3, 4-ethylenedioxythiophene)-based nanocomposites}, journal = {Applied Physics Letters}, volume = {87}, number = {24}, year = {2005}, month = {DEC}, pages = {243511}, publisher = {AMER INST PHYSICS}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

In this letter, we report on the enhanced double-layer capacitance of a layered poly (3, 4-ethylene dioxythiophene) PEDOT-MoO3 nanocomposite, which has been synthesized by a novel microwave irradiation method. The x-ray photoelectron spectroscopy analysis shows the changes in electron density and the shift in binding energy suggesting charge transfer from sulfur atoms upon PEDOT intercalation between MoO3 layers. The room-temperature conductivity for the PEDOT-MoO3 composite is found to be 1.82x10(-1) S cm(-1), which is four orders of magnitude higher than that of the pristine oxide (3.78x10(-5) S cm(-1)). The enhanced double-layer capacitance of the PEDOT-MoO3 nanocomposite (similar to 300 F g(-1)) compared to that (similar to 40 mF g(-1)) of pristine MoO3 is attributed to higher electronic conductivity, enhanced bidimensionality, and increase in surface area of the nanocomposite.

}, issn = {0003-6951}, doi = {10.1063/1.2140468}, author = {Murugan, A. Vadivel and Viswanath, A. K. and Campet, Guy and Gopinath, Chinnakonda S. and Vijayamohanan, K.} } @article { ISI:000226995900011, title = {Entrapment of poly(3,4-ethylenedioxythiophene) between VS2 layers to form a new organic-inorganic intercalative nanocomposite}, journal = {Journal of Materials Chemistry}, volume = {15}, number = {8}, year = {2005}, month = {JAN}, pages = {902-909}, publisher = {ROYAL SOC CHEMISTRY}, type = {Article}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Here we report the synthesis and characterization of a new class of nanocomposite by direct in situ oxidative polymerization of 3,4-ethylenedioxythiophene (EDOT) with VS2 as a host material in the presence of an external oxidizing agent. Upon intercalation, the interlayer spacing of VS2 expands from 5.71 Angstrom to 14.01 Angstrom, followed by exfoliation and a restacking process facilitating expansion of the lattice in a direction perpendicular to the dichalcogenide layers. This change in interlayer separation is consistent with the existence of two phases of organic and inorganic species in the nanocomposites corresponding to the intercalation of PEDOT in the VS2 framework. The resulting nanocomposite is characterized by thermal analysis (TGA), X-ray diffraction, FTIR, SEM, TEM, and four-probe electrical conductivity measurements. The application potential of the nanocomposite as a cathode material for rechargeable lithium batteries is also demonstrated by the electrochemical intercalation of lithium into the PEDOT-VS2 nanocomposite, where a significant enhancement in the discharge capacity is observed (similar to130 mA h g(-1)) compared to that (80 mA h g(-1)) for pristine VS2.

}, issn = {0959-9428}, doi = {10.1039/b414922j}, author = {Murugan, A. Vadivel and Quintin, M. and Delville, M. H. and Campet, Guy and Vijayamohanan, K.} } @article { ISI:000232737900002, title = {Enzymatic hydrolysis of delignified bagasse polysaccharides}, journal = {Carbohydrate Polymers}, volume = {62}, number = {1}, year = {2005}, month = {OCT}, pages = {6-10}, publisher = {ELSEVIER SCI LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Sugarcane bagasse, consisting of cellulose, xylan, and lignin, was chemically treated to generate bagasse samples with continuously decreasing content of lignin. These bagasse samples were hydrolyzed by cellulase and xylanase enzymes, produced earlier by Penicillium janthinellum NCIM 1171 in the same bagasse polysaccharides production medium. The hydrolysis was carried out by using different concentrations of the enzymes at two different temperatures, 30 and 50 degrees C, taking hydrolysis of Avicel as control. It was found that while the maximum hydrolysis for Avicel was 70\% that of some of the bagasse polysaccharides was as high as 95\%. The products of hydrolysis were glucose, xylose, and arabinose, as confirmed by high pressure ion chromatography (HPIC). It is interesting to note that arabinose, which constitutes about 10\% of the weight of bagasse xylan, could also be released easily by the enzymes. Also, the initial rates of hydrolysis was found to be much higher for the bagasse polysaccharides, and in some cases about 90\% of the hydrolysis occurred within 20 h. Amongst all bagasse samples, the sample with (Kappa no. 1.2, lignin content 0.18\%) gave the highest degree of hydrolysis at 50 degrees C. Even the bagasse polysaccharide with Kappa no. 16.8 (lignin content 2.5\%) underwent greater extent of hydrolysis than Avicel. Apparently, the delignified bagasse medium appears to be a facile medium for the combined hydrolytic action of the cellulase and xylanase enzymes. Considering that sugarcane bagasse is a waste biomass material available in abundance annually, this methodology can be used to value-add to this biomass to produce sugars, which can be fermented to produce biofuels like ethanol. (C) 2005 Elsevier Ltd. All rights reserved.

}, keywords = {bagasse polysaccharides, Cellulase, chemical treatment, Enzymatic hydrolysis, Penicillium janthinellum, Sugarcane bagasse, Xylanase}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2005.07.010}, author = {Adsul, Mukund G. and Ghule, J. E. and Shaikh, H. and Singh, R. and Bastawade, Kulbhushan B. and Gokhale, D. V. and Varma, Anjanikumar} } @article { ISI:000232815700010, title = {Formation of nanosized zirconia-supported 12-tungstophosphoric acid in mesoporous silica SBA-15: a stable and versatile solid acid catalyst for benzylation of phenol}, journal = {Journal of Catalysis}, volume = {235}, number = {2}, year = {2005}, month = {OCT}, pages = {341-352}, publisher = {ACADEMIC PRESS INC ELSEVIER SCIENCE}, type = {Article}, address = {525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USA}, abstract = {

A nanosized zirconia-supported 12-tungstophosphoric acid (TPA) in SBA-15 composite was prepared by wet impregnation of TPA/ZrO2 nanoparticles inside the mesoporous channels of SBA-15. The resulting composite material was calcined at 1123 K and characterized by elemental analysis, powder X-ray diffraction, nitrogen adsorption isotherms, transmission electron microscopy (TEM), scanning electron microscopy (SEM), solid-state P-31 CP-MAS NMR, Si-29 MAS NMR, UV-vis diffuse reflectance spectra, FTIR, TPD of ammonia, FTIR pyridine adsorption, and thermogravimetric analysis (TG-DTG). The synthesized TPA/ZrO2/SBA-15 showed a well-ordered hexagonal inesoporous structure and mesoporous support SBA-15 stabilized ZrO2-t (tetragonal) phase with crystal size in the range of 3-4 nm. SBA-15 was a better support than MCM-41 and MCM-48 because it retained its mesostructure even after high TPA loading and high calcination temperatures. Mesoporous silica support plays an important role in stabilizing the catalytically active tetragonal phase of zirconia, which gave the most active catalysts. The catalysts were examined for their catalytic activities in the liquid phase benzylation of phenol with benzyl alcohol and the catalyst 15 wt\% TPA/ 22.4 wt\% ZrO2/SBA-15 calcined at 1123 K was found to have high acidity and to be 10 times more active than neat TPA/ZrO2 Under the reaction conditions studied in benzylation of phenol. (c) 2005 Elsevier Inc. All rights reserved.

}, keywords = {nanosized, phenol benzylation reaction, terragonal phase, TPA/ZrO2}, issn = {0021-9517}, doi = {10.1016/j.jcat.2005.08.010}, author = {Sawant, D. P. and Vinu, A. and Jacob, Nalini E. and Lefebvre, F. and Halligudi, Shivappa B.} } @article { ISI:000232864800021, title = {Growth kinetics and thermodynamic stability of octadecyltrichlorosilane self-assembled monolayer on Si (100) substrate}, journal = {Materials Letters}, volume = {59}, number = {29-30}, year = {2005}, month = {DEC}, pages = {3890-3895}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

We have studied the growth kinetics and thermodynamic stability of octadecyltrichlorosilane (OTS) self-assembled monolayers on Si (100) substrate in order to understand its role in controlling the adhesion and surface hydrophobicity. Time-dependent contact angle measurements, using water as a function of OTS concentration, show rapid monolayer formation in the initial stage followed by a slow attainment of full coverage and the overall kinetics approximately follows the Langmuir adsorption isotherm. The adsorption rate constant (k(a) = 150 M-1 s(-1)) is found to be significantly greater than the desorption rate constant (k(d) = 0.156 s(-1)) while the Gibbs free energy (Delta G(ads)) change amounts to -4.2 kcal/mol suggesting thermodynamic stability of OTS monolayer on a silicon surface. Partial monolayer formation by a {\textquoteleft}uniform{\textquoteright} growth mechanism, even at low coverage, is revealed by atomic force microscopy (AFM) in conjunction with grazing angle FTIR spectroscopy. Analysis of the interfacial adhesion properties using Zisman plot suggests a critical surface tension (gamma(c)) of 20.7 dyn/cm for OTS monolayer on Si (100) surface. (C) 2005 Elsevier B.V. All rights reserved.

}, keywords = {Gibbs{\textquoteright}s free energy (AG), growth kinetics, octadecyltrichlorosilane (OTS), self-assembled monolayers (SAMs), Zisman plot}, issn = {0167-577X}, doi = {10.1016/j.matlet.2005.07.026}, author = {Kulkarni, S. A. and Mirji, S. A. and Mandale, A. B. and Gupta, R. P. and Vijayamohanan, K. P.} } @article { ISI:000227853700025, title = {Highly active and selective AlSBA-15 catalysts for the vapor phase tert-butylation of phenol}, journal = {Applied Catalysis A-General}, volume = {281}, number = {1-2}, year = {2005}, month = {MAR}, pages = {207-213}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Hexagonally ordered mesoporous AISBA-15 catalysts having n(Si)/(nA]) ratios from 7 to 215 have been synthesized hydrothermally using a cheap non-ionic block copolymer as the structure-directing agent. The obtained materials were analyzed by XRD and nitrogen adsorption to determine the structural order and the textural properties. It has been observed by Al-27 MAS NMR spectroscopy that aluminum atoms are exclusively in tetrahedral coordination for all samples except AISBA-15(7), where octahedral aluminum has been detected to some extent. Temperature-programmed desorption of pyridine showed that AISBA-15(45) has a higher number of strong acid sites as compared to other mesoporous materials such as FeMCM-41, AIMCM-41 and FcAlMCM-41. The catalyst AlSBA-15(45)showed superior performance in the acid-catalyzed tertiary butylation of phenol employing tert-butanol as the alkylation agent. A high phenol conversion of 86.3\% is observed for this catalyst at a reaction temperature of 150 degrees C. Over AISBA-15(45), the 4-TBP yield amounts to 40.5\% and the 2,4-DTBP yield corresponds to 37.9\%. (c) 2004 Elsevier B.V. All rights reserved.

}, keywords = {Acidity, AlSBA-15, aluminum incorporation, butylation of phenol, SBA-15}, issn = {0926-860X}, doi = {10.1016/j.apcata.2004.11.031}, author = {Vinu, A. and Devassy, Biju M. and Halligudi, Shivaraj B. and Bohlmann, W. and Hartmann, Martin} } @article { ISI:000227996600003, title = {Hydrogen bond mediated open-frame networks in coordination polymers: supramolecular assemblies of Pr(III) and 3,5-dinitro-4-methylbenzoic acid with aza-donor compounds}, journal = {Chemical Communications}, number = {14}, year = {2005}, month = {FEB}, pages = {1824-1826}, publisher = {ROYAL SOC CHEMISTRY}, type = {Article}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

A coordination assembly of 3,5-dinitro-4-methylbenzoic acid and Pr(III), synthesized by hydrothermal methods forms a host structure, which is stable up to 300 degrees C, through C-H center dot center dot center dot O hydrogen bonds and accommodates different types of guest species varying from simple molecules like water to larger molecules like trans-1,2-bis(4-pyridyl) ethene.

}, issn = {1359-7345}, doi = {10.1039/b417754a}, author = {Varughese, S and Pedireddi, VR} } @article { ISI:000232596300002, title = {Identification of coding and non-coding sequences using local holder exponent formalism}, journal = {Bioinformatics}, volume = {21}, number = {20}, year = {2005}, month = {OCT}, pages = {3818-3823}, publisher = {OXFORD UNIV PRESS}, type = {Article}, address = {GREAT CLARENDON ST, OXFORD OX2 6DP, ENGLAND}, abstract = {

Motivation: Accurate prediction of genes in genomes has always been a challenging task for bioinformaticians and computational biologists. The discovery of existence of distinct scaling relations in coding and non-coding sequences has led to new perspectives in the understanding of the DNA sequences. This has motivated us to exploit the differences in the local singularity distributions for characterization and classification of coding and non-coding sequences. Results: The local singularity density distribution in the coding and non-coding sequences of four genomes was first estimated using the wavelet transform modulus maxima methodology. Support vector machines classifier was then trained with the extracted features. The trained classifier is able to provide an average test accuracy of 97.7\%. The local singularity features in a DNA sequence can be exploited for successful identification of coding and non-coding sequences.

}, issn = {1367-4803}, doi = {10.1093/bioinformatics/bti639}, author = {Kulkarni, O. C. and Vigneshwar, R. and Jayaraman, Valadi K. and Kulkarni, B. D.} } @article { ISI:000227016500007, title = {In situ XPS investigations of Cu1-xNixZnAl-mixed metal oxide catalysts used in the oxidative steam reforming of bio-ethanol}, journal = {Applied Catalysis B - Environmental}, volume = {55}, number = {4}, year = {2005}, month = {FEB}, pages = {287-299}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

A series of CuNiZnAl-multicomponent mixed metal oxide catalysts with various Cu/Ni ratios were prepared by the thermal decomposition of Cu1-xNixZnAl-hydrotalcite-like precursors and tested for oxidative steam reforming of bio-ethanol. Dehydrogenation of EtOH to CH3CHO is favored by Cu-rich catalyst. Introduction of Ni leads to C-C bond rupture and producing CO, CO2 and CH4. H-2 yield (selectivity) varied between 2.6-3.0 mol/mol of ethanol converted (50-55\%) for all catalysts at 300 degreesC. The above catalysts were subjected to in situ XPS studies to understand the nature of active species involved in the catalytic reaction. Core level and valence band XPS as well as Auger electron spectroscopy revealed the existence of Cu2+, Ni2+ and Zn2+ ions on calcined materials. Upon in situ reduction at reactions temperatures, the Cu2+ was fully reduced to Cu-0. while Ni2+ and Zn2+ were partially reduced to Ni-0 and Zn-0, respectively. On reduction, the nature of ZnO on Cu-rich catalyst changes from crystalline to amorphous, relatively inert and highly stabilized electronically. Relative concentration of the Ni-0 and Zn-0 increases upon reduction with decreasing Cu-content. Valence band results demonstrated that the overlap between 3d bands of Cu and Ni was marginal on calcined materials, and no overlap due to metallic clusters formation after reduction. Nonetheless, the density of states at Fermi level increases dramatically for Ni-rich catalysts and likely this influences the product selectivity. (C) 2004 Elsevier B.V. All rights reserved.

}, keywords = {auger electron spectroscopy, Autothermal reforming, Bio-ethanol, copper oxide, fuel cell, Hydrogen, hydrotalcite, mixed metal oxides, nickel oxide, oxidative steam reforming, Steam reforming, XPS}, issn = {0926-3373}, doi = {10.1016/j.apcatb.2004.09.007}, author = {Velu, S. and Suzuki, K. and Vijayaraj, M. and Barman, S. and Gopinath, Chinnakonda S.} } @article { ISI:000227966600021, title = {Insight into the mechanism of selective mono-N-methylation of aniline on Cu1-xZnxFe2O4: a DRIFTS study}, journal = {Journal of Molecular Catalysis A - Chemical}, volume = {231}, number = {1-2}, year = {2005}, month = {APR}, pages = {169-180}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Mechanism of selective mono-N-methylation of aniline with methanol on Cu1-xZn2FeO4 catalysts was investigated in detail. The interaction of reactants (aniline. methanol and methanol: aniline) and possible products (N-methylaniline (NMA), N,N-dimethylaniline (DMA) and o-toluidine (OT)) on catalysts surface was studied by temperature-dependent in situ FTIR spectroscopy. Methanol adsorbs dissociatively over catalysts surface at 373 K as methoxy species and is oxidized to formate species at high temperature through dioxymethylene and/or formaldehyde as a surface intermediate species. On the other hand, adsorption of aniline:methanol mixtures shows that methanol oxidation was completely hindered in the presence of aniline. Aniline adsorbs on the Lewis acid sites at \<= 373 K with phenyl ring oriented in a perpendicular manner to the catalyst surfaced however, N-H bond scission occurs above 373 K. A comparison of adsorbed NMA and methanol: am line (3:1) mixture on Cu0.5Zn0.5Fe2O4 shows NMA forms from the reaction mixture at 473 K. However, maximum activity at 573 K in catalytic reaction studies suggests that desorption limits the methylation kinetics. FTIR study displays stable aniline and methyl species on ZnFe2O4 even at 573 K; however. no methyl species is detected on Cr0.95Zn0.05Fe2O4 at 473 K due to methanol reforming reaction and that limits the overall reaction and hence low catalytic activity. It is proposed that methanol is protonated on catalysts surface by the labile H+ due to N-H bond scission. Co-adsorption of acidity probes with aniline and methanol indicates that aniline methylation takes place at single acid-base site. (c) 2005 Elsevier B.V. All rights reserved.

}, keywords = {Aniline, Cu1-xZnxFe2O4, desorption limited, DRIFT, IR, Methanol, N-methylaniline, N-methylation, reaction mechanism}, issn = {1381-1169}, doi = {10.1016/j.molcata.2005.01.014}, author = {Vijayaraj, M. and Murugan, B. and Shubhangi B. Umbarkar and Hegde, S. G. and Gopinath, Chinnakonda S.} } @article { ISI:000232737900009, title = {Lignin-carbohydrate complexes from sugarcane bagasse: preparation, purification, and characterization}, journal = {Carbohydrate Polymers}, volume = {62}, number = {1}, year = {2005}, month = {OCT}, pages = {57-66}, publisher = {ELSEVIER SCI LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Lignin-carbohydrate complexes were isolated from sugarcane bagasse by a process, which yielded sulfur-free lignins. These could be made carbohydrate-free, if necessary, by treatment with xylanase enzyme. A study of the preparation, purification, and characterization of such lignin-carbohydrate complexes, comparison with commercial lignin samples (wood based as well as bagasse based) and some other lignin derivatives was made by using a variety of analytical tools such as FTIR, HPLC at three different UV-wavelengths, GPC, thermal analysis and elemental analysis. The use of such a diverse range of lignin-carbohydrate complex samples enabled us to predict the sensitivity of the various analytical techniques for characterization of complex polymers containing carbohydrate moieties. Evidence for lignin-carbohydrate complex was detectable by FTIR as well as HPLC studies. Thermal analysis studies showed the crucial effect of carbohydrate groups, the content of aliphatic chains, and the sulfur content of the lignins. Generalized structures of lignin-carbohydrate complexes obtained from various sources using different preparation methods and chemical modifications are presented. This will aid the applications development effort with advantageously using lignins containing low levels of carbohydrate moieties as reactive sites as well as biodegradability inducing sites. (C) 2005 Elsevier Ltd. All rights reserved.

}, keywords = {biodegradability, hardwood lignins, lignin-carbohydrate complex, softwood lignins, Sugarcane bagasse, sulfur-free lignins, xylanase enzyme}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2005.07.011}, author = {Singh, R. and Singh, S. and Trimukhe, K. D. and Pandare, K. V. and Bastawade, Kulbhushan B. and Gokhale, D. V. and Varma, Anjanikumar} } @article { ISI:000230338900005, title = {Low-temperature synthesis of nanocrystalline powders of lithium ferrite by an autocombustion method using citric acid and glycine}, journal = {Materials Letters}, volume = {59}, number = {21}, year = {2005}, month = {SEP}, pages = {2630-2633}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Nanocrystalline lithium ferrite is synthesized by an autocombustion method from the corresponding metal nitrates using citric acid as well as glycine as fuels. The ordered phase of lithium ferrite, in single phase form, with particle size of 32-36 nm and large coercivity, is obtained by this method at a low temperature of 200 degrees C. (c) 2005 Elsevier B.V. All rights reserved.

}, keywords = {Combustion synthesis, LiFe5O8, lithium ferrite, low-temperature synthesis, Magnetic materials, Nanomaterials}, issn = {0167-577X}, doi = {10.1016/j.matlet.2005.04.005}, author = {Verma, S. and Karande, J. and Patidar, A. and Joy, Pattayil Alias} } @conference { ISI:000227460600023, title = {Magnetic properties of nanosized ferrite powders synthesized by microwave-hydrothermal method}, booktitle = {Ninth International Conference on Ferrites (ICF-9)}, year = {2005}, note = {9th International Conference on Ferrites (ICF-9), San Francisco, CA, AUG 22-27, 2004}, month = {AUG}, pages = {143-148}, publisher = {Amer Ceramic Soc, 735 Ceramic Place, Westerville, OH 43081-8720 USA}, organization = {Amer Ceramic Soc, 735 Ceramic Place, Westerville, OH 43081-8720 USA}, address = {San Francisco, CA}, abstract = {

Nanosized powders of Fe3O4 and MgFe2O4 are synthesized by microwave-hydrothermal (MH) method. The ferrite powders thus obtained are characterized by powder X-ray diffraction, Mossbauer spectroscopy, scanning and transmission electron microscopies, vibrating sample magnetometer and AC magnetic susceptibility studies. Stoichiometric, nanosized (similar to 34 nm) Fe3O4 particles, having cubic symmetry with a(0) approximate to 8.39 angstrom, are obtained when molar ratio of Fe/NaOH used for the synthesis is 0.133. On the other hand, non-stoichiometric Fe3O4 is obtained when Fe/NaOH molar ratio is increased to 0.4. Though the powder XRD patterns of both stoichiometric and non-stoichiometric Fe3O4 are identical, Mossbauer spectroscopic studies showed different features in terms of asymmetry, intensity, isomer shift, etc. Saturation magnetization, M-s = 70 emu/g and coercivity, H-c = 178 Oe, at room temperature, are obtained for stoichiometric Fe3O4 powders. In the case of MgFe2O4, spherical, nanosized (similar to 3 nm) powders with cubic symmetry (a(0) approximate to 8.30 angstrom) and having very narrow size distribution are obtained under the MH conditions. The temperature and field dependent magnetic measurements on MgFe2O4 powders confirmed the existence of superparamagnetic state in this material with a superparamagnetic blocking temperature of 38 K below which typical magnetic hysteresis behaviour is observed.

}, isbn = {1-57498-218-4}, author = {Khollam, Y. B. and Dhage, S. R. and Verma, S. and Potdar, H. S. and Deshpande, S. B. and Joy, Pattayil Alias and Date, Sadgopal K.}, editor = {Soohoo, R. F.} } @article { ISI:000226669000004, title = {New bis-andrographolide ether from androgphis paniculata nees and evaluation of anti-HIV activity}, journal = {Natural Product Research}, volume = {19}, number = {3}, year = {2005}, month = {APR}, pages = {223-230}, publisher = {TAYLOR \& FRANCIS LTD}, type = {Article}, address = {4 PARK SQUARE, MILTON PARK, ABINGDON OX14 4RN, OXON, ENGLAND}, abstract = {

Novel bis-andrographolide ether (1) and six known compounds andrographolide, 14-deoxy-11,12-didehydroandrographolide, andrograpanin, 14-deoxyandrographolide, (+/-)-5- hydroxy-7,8-dimethoxyflavanone, and 5-hydroxy-7,8-dimethoxyflavone have been isolated from the aerial parts of Andrographis paniculota and their structures were established by spectral data. All the isolates were tested for the anti-HIV and cytotoxic activity.

}, keywords = {Acanthaceae, Andrographis paniculata, anti-HIV, bis-andrographolide ether, Cytotoxic activity}, issn = {1478-6419}, doi = {10.1080/14786410410001709197}, author = {Reddy, V. L. N. and Reddy, S. M. and Ravikanth, V. and Krishnaiah, P. and Goud, T. V. and Rao, T. P. and Ram, T. S. and Gonnade, Rajesh G. and Bhadbhade, Mohan M. and Venkateswarlu, Y} } @article { ISI:000232815200010, title = {Novel enzymatic route for kinetic resolution of (+/-)1,4-benzodioxan-2-carboxylic acid}, journal = {Biochemical Engineering Journal}, volume = {27}, number = {1}, year = {2005}, month = {DEC}, pages = {66-71}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {Ethyl 1,4-benzodioxan-2-carboxylate is used as an intermediate compound for the production of drug doxazosin mesylate. The title compound was kinetically resolved to get S-enantiomer of ethyl 1,4-benzodioxan 2-carboxylate in a simple lipase catalyzed transesterificafion reaction. Ethyl acetate was used as reaction medium as well as acyl donor. The influence of the enzyme source and time of reaction on the enantio selectivity of product were studied. Lipase from Candida antartica-B (Novozyme A/S) catalyzed transesterification reaction with good enantio selectivity towards S-enantiomer. The high enantiomeric ratio, E= 160, provided S-2 an acceptable chemical yield (50\%) and enaritiomeric excess (>95\%). (c) 2005 Elsevier B.V. All rights reserved.}, keywords = {1, 4-benzodioxan-2-carboxylate, 4-benzodioxan-2-carboxylic acid, doxazosin, enantio selectivity, enantiomeric ratio, ethyl 1, ethyl acetate, Lipases, transesterfication}, issn = {1369-703X}, doi = {10.1016/j.bej.2005.06.014}, author = {Kasture, Sangita M. and Varma, R and Kalkote, Uttam R. and Nene, S and Kulkarni, Bhaskar D.} } @article { ISI:000231634800045, title = {Novel low-temperature synthesis of nanosized NiZn ferrite}, journal = {Journal of the American Ceramic Society}, volume = {88}, number = {9}, year = {2005}, month = {SEP}, pages = {2597-2599}, publisher = {BLACKWELL PUBLISHING}, type = {Article}, address = {9600 GARSINGTON RD, OXFORD OX4 2DQ, OXON, ENGLAND}, abstract = {

Nanosized NiZn ferrite powder is synthesized by a low-temperature method, using a unique combination of citric acid and glycine. An appropriate molar ratio of both citric acid and glycine offers a low-temperature synthetic route by incorporating the complexation behavior of citric acid and the combustion nature of glycine. Thermal decomposition/controlled autocatalytic combustion of the composite gel occurs at a low temperature of around 175 degrees C, with the evolution of a large amount of gases. Transmission electron microscopic studies showed that the average particle size of the ferrite obtained is similar to 2.5 nm, with a narrow size distribution. Uniformly distributed fine-grained microstructure with low porosity is obtained for a sample sintered at 1000 degrees C.

}, issn = {0002-7820}, doi = {10.1111/j.1551-2916.2005.00445.x}, author = {Verma, S. and Pradhan, S. D. and Pasricha, R. and Sainkar, S. R. and Joy, Pattayil Alias} } @article { ISI:000227932000012, title = {Novel supramolecular assembly of 3,5-dinitro-4-methylbenzoic acid and trans-1,2-bis(4-pyridyl)ethene}, journal = {Tetrahedron Letters}, volume = {46}, number = {14}, year = {2005}, month = {APR}, pages = {2411-2415}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

A novel organic assembly, formed between 3,5-dinitro-4-methylbenzoic acid and trans-1,2-bis(4-pyridyl)ethene under hydrothermal conditions in the presence of Pr(III) and a layered structure obtained by direct co-crystallization of the reactants at ambient conditions is reported. The structures of the complexes were established, unambiguously, by single crystal X-ray diffraction methods. (c) 2005 Elsevier Ltd. All rights reserved.

}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2005.02.070}, author = {Varughese, S and Pedireddi, VR} } @article { ISI:000226887500027, title = {Phase transitions in octanethiol-capped Ag nanocluster microfilm assemblies}, journal = {Thermochimica Acta}, volume = {426}, number = {1-2}, year = {2005}, month = {FEB}, pages = {207-212}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

We describe phase transitions in microfilm assemblies of octanethiol (OT)-capped 2-4 nm-diameter Ag nanoclusters prepared from solutions with OT/Ag+ ratios of similar to50. Using DSC we observe two melting/crystallization-type reversible phase transitions: one at similar to61 degreesC due to interdigiated unattached octanethiol, and the other at similar to125 degreesC due to the phase comprised of the assembly of OT-capped nanoclusters. Increased thermal fluctuations weaken the inter-chain hydrophobic interactions between interdigitated OT molecules, leading to both phase transitions. The thiolate bond of OT-molecules bound to Ag nanoclusters are more rigid, thereby requiring a higher temperature to increase the flexibility of the alkyl chain of OT, and to melt the nanocluster assembly. The mobility of the nanoclusters in the melt is limited, and morphological features of the original assemblies are retained during recrystallization. No observable mass loss is detected up to similar to180 degreesC, above which OT molecules desorb from the Ag nanoclusters. (C) 2004 Elsevier B.V. All rights reserved.

}, keywords = {differential thermal analysis, infrared spectroscopy, phase transitions, silver nanoclusters}, issn = {0040-6031}, doi = {10.1016/j.tca.2004.08.009}, author = {Ellis, A. and D{\textquoteright}Arcy-Galla, J. and Vijayamohanan, K. and Goswami, R. and Ganesan, P. G. and Ryu, C. and Ramanath, G.} } @article { ISI:000227046400028, title = {Preparation and characterization of composite electrodes of coconut-shell-based activated carbon and hydrous ruthenium oxide for supercapacitors}, journal = {Journal of Power Sources}, volume = {141}, number = {1}, year = {2005}, month = {FEB}, pages = {198-203}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The relationship between the structure-specific capacitance (F g(-1)) of a composite electrode consisting of activated coconut-shell carbon and hydrous ruthenium oxide (RuOx(OH)(y)) has been evaluated by impregnating various amounts of RuOx(OH)(y) into activated carbon that is specially prepared with optimum pore-size distribution. The composite electrode shows an enhanced specific capacitance of 250 F g(-1) in 1 M H2SO4 with 9 wt.\% ruthenium incorporated. Chemical and structural characterization of the composites reveals a homogeneous distribution of amorphous RuOx(OH)(y) throughout the porous network of the activated carbon. Electrochemical characterization indicates an almost linear dependence of capacitance on the amount of ruthenium owing to its pseudocapacitive nature. (C) 2004 Elsevier B.V. All rights reserved.

}, keywords = {activated carbon, Composite, Electrochemical characterization, pseudocapacitance, specific capacitance, supercapacitor}, issn = {0378-7753}, doi = {10.1016/j.powsour.2004.09.008}, author = {Dandekar, M. S. and Arabale, G. and Vijayamohanan, K.} } @article { ISI:000228698900038, title = {PVA stabilized gold nanoparticles by use of unexplored albeit conventional reducing agent}, journal = {Materials Chemistry and Physics}, volume = {92}, number = {1}, year = {2005}, month = {JUL}, pages = {229-233}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

Poly(vinyl alcohol) (PVA) stabilized gold nanoparticles have been prepared in aqueous medium using two different reducing viz.; hydrazine hydrate, a stronger reducing agent and sodium formaldehydesulfoxylate (SFS), a slightly weaker reducing agent. SFS is used for first ever time for reduction of gold metal salt. The PVA stabilized gold nanoparticles solutions are wine red to blood red coloured and are stable over a long period of time with no indication of aggregation. The solution shows strong visible light absorptions in the range of 520-540 nm, characteristics of gold nanoparticles. Powder X-ray diffraction patterns of freshly prepared films containing gold nanoparticles indicated particles size to be about 15 nm. Transmission electron microscopy (TEM) of a more than two-week-old sample revealed well-defined non-agglomerated spherical particles of about 50 nm diameter in solutions. (c) 2005 Elsevier B.V. All rights reserved.

}, keywords = {Chemical synthesis, electronic materials, Nanostructures, Polymer}, issn = {0254-0584}, doi = {10.1016/j.matchemphys.2005.01.016}, author = {Khanna, P. K. and Gokhale, R. and Subbarao, V. V. V. S. and Vishwanath, A. K. and Das, B. K. and Satyanarayana, C. V. V.} } @article {42473, title = {Reaction of huisgen zwitterion with 1,2-benzoquinones and isatins: expeditious synthesis of dihydro-1,2,3-benzoxadiazoles and spirooxadiazolines}, journal = {Organic Letters}, volume = {7}, year = {2005}, month = {OCT}, pages = {5139{\textendash}5142}, type = {Article}, abstract = {

The zwitterionic intermediate generated from dialkyl azodicarboxylate and triphenylphosphine on reaction with 3-methoxy-1,2-benzoquinones afforded dihydro-1,2,3-benzoxadiazoles. N-Substituted isatins furnished spirooxadiazolines under similar conditions.

}, doi = {10.1021/ol051956n}, author = {Nair, Vijay and Biju, Akkattu T. and Vinod, A. V. and Eringathodi, Suresh} } @article { ISI:000229567400027, title = {Room temperature nitric oxide sensor actualized from Ru-doped SnO2 nanowires}, journal = {Sensors and Actuators B - Chemical}, volume = {107}, number = {2}, year = {2005}, month = {JUN}, pages = {708-715}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

We report synthesis of the novel Ru-doped SnO2 nanowires and their distinctive response towards NO., and liquefied petroleum gas (LPG) in air. These nanowires have been prepared by a simple approach of evaporation of metal oxide at elevated temperature, The sensor exhibits three order of magnitude changes in the conductivity on exposure to NO2 in air at room temperature, Furthermore. Ru being one of the excellent sensitizers towards LPG these wires also exhibits sensitivity at 250\&DEG; C. The amount of Ru plays a crucial role in modulating the sensitivity and lowering the operating temperature. {\textcopyright} 2005 Elsevier B.V. All rights reserved.

}, keywords = {LPG, Nanowires, NO2, tin oxide ruthenium oxide}, issn = {0925-4005}, doi = {10.1016/j.snb.2004.12.073}, author = {Ramgir, N. S. and Mulla, Imtiaz S. and Vijayamohanan, K. P.} } @article { ISI:000230729300026, title = {Study of correlation of structural and surface properties with electrochemical behaviour in carbon aerogels}, journal = {Journal of Materials Science}, volume = {40}, number = {14}, year = {2005}, month = {JUL}, pages = {3777-3782}, publisher = {SPRINGER}, address = {VAN GODEWIJCKSTRAAT 30, 3311 GZ DORDRECHT, NETHERLANDS}, abstract = {

Carbon aerogel is a promising material for electrochemical double layer capacitors. In this paper carbon aerogels prepared by subcritical drying method are investigated for the change in the structure and surface properties at different pyrolysis temperatures. The important relations between structure, morphology, surface area and electrical properties were studied using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), surface area measurement and cyclic voltametry. It is shown that structure and the surface functional groups play important role in enhancement of electrochemical capacitance. The specific capacitance achieved was 114 F/gm which is quite large value for subcritically prepared carbon aerogels without any kind of activation process. (c) 2005 Springer Science + Business Media, Inc.

}, issn = {0022-2461}, doi = {10.1007/s10853-005-3318-4}, author = {Hebalkar, Neha and Arabale, G. and Sainkar, S. R. and Pradhan, S. D. and Mulla, Imtiaz S. and Vijayamohanan, K. and Ayyub, P. and Kulkarni, S. K.} } @article { ISI:000227248600018, title = {Synthesis and characterization of a novel extra large pore aluminophosphate molecular sieve, NCL-6}, journal = {Journal of the Indian Chemical Society}, volume = {82}, number = {1}, year = {2005}, month = {JAN}, pages = {77-78}, publisher = {INDIAN CHEMICAL SOC}, type = {Article}, address = {92 ACHARYA PRAFULLA CHANDRA RD ATTN:DR INDRAJIT KAR/EXEC SEC, CALCUTTA 700009, INDIA}, abstract = {

A novel extra large pore aluminophosphate molecular sieve NCL-6, has been prepared and characterized by various techniques such as XRD, SEM, TG/DTA, carbon and nitrogen analysis, FT-IR and MAS NMR are reported. X-Ray diffraction pattern shows that the synthesized sample is crystalline and have novel structure. SEM analysis indicate the phase purity and having granules morphology with 3 x 5 mum particle size. FT-IR spectrum in the framework region shows that the sample is similar to the other known aluminophosphates. TG/DTA shows that the sample losses 30.45\% due to the loss of water and organic molecules. Aluminium and phosphorous NMR shows that the presence of four different aluminium and three different phosphorous sites. The NMR are similar to VPI-5, NCL-2 and NCL-3.

}, issn = {0019-4522}, author = {Venkatathri, N} } @article { ISI:000229051200014, title = {Synthesis and characterization of polyimides and co-polyimides having pendant benzoic acid moiety}, journal = {Polymer}, volume = {46}, number = {11}, year = {2005}, month = {MAY}, pages = {3669-3676}, publisher = {ELSEVIER SCI LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

A novel diamine monomer, 2,4-diamino-4{\textquoteright}-carboxy diphenyl ether had been synthesized. Several polyimides were prepared by reacting this diamine with commercially available dianhydrides, such as benzophenone tetracarboxylic acid dianhydride (BTDA), 4,4{\textquoteright}bis{hexafluoroisopropylidene his (phthalic anhydride)} (6-FDA), oxydiphthalic anhydride (ODPA) and 3,3{\textquoteright},4,4{\textquoteright}-biphenyltetracarboxylic acid dianhydride (BPDA). Furthermore, copolymers from the resulting diamine and oxydianiline (ODA) with 6 FDA were also synthesized. The inherent viscosities of the polymers were 0.42-0.67 dl g(-1). The polymers have good solubility in polar aprotic solvents, high thermal stability up to 410 \&DEG; C in nitrogen and high glass transition temperatures (T-g) ranging from 260-330 \&DEG; C. These polymers formed tough flexible films by solution casting. {\textcopyright} 2005 Elsevier Ltd. All rights reserved.

}, keywords = {co-polyimides, diamine with pendant benzoic acid, polyimides with pendant benzoic acid}, issn = {0032-3861}, doi = {10.1016/j.polymer.2005.03.001}, author = {Kulkarni, M and Kothawade, S and Arabale, G. and Wagh, D and Vijayamohanan, K and Kulkarni, RA and Vernekar, SP} } @article { ISI:000229899200012, title = {Synthesis and NMR characterization of SAPO-35 from non-aqueous systems using hexamethyleneimine template}, journal = {Materials Research Bulletin }, volume = {40}, number = {7}, year = {2005}, month = {JUL}, pages = {1157-1165}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

SAPO-35 was synthesized using hexamethyleneimine template in non-aqueous systems. X-ray diffraction and scanning electron micrograph analysis shows the synthesized sample is pure and well crystalline. Presence of four stages (1.6\%, 0.8\%, 7.8\% and 8.4\%) of weight loss is observed by TG/DTA analysis. FT-IR analysis in the framework region shows the presence of tetrahedral T-O-T vibrations is similar to the other known aluminophosphate molecular sieves. FT-IR spectrum in the -OH region shows stretching vibrations at 3631, 3604 and 3580 cm(-1) can be assigned to OH groups in bigger cages near S6R, in bigger cages near D6R and those actually confined inside the D6R, respectively. The spectra for the as-synthesized sample show a single symmetrical Al-27 MAS NMR line at delta = 36.26 indicating the presence of a single tetrahedral aluminium species. Where as Si-29 and P-31 MAS NMR shows the presence of two peaks in both at (-89.9 and -95.15 ppm) and (-34.01 and -40.45 ppm) due to the Si substitution of P present in two different locations in double 6 ring (D6R) and in single 6 ring (S6R). Al-27 3Q-MAS NMR shows two peaks for environmentally different tetrahedral aluminium atoms. This is the first time we are showing such a fact which is not observable using ordinary MAS NMR. (c) 2005 Elsevier Ltd. All rights reserved.

}, keywords = {XRD}, issn = {0025-5408}, doi = {10.1016/j,materresbull.2005.03.008}, author = {Venkatathri, N} } @article { ISI:000227514200002, title = {Synthesis, characterization and catalytic properties of hexagonal mesoporous vanadium aluminophosphate molecular sieves}, journal = {Catalysis Communications}, volume = {6}, number = {3}, year = {2005}, month = {MAR}, pages = {177-183}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Novel vanadium containing hexagonal mesoporous aluminophosphate molecular sieve (VHMA) have been synthesized. XRD and TEM analysis confirm the phase purity of the synthesized samples. FT-IR analysis suggests the incorporation of V4+ in the aluminophosphate framework. ESR, UV-Vis spectroscopic techniques and cyclic voltammetric studies confirm the incorporation of vanadium and reveal its presence of tetrahedral and square pyramidal environments in the as-synthesized samples. Cyclic voltammetry reveals the presence of two redox couples in VHMA. This catalyst is found to be a good oxidation catalyst. (C) 2005 Elsevier B.V. All rights reserved.

}, issn = {1566-7367}, doi = {10.1016/j.catcom.2004.12.005}, author = {Venkatathri, N and Srivastava, R} } @article { ISI:000233846100021, title = {Synthesis, characterization, electronic structure, and photocatalytic activity of nitrogen-doped TiO2 nanocatalyst}, journal = {Chemistry of Materials}, volume = {17}, number = {25}, year = {2005}, month = {DEC}, pages = {6349-6353}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Nitrogen-doped TiO2 (N-TiO2)) nanocatalyst with spherical shape and homogeneous size has been synthesized through a chemical method using TiCl3 as precursor. The light absorption onset shifts from 380 nm on pure TiO2 to the visible region at 550 nm with N-TiO2. A clear decrease in the band gap and the nitrogen 2p states on the top of the valence band on N-TiO2 (compared to TiO2) is deduced from the optical absorption spectroscopy results. The chemical nature of N has been evolved as N-Ti-O in the anatase TiO2 lattice as identified by X-ray photoelectron spectroscopy (XPS). Photocatalytic decomposition of methylene blue has been carried out both in the UV and in the visible region and N-TiO2 shows higher activity than the Degussa P25 TiO2 photocatalyst in the visible region.

}, issn = {0897-4756}, doi = {10.1021/cm052047v}, author = {Sathish, M and Viswanathan, B and Viswanath, RP and Gopinath, Chinnakonda S.} } @article { ISI:000228575900018, title = {Synthesis of (+)-camptothecin}, journal = {Arkivoc}, volume = {2005}, number = {3}, year = {2005}, month = {JAN}, pages = {165-169}, publisher = {ARKAT USA INC}, address = {C/O ALAN R KATRITZKY, UNIV FLORIDA, DEPT CHEMISTRY, PO BOX 117200, GAINESVILLE, FL 32611 USA}, abstract = {

A synthesis of optically pure camptothecin was achieved in 4 steps from previously reported aldehyde employing Sharpless asymmetric dihydroxylation as the key step.

}, keywords = {Anticancer, camptothecin, sharpless asymmetric dihydroxylation}, doi = {10.3998/ark.5550190.0006.318}, author = {Chavan, Subhash P. and Venkatraman, M. S.} } @article { ISI:000232347900014, title = {Synthesis of chromium substituted nano particles of cobalt zinc ferrites by coprecipitation}, journal = {Materials Letters}, volume = {59}, number = {27}, year = {2005}, month = {NOV}, pages = {3402-3405}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Nano particles of chromium substituted cobalt zinc ferrite have been synthesized by a chemical co-precipitation method. X-ray diffraction studies of the nano particles of CrxCo0.5-xZn0.5Fe2O4 (x = 0.1 to 0.5) heat-treated at 300 degrees C show that the particle sizes are in the range of 2 to 7 nm. Room temperature Fe-57 Mossbauer spectra of all the samples show only two doublets, confirming the presence of superparamagnetic relaxation in the nano particles. An exponential decrease in the superparamagnetic blocking temperature, with increasing chromium concentration, is observed for these samples. (C) 2005 Elsevier B.V. All rights reserved.

}, keywords = {Co0.5Zn0.5Fe2O4, Mossbauer spectroscopy, nano materials}, issn = {0167-577X}, doi = {10.1016/j.matlet.2005.06.004}, author = {Sharma, R. K. and Suwalka, O. and Lakshmi, N. and Venugopalan, K. and Banerjee, Abhik and Joy, Pattayil Alias} } @article { ISI:000230434500007, title = {Synthesis of high silica content silicoaluminophosphate-5 (SAPO-5) from non-aqueous medium using hexamethyleneimine template}, journal = {Journal of Scientific \& Industrial Research}, volume = {64}, number = {7}, year = {2005}, month = {JUL}, pages = {509-514}, publisher = {NATL INST SCIENCE COMMUNICATION}, type = {Article}, address = {DR K S KRISHNAN MARG, NEW DELHI 110 012, INDIA}, abstract = {

Silicoaluminophosphate-5 (SAPO-5) molecular sieve with up to 2.4 Si atom per unit cell have been synthesized using hexamethyleneimine template in ethylene glycol medium (molar ratio of silica in the reaction gels up to 0.3). Crystallinity and silicon incorporation are confirmed by XRD, XRF, N, sorption study, TG/DTA, SEM. pyridine TPD technique and hydroxyl region FT-IR. These materials with high Si concentration show higher activity for toluene alkylation reaction than samples prepared with up to 0.1 molar ratio of silica in the gel of aqueous media.

}, keywords = {aqueous, FT-IR, hydroxyl region, non-aqueous, SAPO-5, SEM, TG/DTA, XRD}, issn = {0022-4456}, author = {Venkatathri, N} } @article { ISI:000227108800014, title = {Temperature-induced phase transitions of the ordered superlattice assembly of Au nanoclusters}, journal = {Journal of Physical Chemistry B}, volume = {109}, number = {7}, year = {2005}, month = {FEB}, pages = {2552-2558}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Superlattices of monolayer protected metallic and semiconducting nanoclusters have attracted significant attention due to their promising applications in nanotechnology. In this paper, we investigate the effect of temperature on the ordered superlattice structure of relatively larger sized An nanoclusters passivated with dodecanethiol [ca. Au-1415(RS)(328)] with the help of in situ temperature controlled X-ray diffraction (XRD) and infrared spectroscopy (IR) in conjunction with thermogravimetric (TG) and differential scanning calorimetric (DSC) analysis. In brief, monolayer protected Au nanoclusters (AuMPC) were prepared by a modified Brust synthesis technique, where dodecanethiol itself acts as both phase transfer and simultaneous capping agent during the reduction process, generating an average particle size of 3.72+/-0.4 nm after repeated solvent extraction and careful fractionation experiments. These particles are characterized with the help of UV-vis, transmission electron microscopic (TEM), IR, and NMR techniques, where effective capping as well as the superlattice formation on the TEM grid is evident from the combined analysis of these results. In situ low-angle XRD analysis shows that the particles undergo an irreversible phase transition in the temperature range of 100-115degreesC, which is also reflected in the data from in situ IR analysis. However, the DSC analysis does not account for this phase transition, although the reversible phase transition due to the alkyl chain dynamics is in good agreement with the previously reported results. These results indicate the formation of temperature-induced, diffusion-limited phase transition involving nonequilibrium fractal structures, which is in good agreement with the previous available theoretical studies. The determination of the temperature window for the stability of these ordered assemblies would be used to understand the effect of thermal stress for device applications.

}, issn = {1520-6106}, doi = {10.1021/jp045709x}, author = {Chaki, N. K. and Vijayamohanan, K. P.} } @article { ISI:000227960800029, title = {Thermal, magnetic and spectral studies of metal-quinone complexes Part III. radical coordination and hydrogen bonding mediated exchange interaction in copper-hydroxyquinone complex}, journal = {Journal of Thermal Analysis and Calorimetry}, volume = {79}, number = {3}, year = {2005}, month = {FEB}, pages = {669-675}, publisher = {SPRINGER}, type = {Article}, address = {VAN GODEWIJCKSTRAAT 30, 3311 GZ DORDRECHT, NETHERLANDS}, abstract = {

The reaction of CuCl with 2HNQ, ( viz. 2- hydroxy- 1,4- naphthoquinone), in methanol results in [Cu-2( II, II)(4HNSQ)(2)(ONQ)(2)(H2O)(4)], Cu- 3 complex; [ where ONQ is the deprotonated oxidized form of ligand ( viz. 2- oxido- 1,4- naphthoquinone) and 4HNSQ one electron reduced tautomeric form of the ligand (i.e. 4- hydroxy - 1,2- naphthosemiquinone)]. The mixed valent redox ligation is confirmed in [ 9] by us. In present report complex Cu- 3 investigated by variable temperature magnetic susceptibility measurements ( SQUID), X and Q- band EPR, DSC and CV techniques. A break is observed in the chi(m)(-1) vs. T plot similar to 200 K in Cu- 3 which is attributed to a phase transition. In Cu- 3 a quintet state ( S= 2) is populated above 200 K by the molecular association of two exo Cu( II)( 4HNSQ) units via hydrogen bonding between Cu(ONQ) unit of endo ligands in dimer. Magnetic susceptibility data is treated with tetramer model with S= 1/2,1/2,1/2,1/2. The interdimer triplet- triplet interaction ( J) in two [ Cu( 4HNSQ)] units and intradimer ( zJ(1)) interaction between [ Cu( II)( 4HNSQ)] are best fitted with J= -50 cm(-1) and zJ(1)= 28 cm(-1), respectively, using g= 2.2. {\textquoteleft}Quintet- triplet{\textquoteright} phase transition occurs with an enthalpy change of 31.83 kJ mol(-1) estimated from DSC. Cu( II)double left right arrow Cu( I) and NSQ double left right arrow CAT redox couples at E-1/2= 0.68 V and E-1/2 = -1.12 V, respectively are result of exo ligands and Cu( II) ions interaction, while shifts of ligand based peaks viz. NQ -\> NSQ and NSQ double left right arrow CAT at - 0.44 and - 0.67 V towards positive potential on complexation are due to electron transfer interactions between endo ligand and Cu( II) ion.

}, keywords = {antiferromagnetic coupling, copper complexes, Lawsone, model complexes, quinones, triplet state}, issn = {1388-6150}, author = {Salunke-Gawali, S. and Rane, S. Y. and Boukheddaden, K. and Codjovi, E. and Linares, J. and Varret, F. and Bakare, P. P.} } @article { ISI:000227566200019, title = {Wet-chemical templateless assembly of metal nanowires from nanoparticles}, journal = {Chemical Communications}, number = {11}, year = {2005}, month = {JAN}, pages = {1435-1437}, publisher = {ROYAL SOC CHEMISTRY}, type = {Article}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

We describe a new, simple, room-temperature wet-chemical approach for assembling Au and Ag nanoparticles into nanowire networks, without the use of lithographic templates. Five to 35 nm-diameter nanowires passivated with a thin organic layer were synthesized by mechanically agitating a biphasic liquid mixture of an aqueous hydrosol containing the nanoparticles, and toluene. Nanowire structure and surface chemistry are discussed based on electron microscopy, UV-visible spectroscopy and thermogravimetric analyses.

}, issn = {1359-7345}, doi = {10.1039/b414447n}, author = {Maddanimath, Trupti and Kumar, Anil and D{\textquoteright}Arcy-Galla, J. and Ganesan, P. G. and Vijayamohanan, K. and Ramanath, G.} } @article { ISI:000239326400010, title = {On the {\textquoteleft}{\textquoteleft}Active spacer and stabilizer{\textquoteright}{\textquoteright} role of Zn in Cu1-xZnxFe2O4 in the selective mono-N-methylation of aniline: XPS and catalysis study}, journal = {Journal of Catalysis}, volume = {241}, number = {1}, year = {2006}, month = {JUL}, pages = {83-95}, publisher = {ACADEMIC PRESS INC ELSEVIER SCIENCE}, type = {Article}, address = {525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USA}, abstract = {

A systematic catalytic methylation study on ferrospinel materials led to the selective production of N-methylaniline (NMA) with Cu1-xZnxFe2O4. Aniline methylation was carried out on Cu1-xZnxFe2O4 with a feed composition of CH3OH:PhNH2:H2O = 3:1:1 at 513-633 K. NMA was formed selectively on all of the catalyst compositions, with trace amounts of secondary products under most of the conditions. Cu0.5Zn0.5Fe2O4 composition showed high catalytic activity and stability up to 100 h. Although the Cu2+ was responsible for methylation activity, Zn2+ enhanced the overall stability of the catalyst system. XPS investigations revealed that the degree of Cu2+ reduction decreased dramatically from x = 0.05/0.25 to 0.5/0.75 on spent catalysts. TPR studies indicated that the reducibility of Cu2+ decreased from fully reducible at 523 K with Cu-rich compositions to partially reducible at 573 K on x = 0.5. Stable activity observed on Cu0.5Zn0.5Fe2O4 can be attributed to the highly heterogeneous distribution of metal ions. This heterogeneous distribution indicates an important role of zinc, likely as an {\textquoteleft}{\textquoteleft}active spacer cum stabilizee{\textquoteright} that hinders the reduction of active Cu2+ and contributes to prolonged activity. (c) 2006 Elsevier Inc. All rights reserved.

}, keywords = {Aniline, Ferrite, N-methylaniline, N-methylation, spacer, stabilizer, surface distribution, TPR, XPS}, issn = {0021-9517}, doi = {10.1016/j.jcat.2006.04.010}, author = {Vijayaraj, Munusamy and Gopinath, Chinnakonda S.} } @article { ISI:000241574500031, title = {Analytically continued fock space multi-reference coupled-cluster theory: application to the shape resonance}, journal = {Chemical Physics}, volume = {329}, number = {1-3, SI}, year = {2006}, month = {OCT}, pages = {283-289}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The Fock space multi-reference coupled-cluster (FSMRCC) method is used for the study of the shape resonance energy and width in an electron-atom/molecule collision. The procedure is based upon combining a complex absorbing potential (CAP) with FSMRCC theory. Accurate resonance parameters are obtained by solving a small non-Hermitian eigen-value problem. We study the shape resonances in e(-)-C2H4 and e(-)-Mg. (c) 2006 Elsevier B.V. All rights reserved.

}, keywords = {complex absorbing potential, correlated independent particle potential, Fock space multi-reference coupled-cluster theory, shape resonance}, issn = {0301-0104}, doi = {10.1016/j.chemphys.2006.07.002}, author = {Pal, Sourav and Sajeev, Y. and Vaval, Nayana} } @article { ISI:000207781603334, title = {COLL 613-Studies on the vapor-phase photo-oxidation of methanol over nano-size titania clusters dispersed in MCM-41 mesoporous silica}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {232}, year = {2006}, month = {SEP}, pages = {613-COLL}, publisher = {AMER CHEMICAL SOC}, type = {Meeting Abstract}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, issn = {0065-7727}, author = {Kumar, Dharmesh and Bhattacharyya, Kaustav and Tripathi, Arvind and Varma, Salil and Gupta, Narendra M.} } @article { ISI:000241168600010, title = {Constrained variational response to Fock-space multi-reference coupled-cluster theory: Some pilot applications}, journal = {Journal of Molecular Structure-Theochem}, volume = {768}, number = {1-3}, year = {2006}, month = {AUG}, pages = {91-96}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Fock space (FS) multi-reference (MR) coupled-cluster (CC) has been established to be state-of-the-art method for energies of open-shell radicals, ionized, electron attached states and excited states. Due to the multi-root nature of the method, the linear response of MRCC, however, is non-trivial. Constrained variation approach (CVA) makes it plausible to calculate response of the MRCC method efficiently. However, the approach is used for only one root of the problem at a time. In the present article, we make first implementation of the approach and present test results of dipole moments of small radicals. (c) 2006 Elsevier B.V. All rights reserved.

}, keywords = {constrained variation, coupled-cluster, Dipole moment, Multi-reference, response}, issn = {0166-1280}, doi = {10.1016/j.theochem.2006.05.022}, author = {Manohar, Prashant Uday and Vaval, Nayana and Pal, Sourav} } @article { ISI:000237477400077, title = {Directed organization of gold nanoclusters on silver nanowires: a step forward in heterostructure assembly}, journal = {Applied Physics Letters}, volume = {88}, number = {19}, year = {2006}, month = {MAY}, pages = {193103}, publisher = {AMER INST PHYSICS}, type = {Article}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

We investigate the directed assembly of tridecylamine protected gold nanoclusters of 4-5 nm size on functionalized silver nanowires of 55-60 nm diameter and the electron transfer behavior of this integrated structure using transmission electron microscopy, non-contact atomic force microscopy, and scanning tunneling microscopy/spectroscopy. Linear I-V for bare silver nanowire suggests metallic behavior but high tunnel resistance indicates presence of insulating layer on the surface. Identical I-Vs obtained for isolated gold nanoparticle and heterostructure suggests that electron transport across nanowires in the latter is governed by gold nanoparticles in contrast to expected ballistic or diffusive transport along their length.(c) 2006 American Institute of Physics.

}, issn = {0003-6951}, doi = {10.1063/1.2200284}, author = {Sharma, J. and Vivek, J. P. and Vijayamohanan, K. P. and Singh, P. and Dharmadhikari, C. V.} } @article {42469, title = {DMAP-catalyzed reaction of beta-ketoesters and dimethyl acetylenedicarboxylate: an efficient synthesis of polysubstituted benzenes and biaryls}, journal = {Tetrahedron}, volume = {62}, year = {2006}, month = {SEP}, pages = {10136{\textendash}10140}, type = {Article}, abstract = {

A DMAP catalyzed tandem addition{\textendash}cyclization{\textendash}dehydration sequence involving dimethyl acetylenedicarboxylate and β-ketoesters leading to polysubstituted benzene/biaryl derivatives is presented.

}, doi = {10.1016/j.tet.2006.08.031}, author = {Nair, Vijay and Vidya, N. and Biju, Akkattu T. and Deepthi, Ani B. and Abhilash, K. G. and Eringathodi, Suresh} } @article {42506, title = {Efficient protocol for genetic transformation and shoot regeneration of turmeric (Curcuma longa L.) via particle bombardment}, journal = {Plant Cell Reports}, volume = {25}, year = {2006}, month = {MAR}, pages = {112-116}, type = {Article}, doi = {10.1007/s00299-005-0033-1}, author = {Shirgurkar, M. V. and Naik, V. B. and von Arnold, S. and Nadgauda, R. S. and Clapham, D. H.} } @article { ISI:000238030200026, title = {Electrochemical organization of monolayer protected gold nanoclusters on single-walled carbon nanotubes: significantly enhanced double layer capacitance}, journal = {Journal of Nanoscience and Nanotechnology}, volume = {6}, number = {5}, year = {2006}, month = {MAY}, pages = {1387-1391}, publisher = {AMER SCIENTIFIC PUBLISHERS}, type = {Article}, address = {25650 NORTH LEWIS WAY, STEVENSON RANCH, CA 91381-1439 USA}, abstract = {

This paper reports a novel electrochemical route for anchoring monolayer protected gold nanoclusters (size 8 +/- 0.2 nm) on single-walled carbon nanotube bundles, resulting in the formation of hybrid materials. Monolayer protected gold nanoclusters prepared by modified Brust synthesis route were organized on SWNT bundles by cycling-the potential in dichloromethane between -1 to +1 V at a scan rate of 50 mV/s. Monolayer protected nanoclusters in electrolyte solutions possess ionic space charge around them (double layer charging), making them suitable for organization on nanotube bundles, by tuning the electrostatic interactions. More significantly, analysis of the double layer capacitance of these hybrid materials shows almost ten times increase in capacitance compared to that of bare SWNT bundles. We believe that these hybrid materials are potentially useful in nanoelectronics.

}, keywords = {double layer capacitance, double layer charging, hybrid materials, monolayer protected gold nanoclusters, single-walled carbon nanotubes}, issn = {1533-4880}, doi = {10.1166/jnn.2006.323}, author = {Mahima, Subhramanyam and Chaki, N. K. and Sharma, J. and Kakade, Bhalchandra A. and Pasricha, R. and Rao, A. M. and Vijayamohanan, K.} } @article { ISI:000242601000036, title = {Electron transfer behavior of monolayer protected nanoclusters and nanowires of silver and gold}, journal = {Journal of Nanoscience and Nanotechnology}, volume = {6}, number = {11}, year = {2006}, note = {International Conference on Nanoscience and Nanotechnology, Gwangju Inst Sci \& Technol, Gwangju, SOUTH KOREA, NOV 10-12, 2005}, month = {NOV}, pages = {3464-3469}, publisher = {Gwangju Jeonnam Nano Technol Union}, type = {Article}, address = {25650 NORTH LEWIS WAY, STEVENSON RANCH, CA 91381-1439 USA}, abstract = {

Understanding the electron transfer behavior of nanometer sized, both metallic and semiconducting particles and wires is important due to the fundamental interest in size and shape dependent electronic properties and also because of its applications in nano-electronic devices like single electron transistors and molecular switches. Monolayer protected nanoclusters enable one simple and elegant method of synthesis of these types of metallic and semiconducting materials using interfacial chemistry as has been successfully used in several applications ranging from catalysis to molecular electronics. The success of this type of nanostructured materials is due in part to the well known protecting/stabilizing action of the ligands (also known as surface passivating/capping agents), which facilitate the synthesis and processing of these hydrophobic colloids in solution form. The present article discusses the electron transfer behavior of silver nanowires and nanoparticles with varied sizes. In particular, we have investigated the electrochemical properties of silver nanowires (diameter 70 nm, length several micrometers) and compared with the behavior of similar relatively larger sized nanoparticles (size 40 nm). A critical analysis of the redox behavior of silver nanowires and nanoparticles is presented in aqueous medium under various electrolytic conditions along with a comparison of analogous properties of smaller sized (2-7 nm) silver and gold nanoclusters.

}, keywords = {cyclic voltammetry, nanoclusters/nanoparticles, Nanowires}, issn = {1533-4880}, doi = {10.1166/jnn.2006.035}, author = {Sharma, Jadab and Vivek, J. P. and Vijayamohanan, Kunjukrishna P.} } @article { ISI:000241767100009, title = {Eu3+ doped lanthanum oxide nanowhiskers: microwave hydrothermal synthesis, characterization and photoluminescence properties}, journal = {Journal of Physics D-Applied Physics}, volume = {39}, number = {18}, year = {2006}, month = {SEP}, pages = {3974-3977}, publisher = {IOP PUBLISHING LTD}, type = {Article}, address = {DIRAC HOUSE, TEMPLE BACK, BRISTOL BS1 6BE, ENGLAND}, abstract = {

We report here a straightforward and rapid microwave - hydrothermal route providing an easy synthesis of Eu3+ doped La2O3 nanowhiskers. The nanostructured Eu3+ doped La2O3 is characterized by x-ray diffraction studies, scanning electron microscopy and photoluminescence (PL). The emission spectrum shows transitions from the excited 5D(0) state to F-7(J) (J = 0, 1, 2, 3, 4) levels of the Eu3+ ion. The most intense peak around 611 nm is due to the D-5(0) -\> F-7(2) transition, expected from the Judd-Ofelt selection rules. PL spectra measurements demonstrate that the lanthanum oxide nanowhisker shows higher PL intensity.

}, issn = {0022-3727}, doi = {10.1088/0022-3727/39/18/008}, author = {Murugan, A. Vadivel and Viswanath, Annamraju Kasi and Kakade, Bhalchandra A. and Ravi, V. and Saaminathan, V.} } @article { ISI:000238412100062, title = {Exfoliation-induced nanoribbon formation of poly(3,4-ethylene dioxythiophene) PEDOT between MoS2 layers as cathode material for lithium batteries}, journal = {Journal of Power Sources}, volume = {156}, number = {2}, year = {2006}, month = {JUN}, pages = {615-619}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

A new type of layered nanocomposite synthesized by delaminated MoS2 nanosheets and poly(3,4-ethylenedioxythiophene) (PEDOT) are restacked to produce alternate polymer nanoribbons between layers Of MoS2 with an interlayer distance of similar to 1.38 nm. The unique properties of resulting nanocomposite are investigated by powder XRD, XPS, SEM, TEM, and four-probe conductivity measurements. The obtained nanocomposite can be used as a cathode material for a small power rechargeable lithium battery as demonstrated by the electrochemical insertion of lithium into the PEDOT/MoS2 nanocomposite. A significant enhancement in the discharge capacity (100 mAh g(-1)) is observed compared with that (40 mAh g(-1)) for MoS2. (c) 2005 Elsevier B.V All rights reserved.

}, keywords = {cathode material, lithium batteries, MoS2, organic-inorganic nanocomposite, PEDOT-nanoribbons}, issn = {0378-7753}, doi = {10.1016/j.jpowsour.2005.06.022}, author = {Murugan, A. Vadivel and Quintin, M. and Delville, M. H. and Campet, Guy and Gopinath, Chinnakonda S. and Vijayamohanan, K.} } @article { ISI:000241248000088, title = {Highly efficient organic-inorganic poly(3,4-ethylenedioxythiophene)-molybdenum trioxide nanocomposite electrodes for electrochemical supercapacitor}, journal = {Journal of Applied Physics}, volume = {100}, number = {7}, year = {2006}, month = {OCT}, pages = {Article No. 074319}, publisher = {AMER INST PHYSICS}, type = {Article}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

In this paper, we report a highly efficient organic-inorganic nanocomposite electrode with enhanced double layer capacitance, which has been synthesized using 3,4-ethylenedioxythiophene and crystalline molybdenum trioxide (MoO3) in the presence of an external oxidizing agent. The interlayer spacing of MoO3 upon intercalation expands from 6.93 to 13.46 A and is followed by an exfoliation and restacking process. The resulting nanocomposite is characterized by powder x-ray diffraction, scanning electron microscopy, transmission electron microscopy, x-ray photoelectron spectroscopy, and four probe conductivity measurements. The application potential of this nanocomposite as an electrode material for electrochemical supercapacitors has been investigated, highlighting the unusual enhancement of double layer capacitance of poly(3,4-ethylenedioxythiphene) (PEDOT-MoO3) nanocomposites (similar to 300 F g(-1)) compared to that of pristine MoO3 (similar to 40 mF g(-1)). The improved electrochemical performance is attributed to the intercalation of electronically conducting PEDOT between MoO3 layers with enhanced bidimensionality and an increase in the surface area. (c) 2006 American Institute of Physics.

}, issn = {0021-8979}, doi = {10.1063/1.2356788}, author = {Murugan, A. Vadivel and Viswanath, Annamraju Kasi and Gopinath, Chinnakonda S. and Vijayamohanan, K.} } @article { ISI:000241506400143, title = {Intact cell MALDI mass spectrometry as a tool to screen drugs in vivo for regulation of protein expression}, journal = {Molecular \& Cellular Proteomics}, volume = {5}, number = {10, S}, year = {2006}, month = {OCT}, pages = {S62}, publisher = {AMER SOC BIOCHEMISTRY MOLECULAR BIOLOGY INC}, type = {Meeting Abstract}, address = {9650 ROCKVILLE PIKE, BETHESDA, MD 20814-3996 USA}, issn = {1535-9476}, author = {Kulkarni, Mahesh J. and Vinod, V. P. and Umashankar, P. K. and Patole, M. and Rao, M.} } @article { ISI:000241203400011, title = {Nanocomposites of polypropylene impact copolymer and organoclays: role of compatibilizers}, journal = {Polymer International}, volume = {55}, number = {11}, year = {2006}, month = {NOV}, pages = {1270-1276}, publisher = {JOHN WILEY \& SONS LTD}, type = {Article}, address = {THE ATRIUM, SOUTHERN GATE, CHICHESTER PO19 8SQ, W SUSSEX, ENGLAND}, abstract = {

Nanocomposites of polypropylene impact copolymer and organoclays were prepared using different compatibilizers (polypropylene-graft-(maleic anhydride) (PPMA), polyethylene-graft-(maleic anhydride) (PEMA) and their mixture) and varying percentages of clay (3 and 6\%) in an attempt to obtain balanced mechanical properties. The nanocomposites were prepared by melt compounding and test specimens were prepared by injection molding. Mechanical properties such as tensile, flexural and Izod impact strength are reported. The clay dispersion was investigated using wide-angle X-ray diffraction while the phase morphology was characterized using scanning electron microscopy. It is shown that the mechanical properties of the system with mixed PPMA and PEMA compatibilizers showed the best balance of mechanical properties among the nanocomposites explored. (C) 2006 Society of Chemical Industry.

}, keywords = {clay, compatibilizers, Nanocomposites, polypropylene}, issn = {0959-8103}, doi = {10.1002/pi.2077}, author = {Deenadayalan, E. and Vidhate, Shailesh and Lele, Ashish K.} } @article { ISI:000237909100023, title = {Organic dye molecules as reducing agent for the synthesis of electroactive gold nanoplates}, journal = {Journal of Colloid and Interface Science}, volume = {298}, number = {2}, year = {2006}, month = {JUN}, pages = {679-684}, publisher = {ACADEMIC PRESS INC ELSEVIER SCIENCE}, type = {Article}, address = {525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USA}, abstract = {

Highly crystalline, hexagonal and triangular nanoplates of gold are synthesized in high yield by a new wet chemical method using multifunctional molecules. Bismarck brown R (BBR) and Bismarck brown Y (BBY). This method involves a simple approach by keeping a mixture of aqueous HAuCl(4) solution and BBR/BBY solution in presence of poly(vinyl pyrrolidone) for 24 h. These nanostructures show unprecedented electrochemical properties exhibiting Surface confinement effect. The UV-visible (UV-vis) spectrum shows certain distinct features with absorptions at 300, 400,and 650 nm extending up to the near infrared region. Selected area electron diffraction patterns of these nanoparticles show highly oriented (111) crystal facets. X-ray diffraction analysis also confirms the Predominant orientation in the (111) crystal planes with lattice constant similar to 4.07 angstrom of face-centered-cubic (fcc) gold. X-ray photoelectron (XP) and Fourier transform infrared (FTIR) spectroscopic analysis shows the presence of a fraction of reducing molecules as surface passivating agent either in the unreacted molecular state or as a mixture of reacted and unreacted product which probably undergoes charge transfer with gold nanocrystals giving absorption at similar to 300 nm. (c) 2005 Elsevier Inc. All rights reserved.

}, keywords = {Bismarck brown, cyclic voltammetry, gold nanoplates, poly(vinyl pyrrolidone), surface plasmon resonance}, issn = {0021-9797}, doi = {10.1016/j.jcis.2005.12.048}, author = {Sharma, Jadab and Vijayamohanan, Kunjukrishna P.} } @article { ISI:000239869200010, title = {Organosilanesulfonic acid-functionalized Zr-TMS catalysts: synthesis, characterization and catalytic applications in condensation reactions}, journal = {Applied Catalysis A-General}, volume = {310}, year = {2006}, month = {AUG}, pages = {79-90}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Organosilanesulfonic acid (-Si-R3S-R4SO3H, OSA)-functionalized mesoporous Zr-TMS (Zr-TMS-Si-R3S-R4SO3H, Zr-TMS-OSA) was synthesized either by post-synthetic modification of Zr-TMS (zirconia-based transition metal oxide mesoporous molecular sieves) with 3-mercaptopropyltrimethoxysilane (3-MPTS) and further with 1,4-butanesultone (1,4-BS) or by in situ one-pot synthesis procedure. A number of physico-chemical characterization techniques have been used to show that the organosilanesulfonic acid groups were anchored on to the walls of Zr-TMS. MCM-41-Si-R3S-R4SO3H-20 (MCM-41-OSA-20) was also prepared by post-synthesis procedure for comparison. Physico-chemical properties of in situ made A-Zr-OSA-20, Zr-TMS-SO3H-20 and MCM-41-OSA-20 were compared with Zr-TMS-OSA catalysts. The catalytic activity of the materials was tested in liquid phase condensation of aniline with p-formaldehyde to 4,4{\textquoteright}-diaminodiphenylmethane (4,4{\textquoteright}-DADPM). Results showed that Zr-TMS-OSA catalysts were more active than Zr-TMS-SO3H-20, MCM-41-OSA-20 and A-Zr-OSA-20 and more selective than Zr-TMS-SO3H-20 and A-Zr-OSA-20 catalysts. (C) 2006 Elsevier B.V. All rights reserved.

}, keywords = {Acid catalyst, condensation of aniline, mesoporous ZrO2, organic functionalization, organosilanesulfonic acid}, issn = {0926-860X}, doi = {10.1016/j.apcata.2006.05.024}, author = {Chidambaram, M. and Venkatesan, C. and Singh, A. P.} } @article { ISI:000240680300119, title = {Photoluminescence studies of Eu3+ doped Y2O3 nanophosphor prepared by microwave hydrothermal method}, journal = {Applied Physics Letters}, volume = {89}, number = {12}, year = {2006}, month = {SEP}, pages = {123120}, publisher = {AMER INST PHYSICS}, type = {Article}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

In this letter, the authors report the photoluminescence studies of Eu3+ doped Y2O3 nanorods, which have been synthesized by rapid microwave hydrothermal route within 6 min. The nanostructured Eu3+ doped Y2O3 is characterized by x-ray diffraction, transmission electron microscopy, and photoluminescence. The emission spectrum shows transitions from the excited 5D(0) state to F-7(J) (J=0,1,2,3,4) levels of the Eu3+ ion. The most intense peak around 612 nm is due to the D-5(0)-\> F-7(2) transition, expected from the Judd-Ofelt selection rules [B. R. Judd, Phys. Rev. 127, 750 (1962); G. S. Ofelt, J. Chem. Phys. 37, 511 (1962)]. Photoluminescence measurements demonstrated that the nanocrystalline Eu3+:Y2O3 phase shows higher photoluminescence intensity. (c) 2006 American Institute of Physics.

}, issn = {0003-6951}, doi = {10.1063/1.2356694}, author = {Murugan, A. Vadivel and Viswanath, Annamraju Kasi and Ravi, V. and Kakade, Bhalchandra A. and Saaminathan, V.} } @article { ISI:000242209000043, title = {Poly(urethane methacrylate-co-glycidyl methacrylate)-supported-polypropylene biphasic membrane for lipase immobilization}, journal = {Journal of Membrane Science}, volume = {285}, number = {1-2}, year = {2006}, month = {NOV}, pages = {395-403}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Polypropylene (PP) was hydrophilized by coating followed by UV curing of a blend of 2-hydroxyethyl methacrylate (HEMA) terminated polyurethane prepolymer and glycidyl methacrylate (GMA). This allows formation of a hydrophobic membrane with increased surface hydrophilicity, biocompatibility and stability. Candida rugosa lipase (CRL) was covalently immobilized on this membrane using 5\% glutaraldehyde as a crosslinking agent for post immobilization stabilization of enzyme on membrane. The membrane obtained was placed in a batch membrane reactor where a model esterification of oleic acid with octanol was studied. Under optimum conditions, the biocatalytic membrane gave a specific activity of 796.27 units/mg and 90.26\% activity yield. Moreover, there was 85. 10\% retention of specific activity. The biocatalytic membrane was observed to retain about 84.23\% of its synthetic activity after six cycles. (c) 2006 Elsevier B.V. All rights reserved.

}, keywords = {Candida rugosa lipase, Enzyme immobilization, membrane bioreactor, urethane methacrylate}, issn = {0376-7388}, doi = {10.1016/j.memsci.2006.09.009}, author = {Pujari, N. S. and Vaidya, Bx and Bagalkote, S. and Ponrathnam, S. and Nene, Sanjay} } @article { ISI:000242427200014, title = {Preparation and characterization of urea-formaldehyde-pepsin bioconjugate: a new biocatalyst system}, journal = {Biotechnology Progress}, volume = {22}, number = {6}, year = {2006}, month = {DEC}, pages = {1585-1590}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

This study describes the synthesis of urea formaldehyde (UF) microspheres by a dispersion polycondensation polymerization method. These microspheres with proper F/U molar ratio can provide highly reactive groups, capable of further condensation with the amino acid residues of enzyme/proteins. Presence of methylols groups in UF microspheres was confirmed by C-13 NMR study. Pepsin, a proteolytic enzyme, was immobilized on the UF microspheres to form bioconjugate system. As compared to the free enzyme in solution, the pepsin in the bioconjugate system exhibited significantly enhanced pH and temperature stability. The urea-formaldehydepepsin bioconjugate system also exhibited excellent proteolytic activity over eight successive reuse cycles with more than 50\% of initial activity. A highlight of this new biocatalyst is the ease with which separation of this biocatalyst from the reaction medium may be achieved by mild centrifugation.

}, issn = {8756-7938}, doi = {10.1021/bp0602247}, author = {Vinod, V. P. and Shinde, Sudhirkumar and D{\textquoteright}Britto, Virginia and Shukla, P. G. and Rao, Mala} } @article { ISI:000239739400011, title = {Promoter induced rapid synthesis of AlPO4-5 molecular sieve in non-aqueous media using hexamethyleneimine template}, journal = {Journal of the Indian Chemical Society}, volume = {83}, number = {7}, year = {2006}, month = {JUL}, pages = {692-696}, publisher = {INDIAN CHEMICAL SOC}, type = {Article}, address = {92 ACHARYA PRAFULLA CHANDRA RD ATTN:DR INDRAJIT KAR/EXEC SEC, CALCUTTA 700009, INDIA}, abstract = {

AlPO4-5 have been synthesized from non-aqueous media using hexamethyleneimine template in presence of sodium ions. The results show that the sodium catalyses the nucleation and crystallization process of the formation of AlPO4-5 molecular sieve. The material synthesized was characterized by XRD, SEM, carbon and nitrogen analysis, TG/DTA, FT-IR, Al-27 and P-31 MASNMR. The results show that the samples are highly crystalline. The presence of octahedral and tetrahedral sites are observed in 27 At MASNMR, P-31 MASNMR gives only a single peak for tetrahedral phosphorous atoms.

}, keywords = {aluminophosphates, Molecular sieve, non-aqueous media}, issn = {0019-4522}, author = {Venkatathri, N.} } @article { ISI:000241591900017, title = {Selective production of methoxyphenols from dihydroxybenzenes on alkali metal ion-loaded MgO}, journal = {Journal of Catalysis}, volume = {243}, number = {2}, year = {2006}, month = {OCT}, pages = {376-388}, publisher = {ACADEMIC PRESS INC ELSEVIER SCIENCE}, type = {Article}, address = {525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USA}, abstract = {

Selective O-methylation of dihydroxybenzenes (DHBs; catechol, resorcinol, and hydroquinone) to methoxyphenols (MPs) was carried out with dimethylcarbonate on MgO and alkali metal ion (Li, K, and Cs)-loaded MgO between 523 and 603 K. Catalytic activity and product selectivity varied with respect to DHB substrates. Selectivity for O-methylated products increased with increasing basicity of alkali ions; however, K-MgO showed high and stable activity toward MPs. Selectivity for MPs obtained from three substrates increased in the following order: catechol \< resorcinol \< hydroquinone. The mode of interaction of substrates on the catalysts surface influenced reactivity and product selectivity. It is likely that the low reaction temperatures used (\< 603 K) kinetically control and favor high MP selectivity from DHBs. Calcined and spent catalysts were characterized by XRD, surface area, SEM, thermal analysis, NMR, and XPS. XRD analysis revealed the formation of alkali oxide phases on alkali-loaded MgO. Crystallite size and surface area of the catalysts decreased after methylation reactions, except on K-MgO. TGA showed 4060 wt\% coke deposition on spent catalysts. TGA in N-2 followed by air and C-13 CP-MAS NMR measurements indicated the nature of deposited carbon to be molecular species, graphite, MgCO3 and polyaromatics. XPS revealed the nature and availability of active sites on the spent catalysts, as well as the same changes with reaction conditions and correlated with catalytic activity. (c) 2006 Elsevier Inc. All rights reserved.

}, keywords = {alkali-loaded MgO, dihydroxybenzene, K-MgO, methoxyphenol, MgO, O-methylation, thermal analysis, XPS}, issn = {0021-9517}, doi = {10.1016/j.jcat.2006.08.009}, author = {Vijayaraj, Munusamy and Gopinath, Chinnakonda S.} } @article { ISI:000239739400012, title = {Synthesis and characterization of AlPO4-5RT molecular sieve at room temperature}, journal = {Journal of the Indian Chemical Society}, volume = {83}, number = {7}, year = {2006}, month = {JUL}, pages = {697-701}, publisher = {INDIAN CHEMICAL SOC}, type = {Article}, address = {92 ACHARYA PRAFULLA CHANDRA RD ATTN:DR INDRAJIT KAR/EXEC SEC, CALCUTTA 700009, INDIA}, abstract = {

Aluminophosphate molecular sieve AlPO4-5RT (AlPO4-5, prepared at room temperature) have been synthesized using hexamethyleneimine template at room temperature for the first time. Gel composition Al2O3 : P2O5 : 1.16HEM : 45H(2)O aging for 12 h at room temperature, and in 24 h, 473 K are the standard reaction conditions for synthesis of AlPO4-5. Studies on above gel composition at room temperature shows the presence of AlPO4-5 crystals. Both the aluminophosphates have been characterized by elemental analysis, XRD, SEM, FT-IR, TG/DTA, and C-13, Al-27 and P-31 MASNMR techniques. XRD analysis of AlPO4-5RT shows that the presence of low intensed pseudobochmite sample. SEM shows the morphology nanosized crystals along with platelets. TG/DTA analysis reveals the presence of maximum five stages elimination of templates. Carbon and nitrogen analysis shows that the presence of four template molecules per unitcell. C-13 MASNMR analysis shows the interaction of template with structure of the framework. Al-27 MASNMR shows the presence of small amount of octahedral co-ordination besides the rest are in tetrahedral co-ordination. P-31 MASNMR shows the presence of two environmentally different tetrahedrally co-ordinated phosphorous atoms.

}, keywords = {Aluminophosphate, Molecular sieve}, issn = {0019-4522}, author = {Venkatathri, N.} } @article { ISI:000241320000007, title = {Synthesis and characterization of high silica content silicoaluminophosphate SAPO-35 from non-aqueous medium}, journal = {Catalysis Communications}, volume = {7}, number = {10}, year = {2006}, month = {OCT}, pages = {773-777}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

SAPO-35 with up to 15.6 Si atoms per unit cell have been synthesized, using hexamethyleneimine as template in ethylene glycol medium (molar ratio of silica in the reaction gets up to 2.5). Crystallinity and silicon incorporation was confirmed by XRD, XRF, TG/DTA, SEM, FT-IR and Al-27 and Si-29 MASNMR. These SAPO-35 materials with high Si concentration show higher activity for methanol to olefin reaction than samples prepared with up to 0.3 molar ratio of silica in the get. (c) 2005 Elsevier B.V. All rights reserved.

}, keywords = {ammonia adsorption, FT-IR, MASNMR, methanol to olefin, non-aqueous medium, SAPO-35, SEM, TG/DTA, XRD}, issn = {1566-7367}, doi = {10.1016/j.catcom.2005.10.014}, author = {Venkatathri, N.} } @article { ISI:000242793800020, title = {Synthesis and characterization of TAPO-31 molecular sieves using tripropylamine template}, journal = {Catalysis Communications}, volume = {7}, number = {12}, year = {2006}, month = {DEC}, pages = {1015-1021}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

TAPO-31 was synthesized hydrothermally using a novel template tri-n-propylamine for the first time. C and N analysis shows the butanol from titanium tetrabutoxide plays an important role in the synthesis. The incorporation of titanium into framework of phosphorous and both aluminiurn and phosphorous sites was suggested from elemental analysis. Isomorphous substitution of titanium (III) in AlPO framework was confirmed from ESR and (31)p MASNMR spectra. UV-Vis and XPS spectra revealed a partial oxidation of framework titanium (III) into titanium (IV) in the calcined TAPO-31 and thus the presence of redox centers in the products. The higher titanium content (Al/Ti = 10) TAPO-31 sample shows higher activity for phenol hydroxylation compared to lower titanium content (Al/Ti = 20) and Titanium impregnated AIPO(4)-31. (c) 2006 Elsevier B.V. All rights reserved.

}, keywords = {ESR, FT-IR, MASNMR, SEM, TAPO-31, TG/DTA, tripropylamine, UV-Vis, XPS, XRD}, issn = {1566-7367}, doi = {10.1016/j.catcom.2006.05.010}, author = {Venkatathri, N. and Shetty, V. N.} } @article { ISI:000239869200004, title = {Synthesis, characterization and catalytic properties of vanadium aluminophosphate molecular sieves VAPO-31 and VAPSO-Amr from non-aqueous media}, journal = {Applied Catalysis A-General}, volume = {310}, year = {2006}, month = {AUG}, pages = {31-39}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Vanadium samples containing aluminophosphate molecular sieve (VAPO-31) and amorphous vanadium silicoaluminophosphate (VAPSO-Amr) have been synthesized using hexamethyleneimine template from non-aqueous media for the first time. XRD and SEM analyses confirm the phase purity of the synthesized samples. FT-IR analysis suggests the incorporation of V4+ in the aluminophosphate framework. ESR, UV-vis spectroscopic, and XPS techniques and cyclicvoltametric studies confirm the incorporation of vanadium and reveal its presence in tetrahedral and square pyramidal environments in the as-synthesized samples. Cyclic voltammetry reveals the presence of two redox couples in VAPO-31. This catalyst is found to be a good oxidation catalyst. Although most of the properties of VAPO-31NA and VAPSO-Amr are similar, the latter can access more vanadium and V4+ ions. Compared to aqueous media samples, it can incorporate more vanadium especially V5+, ions and has been found to be better oxidation catalyst. The physicochemical properties also change with media. (C) 2006 Elsevier B.V. All rights reserved.

}, keywords = {cyclic voltammetry, ESR, FT-IR, MAS NMR, non-aqueous, SEM, TG/DTA, UV-Vis, VAPO-31, XPS, XRD}, issn = {0926-860X}, doi = {10.1016/j.apcata.2006.05.001}, author = {Venkatathri, N.} } @article { ISI:000239739400010, title = {Synthesis of high alumina ZSM-5 molecular sieve with ethylene diamine as template}, journal = {Journal of the Indian Chemical Society}, volume = {83}, number = {7}, year = {2006}, month = {JUL}, pages = {686-691}, publisher = {INDIAN CHEMICAL SOC}, type = {Article}, address = {92 ACHARYA PRAFULLA CHANDRA RD ATTN:DR INDRAJIT KAR/EXEC SEC, CALCUTTA 700009, INDIA}, abstract = {

Attempts were made to investigate compositional constraints in the synthesis of pentasill molecular sieves, including aluminosilicate zeolites using ethylene diamine (C2DN) template, from the gel composition 1.85Na(2)O : aAl(2)O(3) : 15.2SiO(2) : 592H(2)O : 19.7C(2)DN in the temperature 177 degrees C for ten days. When a = 0.25 the product was ZSM-5 and then a = 1 the product was ZSM-35 and in between compositions the mixture of two were obtained. Reduce the time of crystallization time to 5 days give nanocrystalline material. XRD and FT-IR spectra in framework region of ZSM-5 synthesized using ethylene diamine template and without template are having similar pattern, however the intensity varies. Scanning electron microscopic picture of the both are varies. The structural stability of the zeolite ZSM-5 synthesized using no template was also found to be lower as compared with that for the ZSM-5 synthesized using ethylene diamine template. These differences. may result from the occluded excess sodium.

}, keywords = {ethylenediamine, Molecular sieve, zeolite}, issn = {0019-4522}, author = {Venkatathri, N.} } @article { ISI:000242469000012, title = {Unusual formation of nano-particles of CdO and Cd(OH)(2) from the reaction of dimethyl cadmium with DMF}, journal = {Materials Letters}, volume = {60}, number = {29-30}, year = {2006}, month = {DEC}, pages = {3492-3498}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

This paper presents generation of CdO and Cd(OH)(2) nano-particles from Dimethyl Cadmium in DMF. The CdO nano-particles were obtained instead of CdSe, even when the reaction was done in presence of 1,2,3-selenadiazole (the source of selenium) with Me2Cd in DMF (product-I). The direct reaction of Me2Cd in DMF also leads to formation of CdO (product-II). However, Cd(OH)(2) nano-particles were obtained when Me2Cd was refluxed in DMF for a few hours followed by reaction of H2S gas (product-III). The formation of Cd(OH)(2) was also established via decomposition Of Me2Cd:Et2O adduct (product-IV). Nano-particles of CdO and Cd(OH)(2) (product-I to product-IV) were characterized by X-ray powder diffraction (XRD), TEM and SEM/EDS measurements, FTIR, thermal analysis (TGA) and XPS analysis. The particle size of all the products as calculated by XRD patterns were in the range of about 20 nm. TEM images showed that the products are agglomerated clusters with the particles in the nano-meter regime. The synthesis however, is understood to be unusual as the reactions with selenium source and sulfur source should have generated the CdSe and CdS however, the end products were always found to be the product-I to product-IV (c) 2006 Elsevier B.V. All rights reserved.

}, keywords = {Chemical synthesis, Nanoparticles, Semiconductor, XRD}, issn = {0167-577X}, doi = {10.1016/j.matlet.2006.03.054}, author = {Singh, Narendra and Charan, Shobhit and Patil, K. R. and Viswanath, A. K. and Khanna, P. K.} } @article { ISI:000240496500030, title = {ZnO multipods, submicron wires, and spherical structures and their unique field emission behavior}, journal = {Journal of Physical Chemistry B}, volume = {110}, number = {37}, year = {2006}, month = {SEP}, pages = {18236-18242}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

A simple method of vapor deposition for the shape selective synthesis of ZnO structures, namely, multipods, submicron wires, and spheres, has been successfully demonstrated. A plausible growth mechanism based on the studies of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) is proposed. Our studies suggest that the growth of a multipod structure is governed by the screw dislocation propagation while the vapor-liquid-solid (VLS) mechanism is responsible for the formation of submicron wires and spheres. Moreover, the flow rate of the carrier gas plays a crucial role in governing the morphology. Further, these structures exhibit an enhanced field emission behavior. The nonlinearity in the Fowler-Nordheim (F-N) plot, a characteristic feature of electron emission from semiconductors, is explained by considering the contributions from both the conduction and the valence bands of ZnO.

}, issn = {1520-6106}, doi = {10.1021/jp0628131}, author = {Ramgir, Niranjan S. and Late, Dattatray J. and Bhise, Ashok B. and More, Mahendra A. and Mulla, Imtiaz S. and Joag, Dilip S. and Vijayamohanan, K.} } @article {42681, title = {Ab initio lifetimes in the interatomic coulombic decay of neon clusters computed with propagators}, journal = {Journal of Chemical Physics}, volume = {126}, year = {2007}, month = {APR}, pages = {Article No. 164110}, type = {Article}, doi = {10.1063/1.2723117}, author = {Vaval, Nayana and Cederbaum, Lorenz S.} } @article { ISI:000243163000025, title = {Bimetallic Pt-Sn/gamma-alumina catalyst for highly selective liquid phase hydrogenation of diethyl succinate to gamma-butyrolactone}, journal = {Catalysis Communications}, volume = {8}, number = {3}, year = {2007}, month = {MAR}, pages = {340-344}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Platinum-tin bimetallic catalyst on gamma-alumina support was prepared by impregnation method and was reduced by sodium borohydride at room temperature. XRD and XPS characterization revealed that platinum was reduced to Pt-0 while, tin was probably partially reduced to Sn2+ due to the low temperature reduction method and Sn-0 was completely absent, avoiding the formation of P-Sn alloy. Pt-Sn/gamma-alumina (Pt 1\%, Sn 9\%) thus prepared was found to give almost complete selectivity to gamma-butyrolactone in liquid phase hydrogenation of diethyl succinate. A plausible reaction pathway is proposed involving Pt-O-Sn state and high selectivity to GBL is due to the Lewis acidity of Sn2+/4+ (c) 2006 Elsevier B.V. All rights reserved.

}, keywords = {bimetallic Pt-Sn catalyst, gamma-butyrolactone selectivity, liquid phase hydrogenation of diethyl maleate, XPS of Pt-Sn, XRD of Pt-Sn}, issn = {1566-7367}, doi = {10.1016/j.catcom.2006.06.026}, author = {Vaidya, S. H. and Rode, C. V. and Chaudhari, Raghunath V.} } @article { ISI:000249949800020, title = {Catalytic performances of silicotungstic acid/zirconia supported SBA-15 in an esterification of benzyl alcohol with acetic acid}, journal = {Journal of Molecular Catalysis A-Chemical }, volume = {276 }, number = {1-2}, year = {2007}, month = {OCT}, pages = {150-157}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Liquid phase esterification of benzyl alcohol (BA) to benzyl acetate (Peach fragrance) with an acetic acid (AA) has been investigated with 12-silicotungstic acid supported on zirconia embedded inside SBA-15 (STA/ZrO2/SBA- 15) as the catalyst. Catalysts were unambiguously characterized by XRD, N-2 adsorption-desorption, FF-IR pyridine adsorption techniques and the total amount of acidity of different STA loaded catalysts was estimated by TPD of NH3. The optimization of reaction conditions of an esterification of BA with AA was performed with 15 wt.\% STA/22.4 wt.\% ZrO2/SBA-15 calcined at 1123 K by varying catalyst concentration (1-10 wt.\% of reaction mixture); temperature, 353-383 K and AA:BA molar ratio as 0.5-3. The 15 wt.\% STA/22.4 wt.\% ZrO2/SBA-15 calcined at 1123 K was found to have the highest acidity and more active in the reaction. Under the optimized reaction conditions, the 15 wt.\% STA/22.4 wt.\%ZrO2/SBA-15 calcined at 1123 K gave 59\% BA conversion with selectivity for benzyl acetate as high as 96\% within 2 h of reaction time. (c) 2007 Elsevier B.V. All rights reserved.

}, keywords = {12-silicotungstic acid, Benzyl acetate, Benzyl alcohol, Esterification, SBA-15}, issn = {1381-1169}, doi = {10.1016/j.molcata.2007.07.001}, author = {Sawant, Dhanashri P. and Vinu, A. and Justus, Josena and Srinivasu, P. and Halligudi, Shivaraj B.} } @article { ISI:000246329700015, title = {Cyclic voltammetry, electrochemical impedance and ex situ X-ray diffraction studies of electrochemical insertion and deinsertion of lithium ion into nanostructured organic-inorganic poly(3,4-ethylenedioxythiophene) based hybrids}, journal = {Journal of Electroanalytical Chemistry}, volume = {603}, number = {2}, year = {2007}, month = {MAY}, pages = {287-296}, publisher = {ELSEVIER SCIENCE SA}, type = {Article}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

In this work, we discuss the electrochemical insertion and deinsertion of lithium into poly(3,4-ethylenedioxythiophene) PEDOT-V(2)O(5) nanohybrids by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and powder ex situ X-ray diffraction (XRD) studies with special emphasis on their application potential as cathode materials for rechargeable Lithium batteries. The interlayer spacing of crystalline V(2)O(5) expands from 0.43 to 1.41 nm by the intercalation of PEDOT nanoribbons prepared by a microwave irradiation method. Cyclic voltammetry studies of PEDOT-V(2)O(5) hybrid at a slow scan rate of 0.058 mVs(-1) between 2.0-4.3 V vs. Li/ Li(+), demonstrates that structural transitions Of V(2)O(5) are suppressed and more facile intercalation features appear in terms of well-defined reversible cathodic and anodic peaks when compared to that at higher scan rate. Electrochemical Impedance studies of PEDOT-V(2)O(5) hybrid as cathode at ambient temperature with lithium metal foil as both counter and reference electrodes in 1 M LiPF(6) in a mixture of ethylene and diethylcarbonate (50:50 by volume) between the range 2.0-4.3 V reveals the usefulness of these materials. The observed capacity fading during cycling in terms of surface passivation and structural transformations is also investigated by CV, EIS and XRD analysis. (C) 2007 Elsevier B.V. All rights reserved.

}, keywords = {cyclic voltammetry, ex situ XRD studies, high capacity lithium batteries, impedance studies, nanostructured hybrid materials}, issn = {1572-6657}, doi = {10.1016/j.jelechem.2007.02.013}, author = {Murugan, A. Vadivel and Reddy, M. V. and Campet, Guy and Vijayamohanan, K.} } @article { ISI:000244006000001, title = {Direct comparison of the aging and memory effects of magnetic nanoclusters and nanoparticles}, journal = {Solid State Communications}, volume = {141}, number = {6}, year = {2007}, month = {FEB}, pages = {307-310}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

The magnetic characteristics of a dense magnetic nanoparticle system and a spin glass system consisting of magnetic nanoclusters are compared. Zero field cooled and field cooled magnetization measurements, including aging and memory experiments, of the nanoparticle and the magnetic cluster systems show similar characteristics, suggesting a common origin for the spin glass-type behavior of the magnetic nanoparticle and nanocluster systems. (C) 2006 Published by Elsevier Ltd.

}, keywords = {Magnetic nanoparticles, magnetic properties, spin glasses}, issn = {0038-1098}, doi = {10.1016/j.ssc.2006.11.015}, author = {Sankar, C. Raj and Vijayanand, S. and Verma, Seema and Joy, Pattayil Alias} } @article { ISI:000243366400007, title = {Glycine-assisted enhancement of 1,4-beta-D-xylan xylanohydrolase activity at alkaline pH with a pH optimum shift}, journal = {Biological Chemistry}, volume = {388}, number = {1}, year = {2007}, month = {JAN}, pages = {61-65}, publisher = {WALTER DE GRUYTER GMBH}, type = {Article}, address = {GENTHINER STRASSE 13, D-10785 BERLIN, GERMANY}, abstract = {

This is the first report describing the enhancement of xylanase activity by the neutral amino acid glycine. Xylanase activity is increased seven-fold at alkaline pH in the presence of glycine and its pH optimum is shifted from pH 7 to 8 without using any protein engineering techniques. Analysis of the steady-state kinetics revealed that glycine in the reaction mixture increases the K-m and k(cat) values of the enzyme. Chemoaffinity labeling and studies using glycine esters indicate an involvement of the carboxylate ion of glycine in enhancing xylanase catalytic activity. A novel possible mechanism for the glycine-assisted catalytic action of xylanase is proposed.

}, keywords = {Enzyme catalysis, OPTA, Thermomonospora sp., Xylanase}, issn = {1431-6730}, doi = {10.1515/BC.2007.007}, author = {Vathipadiekal, Vinod and Verma, Anamika and Rao, Mala} } @article { ISI:000250792200005, title = {Immobilization of mushroom polyphenol oxidase on poly(allyl glycidyl ether-co-ethylene glycol dimethacrylate) macroporous beaded copolymers}, journal = {Reactive \& Functional Polymers}, volume = {67}, number = {10}, year = {2007}, month = {OCT}, pages = {905-915}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Functional, macroporous, beaded copolymers containing epoxy groups were synthesized for immobilization of polyphenol oxidase (PPO) from edible mushroom (Agaricus bisporus). The effect of incorporation of two different sets of monomers such as glycidyl methacrylate (GMA) and allyl glycidyl ether (AGE) and the effect of cross-linking agent ethylene glycol dimethacrylate (EGDM) with varying cross-link densities on binding and expression of mushroom PPO activity were studied. The effect of porogen viz. cyclohexanol and hexanol on PPO immobilization was studied. AGE copolymers with hexanol as a porogen were found to give higher binding and expression of PPO activity than GE polymers. Crosslinking of amino groups of enzyme with 5\% glutaraldehyde for 6 h gave a stable binding of PPO on AGE-75(Hex) polymer with storage half-life of approximately 25 days. Under optimum conditions, AGE-75(Hex) polymer gave 70.3\% of activity yield while percent retention of PPO activity was found to be 83.5\%. Immobilized PPO showed a broader pH, higher temperature and excellent storage stability. (c) 2007 Elsevier Ltd. All rights reserved.

}, keywords = {cross-linking agent, Enzyme immobilization, Epoxy-activated support, mushroom PPO}, issn = {1381-5148}, doi = {10.1016/j.reactfunetpolym.2007.05.015}, author = {Vaidya, Bhalchandra K. and Karale, Abhijeet J. and Suthar, Hitesh K. and Ingavle, Ganesh C. and Pathak, Tara Sankar and Ponrathnam, S. and Nene, Sanjay} } @article { ISI:000244902800037, title = {Improve polyethylene process control and product quality - using artificial intelligence-based sensors can improve costs}, journal = {Hydrocarbon Processing }, volume = {86}, number = {3}, year = {2007}, month = {MAR}, pages = {53+}, publisher = {GULF PUBL CO}, type = {Article}, address = {BOX 2608, HOUSTON, TX 77252-2608 USA}, issn = {0018-8190}, author = {Badhe, Yogesh P. and Lonari, J. and Tambe, S. S. and Kulkarni, B. D. and Valecha, N. K. and Deshmukh, S. V. and Ravichandran, S.} } @article { ISI:000243150300031, title = {Interface and defect structures in YBa(2)Cu(3)O(7-delta) and Nb : SrTiO(3) heterojunction}, journal = {Journal of Physics D-Applied Physics}, volume = {40}, number = {1}, year = {2007}, month = {JAN}, pages = {187-191}, publisher = {IOP PUBLISHING LTD}, type = {Article}, address = {TEMPLE CIRCUS, TEMPLE WAY, BRISTOL BS1 6BE, ENGLAND}, abstract = {

YBa(2)Cu(3)O(7-delta) thin films grown on a Nb-doped SrTiO(3) substrate by a pulsed laser deposition method have been fully characterized by scanning transmission electron microscopy Z- contrast imaging and electron energy loss spectroscopy techniques. The Nb distribution was found to be uniform and unchanged across the interface, ensuring a high quality p - n junction heterointerface. We first observed the coexistence of 124 and 125 YBCO defect structure phases, appearing as planar defects in a YBCO thin film. Dispersive Y(2)O(3) nanoparticles have also been observed in the thin film. The interaction of these defect structures and Y(2)O(3) nanoparticles is thought to be beneficial for pinning flux through the entire film thickness.

}, issn = {0022-3727}, doi = {10.1088/0022-3727/40/1/013}, author = {Fu, Lian-feng and Browning, Nigel D. and Ramadan, W. and Ogale, Satishchandra B. and Kundaliya, D. C. and Venkatesan, T.} } @article { ISI:000243268600010, title = {Lactic acid production from waste sugarcane bagasse derived cellulose}, journal = {Green Chemistry}, volume = {9}, number = {1}, year = {2007}, month = {JAN}, pages = {58-62}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Production of L(+) lactic acid from sugarcane bagasse cellulose, one of the abundant biomass materials available in India, was studied. The bagasse was chemically treated to obtain a purified bagasse cellulose sample, which is much more amenable to cellulase enzyme attack than bagasse itself. This sample, at high concentration (10\%), was hydrolyzed by cellulase enzyme preparations (10 FPU g(-1) cellulose) derived from mutants generated in our own laboratory. We obtained maximum hydrolysis (72\%), yielding glucose and cellobiose as the main end products. Lactic acid was produced from this bagasse cellulose sample by simultaneous saccharification and fermentation (SSF) in a media containing a cellulase enzyme preparation derived from Penicillium janthinellum mutant EU1 and cellobiose utilizing Lactobacillus delbrueckii mutant Uc-3. A maximum lactic acid concentration of 67 g l(-1) was produced from a concentration of 80 g l(-1) of bagasse cellulose, the highest productivity and yield being 0.93 g l(-1) h(-1) and 0.83 g g(-1), respectively. The mutant Uc-3 was found to utilize high concentrations of cellobiose (50 g l(-1)) and convert it into lactic acid in a homo-fermentative way. Considering that bagasse is a waste material available in abundance, we propose to valorize this biomass to produce cellulose and then sugars, which can be fermented to products such as ethanol and lactic acid.

}, issn = {1463-9262}, doi = {10.1039/b605839f}, author = {Adsul, Mukund G. and Varma, Anjanikumar and Gokhale, Digambar V.} } @article { ISI:000251068800001, title = {Metal complexes of crosslinked chitosans. part II. an investigation of their hydrolysis to chitooligosaccharides using chitosanase}, journal = {International Journal of Biological Macromolecules}, volume = {41}, number = {5}, year = {2007}, month = {DEC}, pages = {491-496}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

This paper investigates the behavior of crosslinked chitosans and metal-complexed crosslinked chitosans under similar hydrolytic conditions. Crosslinked chitosans with trimellitic anhydride, diisocyanatohexane, and dibromodecane as crosslinking agents under heterogenous reaction conditions were used as metal complexing agents by equilibrating them with metal salts such as ZnCl2, MnSO4, CuSO4, CdSO4, Pb(NO3)(2), and HgCl2. Crosslinked chitosan without metal complexation had the same hydrolytic behavior as uncrosslinked chitosan. However, when the crosslinked chitosans were complexed with metals, their rates of hydrolysis and extent of hydrolysis were significantly reduced. Thus, while for chitosan about 840 mu g/ml reducing sugar was produced in 4 h time, and 780 mu g/ml was produced for diisocyanatohexane crosslinked chitosan, only 400 mu g/ml and 320 [mu g/ml reducing sugars were produced for cadmium sulfate with crosslinked chitosan and diisocyanatohexane crosslinked chitosan, respectively. Similar results are obtained for other crosslinking agents. Studies on preincubation of the metal with the enzyme show that of the metals studied, Mn has no effect on preincubatioin with the enzyme, Hg, Cd, Pb, and Cu completely deactivates the enzyme, while Zn reduces the enzyme activity by about 43.3\%. Preincubation of the metal salts with the chitosan shows that Hg and Cu completely deactivate the molecule from enzyme hydrolysis, Cd and Zn inactivate it to the extent of 56.8\% and 43.3\%, respectively, while Mn has no effect. Availability of the amino functions seems to be a key feature for the chitosanase to hydrolyze the chitosan polymer. This was also proved by the significant increase in the extent of hydrolysis for chitosan samples with 88\% (final value 1120 mu g/ml reducing sugar) and 85\% deacetylation (final value 840 mu g/ml reducing sugar). HPIC studies of the products show that a variety of oligomers are produced in the chitosanase enzyme hydrolytic reaction. (C) 2007 Elsevier B.V. All rights reserved.

}, keywords = {chitooligosaccharides, Chitosan, chitosanase hydrolysis, Crosslinked chitosan, metal-complexed crosslinked chitosan}, issn = {0141-8130}, doi = {10.1016/j.ijbiomac.2007.06.009}, author = {Trimukhe, K. D. and Bachate, S. and Gokhale, D. V. and Varma, Anjanikumar} } @article { ISI:000250931100037, title = {One-step synthesis of SBA-15 containing tungsten oxide nanoclusters: a chemoselective catalyst for oxidation of sulfides to sulfoxides under ambient conditions}, journal = {Chemical Communications}, number = {45}, year = {2007}, month = {SEP}, pages = {4806-4808}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Tungsten oxide nanoclusters supported highly ordered mesoporous SBA-15 material has been successfully synthesized in a single step using a non-ionic surfactant as a template and used for the selective oxidation of sulfur compounds, giving excellent yields at room temperature with exceptional catalyst recyclability.

}, issn = {1359-7345}, doi = {10.1039/b709459k}, author = {Bordoloi, Ankur and Vinu, Ajayan and Halligudi, Shivaraj B.} } @article { ISI:000251200200017, title = {Oxyfunctionalisation of adamantane using inorganic-organic hybrid materials based on isopoly and heteropoly anions: kinetics and mechanistic studies}, journal = {Applied Catalysis A-General}, volume = {333}, number = {1}, year = {2007}, month = {DEC}, pages = {143-152}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

{Oxyfunctionalisation of adamantane with 30\% aq.H2O2 in butyronitrile solvent was efficiently catalyzed by inorganic-organic hybrid materials synthesized by the immobilisation of isopoly (WOx = sodium tungstate

}, keywords = {adamantane, inorganic-organic hybrid materials, oxyfunctionalisation, vanadium (V) superoxo intermediate}, issn = {0926-860X}, doi = {10.1016/j.apcata.2007.09.025}, author = {Bordoloi, Ankur and Vinu, Ajayan and Halligudi, Shivaraj B.} } @article { ISI:000245142600008, title = {Rh(II)-catalyzed intramolecular N-H insertion of D-glucose-derived delta-amino alpha-diazo beta-ketoester: Synthesis of pyrrolidine iminosugars}, journal = {Synlett}, number = {4}, year = {2007}, month = {MAR}, pages = {559-562}, publisher = {GEORG THIEME VERLAG KG}, type = {Article}, address = {RUDIGERSTR 14, D-70469 STUTTGART, GERMANY}, abstract = {

The rhodium acetate catalyzed reaction of D-glucose-derived delta-amino alpha-diazo beta-ketoester allows a stereoselective beta-facial intramolecular N-H insertion reaction that leads to formation of the bicyclic pyrrolidinone ring skeleton in high yield. The sugar-substituted pyrrolidinone thus obtained was elaborated to allow the synthesis of promising glycosidase inhibitors, namely, 2,5-dideoxy2,5-imino-L-glycero-alpha-D-galactoheptitol and 2,5-dideoxy-2,5-imino-D-galactitol.

}, keywords = {alkaloids, azasugars, carbohydrates, N-H insertion, Pyrrolidines, rhodium carbenoid}, issn = {0936-5214}, doi = {10.1055/s-2007-970743}, author = {Vyavahare, Vinod P. and Chattopadhyay, Subrata and Puranik, Vedavati G. and Dhavale, Dilip D.} } @article { ISI:000245534900008, title = {Selective mono-N-methylation of aniline substrates on Cu1-xZnxFe2O4}, journal = {Applied Catalysis A-General}, volume = {320}, year = {2007}, month = {MAR}, pages = {64-68}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Selective mono-N-methylation of substituted anilines (o-, m- and p-toluidines, 2,6-xylidine, p-anisidine and p-aminoacetophenone) was carried out with methanol as methylating agent under vapor phase reaction conditions on Cu1-xZnxFe2O4 systems. The catalytic reactions with each aniline substrate were carried out at optimum reaction conditions (MeOH:anilines:water = 3: 1: 1, space velocity = 3.58 h(-1)) between 543 and 603 K. The presence of a ring-directing group did not have any significant influence on the N-methylaniline(s) selectivity, which remains very high; the same initial conversion/yield was observed for at least 11 h. Electronic effects due to different groups in the above aniline substrates influence the reactivity of the substrates in terms of conversion and yield. Toluidine reactivity varies with respect to the position (ortho, meta and para) of the methyl group on the phenyl ring. Para-substituted anilines (p-toluidine and p-anisidine) exhibit comparable catalytic activity, while p-aminoacetophenone shows higher conversion. The perpendicular orientation of toluidine substrates on catalyst surfaces influences the conversion and N-methyltoluidine yield. Increased crowding at ortho-position and hence steric hindrance (aniline \> o-toluidine \> 2,6-xylidine) restrict the substrates interaction with the catalyst surface, and 2,6-xylidine shows no reactivity. The best catalytic activity observed with Cu0.5Zn0.5Fe2O4 was due to a heterogeneous distribution of metal ions on the surface with Zn serving as active spacer group as well as methyl species source. (c) 2007 Elsevier B.V. All rights reserved.

}, keywords = {mono-N-methylation, N-methylaniline, N-methylation, selective N-methvlation, spinel}, issn = {0926-860X}, doi = {10.1016/j.apcata.2006.12.016}, author = {Vijayaraj, Munusamy and Gopinath, Chinnakonda S.} } @article { ISI:000254309400007, title = {Shape resonance in electron molecule scattering using coupled cluster method}, journal = {Indian Journal of Physics and Proceedings of the Indian Association for the Cultivation of Science}, volume = {81}, number = {10}, year = {2007}, month = {OCT}, pages = {1061-1067}, publisher = {INDIAN ASSOC CULTIVATION SCIENCE}, type = {Article}, address = {INDIAN J PHYSICS, JADAVPUR, KOLKATA 700 032, INDIA}, abstract = {

The Fock space multi-reference coupled-cluster (FSMRCC) method along with the complex absorbing potential (CAP) is used for the study of the shape resonance energy and width in an electron molecule collision. We study the shape resonances in e(-) -H2CO and e(-) -CO.

}, keywords = {electron-molecule scattering, multi-reference coupled-cluster}, issn = {0973-1458}, author = {Pal, Sourav and Vaval, Nayana and Sajeev, Y.} } @article { ISI:000244820500020, title = {Strain improvement of penicillium janthinellum ncim 1171 for increased cellulase production}, journal = {Bioresource Technology}, volume = {98}, number = {7}, year = {2007}, month = {MAY}, pages = {1467-1473}, publisher = {ELSEVIER SCI LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

The strain of Penicilhuinjanthinellunt NOM 1171 was subjected to mutation involving treatment of Ethyl Methyl Sulfonate (EMS) for 24 h followed by UV-irradiation for 3 min. Successive mutants showed enhanced cellulase production (EMS-UV-8), clearance zone on Avicel containing plate (SM2) and rapid growth on Walseth cellulose agar plates containing 0.2\% 2-deoxy-D-glucose (SM3). These mutants were transferred to Walseth cellulose plates containing higher concentration (1.5\%) of 2-deoxy-D-glucose (SM4) in which only five mutants showed clearance zone on SM4. All these mutants showed approximately two-fold increase in activity of both FPase and CMCase in shake flask culture when grown on basal medium containing CP-123 (1\%) and wheat bran (2.5\%). The enzyme preparations from these mutants were used to hydrolyze Avicel. Higher hydrolysis yields of Avicel were obtained with enzyme preparations of EU1. This is the first report on the isolation and selection of mutants based on hydrolysis of Avicel, which is the most crystalline substrate. (c) 2006 Elsevier Ltd. All rights reserved.

}, keywords = {2-deoxy-D-glucose resistant mutants, cellulase activity, EMS and ultraviolet mutation, Penicillium janthinellum}, issn = {0960-8524}, doi = {10.1016/j.biortech.2006.02.036}, author = {Adsul, Mukund G. and Bastawade, Kulbhushan B. and Varma, Anjanikumar and Gokhale, D. V.} } @article { ISI:000244145600014, title = {Sugar-linked biodegradable polymers: regio-specific ester bonds of glucose hydroxyls in their reaction with maleic anhydride functionalized polystyrene and elucidation of the polymer structures formed}, journal = {Carbohydrate Polymers}, volume = {67}, number = {4}, year = {2007}, month = {FEB}, pages = {576-585}, publisher = {ELSEVIER SCI LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

In the development of sugar-linked synthetic polymers as biodegradable polymers, it is imperative to know the variety of polymer structures formed by the reaction of a multi-functional sugar molecule with the functionalized synthetic polymer on which the sugar is to be anchored. Enzymes produced by the microorganisms causing the polymer to biodegrade can be sensitive to the particular type of sugar hydroxyl utilized (such as anomeric, primary, or secondary hydroxyl group) for getting anchored to the polymer. In this paper, we present synthesis of regio-specific ester derivatives of glucose with anhydride, functionalized polymers, i.e., ester formation specifically with the anomeric, primary or secondary hydroxyls of glucose. Characterization of these different esters groups was done using FTIR spectroscopy; each ester peak was further deconvoluted to yield its different components. For this purpose, we studied the reactions of D-glucose, 6-O-trityl glucose, methyl glucoside, 1,2-5,6-diisopropylidene-D-glucose, and 1,2,3,4-tetraacetyl-D-glucose with maleic anhydride functionalized polystyrene (PSMAH). In this study, the primary hydroxyl of glucose was found to be even more reactive than the anomeric hydroxyl. The peaks at similar to 1716, similar to 1725, and 1729-1737 cm(-1) were assigned to the ester carbonyl of the anomeric, primary, and secondary hydroxyls of glucose (C2, C3, and C4), respectively. An attempt was made to quantify the extent to which the different polymer structures are formed in a particular reaction by taking ratios of non-variable reference peaks (polystyrene peak at 1493 cm-1) and variable peaks caused by the reaction (the residual anhydride carbonyl at 1780 cm(-1)). (c) 2007 Published by Elsevier Ltd.

}, keywords = {Biodegradable polymers, functionalized synthetic polymer, glucose, regio-specific, sugar-linked polystyrene}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2006.06.035}, author = {Galgali, P. and Agashe, M. and Varma, Anjanikumar} } @article { ISI:000245341700009, title = {Syntheses of 1,2-amino alcohols and their applications for oxazaborolidine catalyzed enantioselective reduction of aromatic ketones}, journal = {Australian Journal of Chemistry}, volume = {60}, number = {3}, year = {2007}, month = {APR}, pages = {196-204}, publisher = {CSIRO PUBLISHING}, type = {Article}, address = {150 OXFORD ST, PO BOX 1139, COLLINGWOOD, VICTORIA 3066, AUSTRALIA}, abstract = {

Six new chiral 1,2-amino alcohol derivatives have been synthesized starting from (1R, 2R)-2-amino-1-phenylpropane-1,3- diol. Asymmetric reduction of aryl ketones with in-situ generated oxazaborolidine from these amino alcohol derivatives and BH3 center dot Me2S afforded secondary alcohols with good yield and moderate to high enantiomeric excess.

}, issn = {0004-9425}, doi = {10.1071/CH06412}, author = {Vatmurge, Namdev S. and Hazra, Braja G. and Pore, Vandana S.} } @article { ISI:000245634500005, title = {Synthesis and evaluation of 4/5-hydroxy-2,3-diaryl(substituted)-cyclopent-2-en-1-ones as cis-restricted analogues of combretastatin A-4 as novel anticancer agents}, journal = {Journal of Medicinal Chemistry}, volume = {50}, number = {8}, year = {2007}, month = {APR}, pages = {1744-1753}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

A new series of 2,3-diaryl-4/5-hydroxy-cyclopent-2-en-1-one analogues replacing the cis double bond of combretastatin A-4 (CA-4) by 4/5-hydroxy cyclopentenone moieties was designed and synthesized. The analogues displayed potent cytotoxic activity (IC50 \< 1 mu g/mL) against a panel of human cancer cell lines and endothelial cells. The most potent analogues 11 and 42 belonging to the 5-hydroxy cyclopentenone class were further evaluated for their mechanism of action. Both of the analogues led to cell cycle arrest at G2/M phase and induced apoptosis in endothelial cells. Antitubulin property of 42 was superior to 11 and comparable to CA-4. The compound 42 had better aqueous solubility, metabolic stability, and pharmacokinetic profile than CA-4 and also demonstrated significant tumor regression in the human colon xenograft model. Our data suggests that cis-restricted analogues of CA-4 are a new class of molecules that have the potential to be developed as novel agents for the treatment of cancer.

}, issn = {0022-2623}, doi = {10.1021/jm060938o}, author = {Gurjar, Mukund K. and Wakharkar, Radhika D. and Singh, Anu T. and Jaggi, Manu and Borate, Hanumant B. and Shinde, Popat D. and Verma, Ritu and Rajendran, Praveen and Dutt, Sarjana and Singh, Gurvinder and Sanna, Vinod K. and Singh, Manoj K. and Srivastava, Sanjay K. and Mahajan, Vishal A. and Jadhav, Vinod H. and Dutta, Kakali and Krishnan, Karthik and Chaudhary, Anika and Agarwal, Shiv K. and Mukherjee, Rama and Burman, Anand C.} } @article { ISI:000242775700046, title = {Synthesis and MASNMR characterization of VPI-5 molecular sieve}, journal = {Asian Journal of Chemsitry}, volume = {19}, number = {1}, year = {2007}, month = {FEB}, pages = {347-353}, publisher = {ASIAN JOURNAL OF CHEMISTRY}, type = {Article}, address = {11/100 RAJENDRA NAGAR, SECTOR 3,, SAHIBABAD 201 005, GHAZIABAD, INDIA}, abstract = {

The synthesized VPI-5 sample was characterized by XRD, SEM, FTIR, TG/DTA, Al-27, P-31 and 3Q MASNMR techniques, which shows that the sample was highly crystalline. Carbon and nitrogen analysis reveals that the sample contains no template molecules; however, TG/DTA analysis shows the presence of physisorbed template molecules. MASNMR results show the presence of two different types of aluminium and phosphorus, 3Q MASNMR shows the presence of two types of environmentally different tetrahedral aluminium, which are not observable by ordinary MASNMR along with known octahedral aluminium.

}, keywords = {3Q-MASNMR, FTIR, MASNMR, SEM, synthesis, TG/DTA, VPI-5, XRD}, issn = {0970-7077}, author = {Venkatathri, N.} } @article { ISI:000250557100030, title = {Synthesis of 1-deoxy-1-hydroxymethyl- and 1-deoxy-1-epi-hydroxymethyl castanospermine as new potential immunomodulating agents}, journal = {Journal of Medicinal Chemsitry}, volume = {50}, number = {22}, year = {2007}, month = {NOV}, pages = {5519-5523}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Two new C-1 epimeric hydroxymethyl castanospermine congeners 2a and 2b, synthesized by stereocon trolled intramolecular double reductive amination Of D-glucose derived beta-keto ester as a key step, showed impressive immuno-potentiating property. The bioactivity was mediated through up-regulation of T-H1/T-H2 cytokine ratio. The finding suggested that immunmodulatory activity of polyhydroxylated indolizidine alkaloids can be tuned by minor structural/stereochemical alterations.

}, issn = {0022-2623}, doi = {10.1021/jm070660f}, author = {Vyavahare, Vinod P. and Chakraborty, Chaitali and Maity, Biswanath and Chattopadhyay, Subrata and Puranik, Vedavati G. and Dhavale, Dilip D.} } @article { ISI:000251658100005, title = {Synthesis of C-2 methylene glycosides from C-2 propargyloxymethyl glycals exploiting the alkynophilicity of AuCl3}, journal = {Tetrahedron Letters}, volume = {48}, number = {51}, year = {2007}, note = {21st Carbo Symposium 2006, Univ Delhi, Delhi, INDIA, NOV 26-29, 2006}, month = {DEC}, pages = {8960-8962}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

C-2 Methylene glycosides were synthesized from C-2 propargyloxymethyl glycals in a stereoselective manner using a catalytic quantity of AuCl3. The Au-catalyzed reaction was explored using various aglycones. The current protocol enables the preparation of C-2 methylene glycosides, tolerates diverse functional groups and is fast, catalytic and mild. (c) 2007 Elsevier Ltd. All rights reserved.

}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2007.10.144}, author = {Kashyap, Sudhir and Vidadala, Srinivasa Rao and Hotha, Srinivas} } @article { ISI:000244183400015, title = {Tungstophosphoric acid supported over zirconia in mesoporous channels of MCM-41 as catalyst in veratrole acetylation}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {262}, number = {1-2}, year = {2007}, month = {FEB}, pages = {98-108}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Tungstophosphoric acid (TPA) over zirconia dispersed uniformly in mesoporous silica (MS) channels of MCM-41 and MCM-48 were synthesized and tested for their catalytic activity in veratrole acetylation. Catalysts with different TPA loadings (5-50 wt.\%) on 22.4 wt.\%ZrO2/MCM-41 and 15 wt.\%TPA on different zirconia loadings (10-70 wt.\%)/MCM-41 were prepared and calcined at 1123 K. The physico-chemical characterization of the supported catalysts was done by powder X-ray diffraction (XRD), surface area measurement (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transformed-infrared (FT-IR) spectroscopy, UV-vis diffuse reflectance spectra, Temperature programmed desorption (TPD) of ammonia, FT-IR pyridine adsorption and (31) P cross polarization-magic angle spinning (CP-MAS) NMR spectroscopy. The mesoporous silica supports play an important role in stabilizing catalytically active TPA along with tetragonal phase of zirconia. Among the catalysts, 15 wt.\%TPA/22.4 wt.\%ZrO2/MCM-41 calcined at 1123 K was found to have highest acidity and at least four times more active than neat 15 wt.\%TPA/ZrO2 in veratrole acetylation to acetoveratrone by acetic anhydride. Reaction conditions were evaluated with 15 wt.\%TPA/22.4 wt:\%ZrO2/MCM-41 calcined at 1123 K to get higher conversion of acetic anhydride to acetoveratrone. The reaction was found to be heterogeneously catalyzed and no contribution from homogeneous (leached) TPA into the medium under the reaction conditions. (c) 2006 Elsevier B.V. All rights reserved.

}, keywords = {acetoveratrone, acetylation, MCM-41, TPA/ZrO2, veratrole}, issn = {1381-1169}, doi = {10.1016/j.molcata.2006.08.027}, author = {Sawant, Dhanashri P. and Vinu, A. and Lefebvre, F. and Halligudi, Shivaraj B.} } @article { ISI:000254804700001, title = {2(7-3) fractional factorial optimization of polybenzimidazole based membrane electrode assemblies for H-2/O-2 fuel cells}, journal = {Journal of Applied Electrochemistry}, volume = {38}, number = {5}, year = {2008}, month = {MAY}, pages = {583-590}, publisher = {SPRINGER}, type = {Article}, address = {VAN GODEWIJCKSTRAAT 30, 3311 GZ DORDRECHT, NETHERLANDS}, abstract = {

We describe the usefulness of a statistical fractional factorial design to obtain consistent and reproducible behavior of a membrane-electrode-assembly (MEA) based on a phosphoric acid (PA) doped polybenzimidazole (PBI) membrane, which allows a H-2/O-2 fuel cell to operate above 150 degrees C. Different parameters involved during the MEA fabrication including the catalyst loading, amount of binder, processing conditions like temperature and compaction load and also the amount of carbon in the gas diffusion layers (GDL) have been systematically varied according to a 2(7-3) fractional factorial design and the data thus obtained have been analyzed using Yates{\textquoteright}s algorithm. The mean effects estimated in this way suggest the crucial role played by carbon loading in the gas diffusion layer, hot compaction temperature and the binder to catalyst ratio in the catalyst layer for enabling continuous performance. These statistically designed electrodes provide a maximum current density and power density of 1,800 mA cm(-2) and 280 mW cm(-2), respectively, at 160 degrees C using hydrogen and oxygen under ambient pressure.

}, keywords = {Carbon loading, Fractional factorial optimization, MEA, PBI, PEMFC}, issn = {0021-891X}, doi = {10.1007/s10800-007-9475-1}, author = {Kannan, Ramaiyan and Islam, Md. Nazrul and Rathod, D. and Vijay, M. and Kharul, Ulhas K. and Ghosh, P. C. and Vijayamohanan, K.} } @article { ISI:000260978000002, title = {Active sites in vanadia/titania catalysts for selective aerial oxidation of beta-picoline to nicotinic acid}, journal = {Journal of Catalysis}, volume = {259}, number = {2}, year = {2008}, month = {OCT}, pages = {165-173}, publisher = {ACADEMIC PRESS INC ELSEVIER SCIENCE}, type = {Article}, address = {525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USA}, abstract = {

Vanadia/titania catalysts with varying vanadium content were prepared by impregnation using three different titania carrier materials of varying surface area, The structure of active vanadium species for beta-picoline oxidation was investigated. Vanadium is mainly in the +5 oxidation state as revealed by electron paramagnetic resonance (EPR) and V-51 magic-angle spinning nuclear magnetic resonance (V-51 MAS NMR) spectroscopy techniques. Diffuse reflectance UV-visible (DRUV-vis) spectroscopy and spectral deconvolution enabled identification of at least five different types of vanadium oxide species in these catalysts: monomeric tetrahedral VO43-, polymeric distorted tetrahedral VO3-, square pyramidal V2O5, octahedral V2O62- and V4+ oxide species. While both VO43- and VO3- species are active in beta-picoline oxidation, the latter having a distorted tetrahedral geometry yielded the desired products-picolinaldehyde and nicotinic acid. High surface area, anatase structure for the support and dispersed, distorted tetrahedral vanadium oxide species are the key parameters determining the activity and selectivity of these oxidation catalysts. (C) 2008 Elsevier Inc. All rights reserved.

}, keywords = {Active vanadium species, Nicotinic acid, Oxidation of beta-picoline, Selective aerial oxidation, Spectroscopic investigations, Vanadia/titania}, issn = {0021-9517}, doi = {10.1016/j.jcat.2008.07.019}, author = {Srinivas, Darbha and Hoelderich, Wolfgang F. and Kujath, Steffen and Valkenberg, Michael H. and Raja, Thirumalaiswamy and Saikia, Lakshi and Hinze, Ramona and Ramaswamy, Veda} } @article { ISI:000253450900068, title = {Alkene epoxidation catalyzed by vanadomolybdophosphoric acids supported on hydrated titania}, journal = {Catalysis Communications}, volume = {9}, number = {5}, year = {2008}, month = {MAR}, pages = {931-938}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Vanadomolybdophosphoric acids wet-impregnated oil hydrated titania (TiO(2) - xH(2)O), make ail efficient catalytic system for the epoxidation of a variety of alkenes with organic solvent extracted TBHP as the oxidant. By,in appropriate choice of solvent, the catalyst call be reused at least three times without much loss in the activity for subsequent runs. XRD shows that the heteropoly acid is uniformly dispersed over the support and up to 15 wt\% loading of the heteropoly acid, no additional peak of the same call be seen in the XRD pattern of the catalyst. The reactivity varied with the nature of alkene but the major product was always the corresponding epoxide. The catalytic system is free of high temperature calcination steps and tedious multi-step procedures, normally encountered in the heter-ogenization of heteropoly acids. (c) 2007 Elsevier B.V. All rights reserved.

}, keywords = {alkenes, epoxidation, heteropoly acids, TBHP, titania, vanadomolybdophosphoric acids}, issn = {1566-7367}, doi = {10.1016/j.catcom.2007.09.022}, author = {Ingle, Rohit H. and Vinu, A. and Halligudi, Shivaraj B.} } @article { ISI:000253283700034, title = {Chemical inhomogeneity and mixed-state ferromagnetism in diluted magnetic semiconductor Co : TiO2}, journal = {Chemistry of Materials}, volume = {20}, number = {4}, year = {2008}, month = {FEB}, pages = {1344-1352}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Diluted magnetic semiconductors (DMS) are among the most intensely investigated materials in recent times in view of their great application potential. Yet, they are also the most controversial because of the possibility of extrinsic effects attributable to dopant solubility and clustering, point defects, incorporation of unintentional impurities, etc. This has highlighted the central role of materials chemistry in rendering a specific microstate and property response. In this work, we provide a combined window of high-resolution scanning transmission electron microscopy and electron energy-loss spectrometry, X-ray absorption (XAS)/X-ray magnetic circular dichroism (XMCD), and magnetization measurements on epitaxial rutile CoxTi1-xO2 (x = 0-0.06) system (the first discovered oxide-DMS, which continues to be controversial) grown at low temperature (400 degrees C) under different ambient atmospheres. The study brings out a mixed-state scenario of ferromagnetism involving intrinsic DMS (uniform dopant distribution at low dopant concentration) and coupled cluster magnetism, involving cobalt associations within the matrix at higher concentrations. We also show that by matrix valence control during growth, it is possible to realize a uniform embedded cluster state and the related coupled cluster magnetism.

}, issn = {0897-4756}, doi = {10.1021/cm702089z}, author = {Ogale, Satishchandra B. and Kundaliya, Darshan and Mehraeen, Shareghe and Fu, Lian-feng and Zhang, Shixiong and Lussier, Alexandre and Dvorak, Joe and Browning, Nigel D. and Idzerda, Yves and Venkatesan, Thirumalai} } @article { ISI:000251444400008, title = {Complexation of heavy metals by crosslinked chitin and its deacetylated derivatives}, journal = {Carbohydrate Polymers}, volume = {71}, number = {1}, year = {2008}, month = {JAN}, pages = {66-73}, publisher = {ELSEVIER SCI LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Chitin was crosslinked using diisocyanatohexane (HDI), trimellitic anhydride (TMA), and dibromodecane (DBD), then deacetylated in strong aqueous alkali. This led to a product with amine functional groups on the exposed surface of the crosslinked chitin, which could be utilized for complexation with heavy metals. Thus, a key feature of the crosslinked derivatives prepared was that only the hydroxy Groups were utilized in the crosslinking reaction, and the acetylamino groups of chitin were hydrolyzed only after the crosslinking was accomplished. This ensured that all amino groups of the chitosans so produced would be available for metal complexation, and not partially used up in crosslinking. This proposed advantage was proved by the similar binding observed for heavy metals like Hg (348-372 mg/g), Cu (91-119 mg/g), Zn (71-92 mg/g), Mn (3-10 mg/g), Cd (121-160 mg/g), and Pb (32-86 mg/g) using these crosslinked polymers, whereas the control polymer (uncrosslinked chitosan powder) had complexation values for Hg (348-361 mg/g), Cu (100-106 mg/g), Zn (81-92 mg/g), Mn (4-7 mg/g), Cd (135 mg/g), and Pb (25-59 mg/g). Additionally, in a case where chitosan was crosslinked with HDI. the amino groups were consumed in the crosslinking reaction, and the metal complexation capacity has found to be decreased for Cu (91-109 mg/g), Cd (133 mg/g), and Zn (71-77 mg/g), while remaining nearly the same for Hg (362 mg/g). The literature value for Cu complexation is 59.67 mg/g for chitosan crosslinked with glutaraldehyde. The crosslinked derivatives have the added advantage of insolubility even in low pH aqueous media, making their repeated re-use possible. Further, these crosslinked derivatives could be used in powder form, and the additional step of preparing beads was found to be not necessary for ease of separation of the crosslinked powder by filtration. The binding capacity of various crosslinked chitin and deacetylated derivatives for Cu, Cd, Hg, Zn, Mn. and Pb was in the region of 100, 140, 360 88, 5, and 60 mg/g (rounded off values) of polymer, respectively, very close to the values obtained for uncrosslinked chitosan. The metal binding for crosslinked chitosan was slightly lower than that of crosslinked chitin and deacetylated derivatives, due to use of some amino groups in crosslinking. For Cu ions, the Langmuir equation was found to be the best fit for HDI crosslinked deacetylated chitin and TMA crosslinked deacetylated chitin. The morphological studies conducted using WAXRD are in close agreement with the metal complexation data, showing complete loss of original chitosan peaks for the heavily complexed derivatives, and minor changes for the weakly complexed metals. (c) 2007 Elsevier Ltd. All rights reserved.

}, keywords = {Chitosan, Crosslinked chitosan, deacetylated chitin, metal complexation, Morphology}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2007.05.016}, author = {Trimukhe, K. D. and Varma, Anjanikumar} } @article { ISI:000253646700006, title = {Cyanuryl peptide nucleic acid: synthesis and DNA complexation properties}, journal = {Tetrahedron Letters}, volume = {49}, number = {8}, year = {2008}, month = {FEB}, pages = {1314-1318}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

The synthesis of cyanuryl PNA monomer (CyaPNA) 6 was achieved by direct N-monoalkylation of cyanuric acid with N-(2-Boc-aminoethyl)-N{\textquoteright}-(bromoacetyl)glycyl ethyl ester 4. Compound 6 was incorporated as a T-mimic into PNA oligomers and biophysical studies on their triplexes/duplex complexes with complementary DNA oligomers indicated unusual stabilization of PNA:DNA hybrids when the cyanuryl unit was located in the middle of the PNA oligomer. (c) 2008 Elsevier Ltd. All rights reserved.

}, keywords = {cyanuryl PNA, PNA}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2007.12.095}, author = {Vysabhattar, Raman and Ganesh, Krishna N.} } @article { ISI:000258437100008, title = {Effect of synthesis procedure on the structure and properties of palladium/polycarbonate nanocomposites}, journal = {Polymer}, volume = {49}, number = {16}, year = {2008}, month = {JUL}, pages = {3413-3418}, publisher = {ELSEVIER SCI LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

In this paper, we compare two procedures for the synthesis of palladium (Pd)/polycarbonate (PC) nanocomposites as well as their morphological, optical, thermal and electrical properties. Pd nanoclusters were produced by the reduction of palladium chloride using a variation of Brust{\textquoteright}s method. Discrete I{\textquoteright}d nanoclusters of similar to 15 nm size were formed in the absence of PC in the reaction mixture (ex situ method) while agglomeration of Pd nanoclusters was noticed in the presence of PC in the reaction mixture (in situ method). Fourier transform infrared spectroscopy (FTIR) suggests nanoparticle-polymer interactions and polymer conformational changes in the in situ nanocomposite films. Even after having the same Pd content, the ex situ nanocomposites films were found to transmit more light than the in situ nanocomposites. The glass transition temperature (T-g), decreased by similar to 16 degrees C for both the ex situ and in situ samples. Thermogravimetric analysis (TGA) indicated that the presence of Pd nanoclusters significantly improved the thermal stability of the nanocomposites, as evidenced by the enhanced onset of degradation by similar to 20 degrees C and similar to 40 degrees C for the in situ and ex situ nanocomposites, respectively. The electrical conductivity measurement shows a dramatic difference between these nanocomposites with a significantly higher value for the in situ nanocomposite (resistivity = 2.1 X 10(5) Omega m) compared to the ex situ nanocomposite (resistivity = 7.2 x 10(13) Omega m). (c) 2008 Elsevier Ltd. All rights reserved.

}, keywords = {in situ and ex situ syntheses, Morphology, Nanocomposites}, issn = {0032-3861}, doi = {10.1016/j.polymer.2008.05.036}, author = {Valmikanathan, O. P. and Ostroverkhova, O. and Mulla, Imtiaz S. and Vijayamohanan, K. and Atre, S. V.} } @article { ISI:000254443900045, title = {Efficient synthesis of 1,8-dioxo-octahydro-xanthene derivatives promoted by a room temperature ionic liquid at ambient conditions under ultrasound irradiation}, journal = {Ultrasonics Sonochemistry}, volume = {15}, number = {4}, year = {2008}, month = {APR}, pages = {548-553}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The condensation reaction involving an aldehyde and diketone was efficiently promoted by the Ionic liquid, [Hbim]BF(4) (IL) as a reaction medium with methanol as co-solvent at ambient temperature under ultrasonic irradiation to afford the corresponding 1,8-dioxo-octahydroxantliene (xanthene) derivatives in excellent yields. The advantages of this method include among others the use of a recyclable, non-volatile ionic liquid, which promotes this protocol under ambient temperature without the requirement of ally added catalyst. The reaction times and yields are compared with p-TSA catalyzed synthesis of xanthenes under thermal conditions, which is also reported for the first time under our reaction conditions. (c) 2007 Elsevier B.V. All rights reserved.

}, keywords = {aldehydes, ambient conditions, Bronsted acidity, dimedone, Ionic liquid, Ultrasound, Xanthenes}, issn = {1350-4177}, doi = {10.1016/j.ultsonch.2007.06.001}, author = {Venkatesan, K. and Pujari, Suresh S. and Lahoti, Rajgopal J. and Srinivasan, K. V.} } @article { ISI:000261410200003, title = {Environment friendly crosslinked chitosan as a matrix for selective adsorption and purification of lipase of aspergillus niger}, journal = {International Journal of Biological Macromolecules}, volume = {43}, number = {5}, year = {2008}, month = {DEC}, pages = {422-425}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Chitosan and its derivatives have been used as affinity matrices for purification of lipase from Aspergillus niger NCIM 1207. Trimellitic anhydride (TMA)-crosslinked deacetylated chitin adsorbed lipase selectively, yielding approximately 5-fold purification of the crude lipase with 70\% yield. Further 9-fold purification occurred on eluting through Sephacryl-100. These results suggest that chitosan derivatives can be used as inexpensive biopolymer matrices for the purification of lipases for industrial applications. (C) 2008 Elsevier B.V. All rights reserved.

}, keywords = {Adsorption, Chitosan, Lipase, Matrix, Purification}, issn = {0141-8130}, doi = {10.1016/j.ijbiomac.2008.08.005}, author = {Trimukhe, K. D. and Mahadik, N. D. and Gokhale, D. V. and Varma, Anjanikumar} } @article { ISI:000259420300006, title = {Facile synthesis and gas sensing properties of nanotriangular tin oxide}, journal = {Materials Letters}, volume = {62}, number = {28}, year = {2008}, month = {NOV}, pages = {4328-4331}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

In the present study we report a simple and convenient chemical route using pentaerythritol as a structure-directing agent for the synthesis of crystalline nanotriangular SnO2. We propose the scheme for the formation of nanotriangular structures wherein the preliminary spherical nanocrystallites are formed due to the low surface energy associated with them. These spherical nanocrystallites grow into the various linear intermediate shapes like Y, bi and tripods, which finally lead to the triangles, pyramids and bipyramids. Such variation in the structure occurs due to the structure directing pentaerythritol. These polycrystalline SnO2 nanomaterials with structural peculiarities were tested for the gas sensing characteristics. Their response towards ethanol vapor, H-2 and LPG were investigated. It was found to exhibit high response towards ethanol vapors at the operating temperature of 250 degrees C. (C) 2008 Elsevier B.V. All rights reserved.

}, keywords = {Nanomaterials, Oxides, Semiconductors, sensors}, issn = {0167-577X}, doi = {10.1016/j.matlet.2008.07.021}, author = {Deshmukh, Rupali G. and Badadhe, Satish S. and Vaishampayan, Mukta V. and Mulla, Imtiaz S.} } @article { ISI:000255692100010, title = {Fe-doped SnO(2) nanomaterial: a low temperature hydrogen sulfide gas sensor}, journal = {Materials Chemistry and Physics}, volume = {109}, number = {2-3}, year = {2008}, month = {JUN}, pages = {230-234}, publisher = {ELSEVIER SCIENCE SA}, type = {Article}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

The effect of Fe-doping on the surface chemistry and gas-sensing properties of nanocrystalline tin oxide is analyzed. The pristine and Fe-doped SnO(2) are synthesized by the modified Pechini citrate route that produces around 40 and 18 nm sized nanoparticles, respectively. 1 at.\% Fe-doped SnO(2) shows significantly high selectivity towards hydrogen sulfide gas with capability to detect even 10 ppm of hydrogen sulfide at room temperature, with change of about one order of magnitude in the resistance within 5-15 s. In comparison, pristine SnO(2) shows negligible response towards H(2)S at room temperature. The ideal response and recovery of Fe-doped SnO(2) at low concentration of gas suggests Fe-doped SnO(2) nanomaterial as a potential low cost, low temperature H(2)S gas sensor. (C) 2007 Elsevier B.V. All rights reserved.

}, keywords = {Fe-doping, H(2)S, nanomaterial, Sensor, tin oxide}, issn = {0254-0584}, doi = {10.1016/j.matchemphys.2007.11.024}, author = {Vaishampayan, Mukta V. and Deshmukh, Rupah G. and Walke, Pravin and Mulla, Imtiaz S.} } @article { ISI:000254872600028, title = {Heteropoly acid encapsulated SBA-15/TiO(2) nanocomposites and their unusual performance in acid-catalysed organic transformations}, journal = {Chemistry-A European Journal}, volume = {14}, number = {10}, year = {2008}, month = {FEB}, pages = {3200-3212}, publisher = {WILEY-BLACKWELL}, type = {Article}, address = {COMMERCE PLACE, 350 MAIN ST, MALDEN 02148, MA USA}, abstract = {

The preparation of SBA-15/TiO(2) nanocomposites with different loadings of Keggin-type 12-tungsto-phosphoric acid (TPA) nanocrystals in their mesochannels through a simple and effective vacuum impregnation method is reported for the first time. The catalysts have been characterised by various sophisticated techniques, including XRD, HRSEM, and TEM. It has been found that the acidity and the textural parameters of the nanocomposites can be controlled by simply changing the loadings of TPA and TiO(2) or the calcination temperature. TPA and TiO(2) loadings of 15 and 22.4 wt \%, respectively, and a calcination temperature of 1123 K have proved to be optimal for obtaining mesoporous nanocomposite materials with the highest acidity. Moreover, the activities of these catalysts in promoting hydroamination as well as Mannich and Claisen rearrangement reactions have been extensively investigated. The results show that the amount of TPA has a great influence on the activity of the nanocomposites in all of the reactions studied. The effects of other reaction parameters, such as temperature and reaction time, on the conversion and product selectivity have also been studied in detail. A kinetic analysis of the formation of the products under various reaction conditions is presented. It has been found that the activity of the nanocomposite composed of 15 wt \% TPA deposited on 22.4 wt of TiO(2) on SBA-15 in promoting the studied reaction is remarkably higher than the catalytic activities shown by pure TPA, TiO(2)-loaded SBA-15, or TPA-loaded SBA-15. The results obtained have indicated that the acidity and the structural control of the nanocomposite materials are highly critical for obtaining excellent catalytic activity, and the presented highly acidic nanocomposites are considered to show great potential for use as catalysts in promoting many acid-catalysed organic transformations.

}, keywords = {Bronsted acids, mesoporous materials, nanoreactors, nanotechnology, supported catalysts}, issn = {0947-6539}, doi = {10.1002/chem.200701562}, author = {Sawant, Dhanashri P. and Justus, Josena and Balasubramanian, Veerappan V. and Ariga, Katsuhiko and Srinivasu, Pavuluri and Velmathi, Sivan and Halligudi, Shivappa B. and Vinu, Ajayan} } @article { ISI:000255086600041, title = {Highly active nanostructured Co3O4 catalyst with tunable selectivity for liquid phase air oxidation of p-cresol}, journal = {Chemistry Letters}, volume = {37}, number = {3}, year = {2008}, month = {MAR}, pages = {310-311}, publisher = {CHEMICAL SOC JAPAN}, type = {Article}, address = {1-5 KANDA-SURUGADAI CHIYODA-KU, TOKYO, 101-8307, JAPAN}, abstract = {

This is a first report of highly efficient heterogeneous nanostructured Co3O4 catalyst (6-8 nm) having high surface area (95 m(2)/g) developed for selective liquid phase air oxidation of p-cresol under atmospheric pressure conditions.

}, issn = {0366-7022}, doi = {10.1246/cl.2008.310}, author = {Kshirsagar, Vikas S. and Vijayanand, Subramanian and Potdar, Hari S. and Joy, Pattayil Alias and Patil, Kashinath R. and Rode, Chandrashekhar V.} } @article { ISI:000254979800027, title = {Highly efficient and chemo selective catalyst system for the synthesis of blossom orange fragrance and flavoring compounds}, journal = {Catalysis Communications}, volume = {9}, number = {7}, year = {2008}, month = {APR}, pages = {1671-1675}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

{Acetal and acylal formation reactions of organic compounds are efficiently catalyzed by zirconia-supported mixed oxide systems under liquid-phase reaction conditions. 15WZ-750 (where

}, keywords = {Acetal, acylal, Silicotungstic acid, tungsten oxide, tungstophosphoric acid, Zirconia}, issn = {1566-7367}, doi = {10.1016/j.catcom.2008.01.025}, author = {Justus, Josena and Vinu, Ajayan and Devassy, Biju M. and Balasubramanian, Veerappan V. and Bohringer, Walter and Fletcher, Jack C. Q. and Halligudi, Shivaraj B.} } @article { ISI:000254479300039, title = {Immobilization of Candida rugosa lipase on poly(allyl glycidyl ether-co-thylene glycol dimethacrylate) macroporous polymer particles}, journal = {Bioresource Technology}, volume = {99}, number = {9}, year = {2008}, month = {JUN}, pages = {3623-3629}, publisher = {ELSEVIER SCI LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Macroporous polymer particles containing surface epoxy groups were synthesized for immobilization of Candida rugosa lipase (CRL). The effect of incorporation of two different sets of monomers [allyl glycidyl ether (AGE) and glycidyl methacrylate (GMA)] and the effect of crosslinking density on immobilization of lipase were studied. AGE-co-EGDM polymers gave higher binding and expression of lipase than GMA-co-EGDM polymers. Optimization of immobilization parameters was done with respect to immobilization time and enzyme loading. Amongst AGE-co-EGDM polymer series, AGE-150 polymer found to give maximum lipase activity yield and therefore evaluated for temperature, pH and storage stability. Under optimum conditions, AGE-150 polymer gave 78.40\% of activity yield. Immobilized lipase on AGE-150 showed a broader pH, higher temperature and excellent storage stability. (C) 2007 Published by Elsevier Ltd.

}, keywords = {Candida rugosa lipase, Enzyme immobilization, Epoxy-activated support}, issn = {0960-8524}, doi = {10.1016/j.biortech.2007.07-035}, author = {Vaidya, Bhalchandra K. and Ingavle, Ganesh C. and Ponrathnam, S. and Kulkarni, B. D. and Nene, Sanjay N.} } @article { ISI:000256116100044, title = {Influence of Pd doping on morphology and LPG response of SnO2}, journal = {Sensors and Actuators B-Chemical}, volume = {131}, number = {2}, year = {2008}, month = {MAY}, pages = {665-672}, publisher = {ELSEVIER SCIENCE SA}, type = {Article}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

In the present study nanocrystalline pristine and Pd-doped SnO2 (Pd:SnO2) with various mol\% Pd have been synthesized by a modified Pechini citrate route. Transmission electron microscopy and X-ray powder diffraction studies were used to characterize the morphology, crystallinity, and structure of the SnO2 and Pd:SnO2. The response of the pristine SnO2 and Pd:SnO2 was studied towards different reducing gases. The 1.5 mol\% Pd doping showed an enhanced response of 75 and 95\% towards LPG at as low as 50 and 100 degrees C, respectively, which were quite large high value as compared with pristine SnO2 (38 and 35\% at 50 and 100 degrees C, respectively). Structural characterization revealed that Pd doping reduced the crystallite size of SnO2 and helps in the formation of distinct spherical nanospheres at a calcinations temperature of 500 degrees C. Thus the increase in LPG response can be correlated with the spherical morphology, a decrease in the crystallite size (11 nm) due to doping with Pd as compared with the pristine SnO2 (26 nm) and main role of Pd as a catalyst. (c) 2008 Elsevier B.V. All rights reserved.

}, keywords = {LPG sensor, nanospheres, palladium doping, tin oxide}, issn = {0925-4005}, doi = {10.1016/j.snb.2007.12.055}, author = {Vaishampayan, Mukta V. and Deshmukh, Rupali G. and Mulla, Imtiaz S.} } @article { ISI:000254798300018, title = {Lipases catalyzed enantioselective hydrolysis of (R,S)-methyl 1,4-benzodioxan-2-carboxylate intermediate for (S)-doxazosin mesylate}, journal = {World Journal of Microbiology \& Biotechnology}, volume = {24}, number = {4}, year = {2008}, month = {APR}, pages = {577-579}, publisher = {SPRINGER}, address = {233 SPRING STREET, NEW YORK, NY 10013 USA}, abstract = {

(S)-1,4-benzodioxan-2-carboxylic acid-1 is used as starting compound for the production of the more effective (S) enantiomer of the drug doxazosin mesylate. The catalytic ability of some commercial lipases for preparations of (S) enantiomer of 1 from (+/-) methyl 1,4-benzodioxin-2-carboxylate-2 is reported. Lipases from bacterial sources were more successful in resolving the ester than those from the yeast lipases. About 85\% enantiomerically pure ester was achieved by lipase from alcaligenes sp.

}, keywords = {1, 4-benzodioxan-2-carboxylate, 4-benzodioxan-2-carboxylic acid, doxazosin, Enantioselectivity, Lipases}, issn = {0959-3993}, doi = {10.1007/s11274-007-9504-6}, author = {Varma, Rita and Kasture, Sangita M. and Nene, Sanjay and Kalkote, Uttam R.} } @article { ISI:000261361900032, title = {Low temperature synthesis of nanocrystalline lithium ferrite by a modified citrate gel precursor method}, journal = {Materials Research Bulletin}, volume = {43}, number = {12}, year = {2008}, month = {DEC}, pages = {3447-3456}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

Single phase nanocrystalline lithium ferrite is synthesized by a modified citrate gel precursor technique. Ferrite nanoparticles of average size of 8 nm, obtained after calcination of the citrate gel Made by the usual method at 450 degrees C, show superparamagnetic behavior. However, small amounts of alpha-Fe(2)O(3) is formed as an impurity phase clue to the initial formation of some gamma-Fe(2)O(3) phase. Oil the other hand, when the pH of the mixed Solution is increased to 7 after the addition of ammonia Solution, a lower calcination temperature of 200 degrees C is sufficient for the formation of single phase lithium ferrite nanoparticles of size 30 nm. No impurity phases are detected when the nanocrystalline powders arc calcined at higher temperatures. The magnetic properties of the ferrite nanoparticles of different sizes obtained by calcining the powders at different temperatures are studied. (C) 2008 Elsevier Ltd. All rights reserved.

}, keywords = {Chemical synthesis, Magnetic materials, magnetic properties, Nanostructures, Oxides}, issn = {0025-5408}, doi = {10.1016/j.materresbull.2008.01.023}, author = {Verma, Seema and Joy, Pattayil Alias} } @article { ISI:000261061100016, title = {Magnetic and Mossbauer spectroscopic studies of NiZn ferrite nanoparticles synthesized by a combustion method}, journal = {Hyperfine Interactions}, volume = {183}, number = {1-3}, year = {2008}, month = {APR}, pages = {99-107}, publisher = {SPRINGER}, address = {VAN GODEWIJCKSTRAAT 30, 3311 GZ DORDRECHT, NETHERLANDS}, abstract = {

The properties of nanocrystalline Ni(0.5)Zn(0.5)Fe(2)O(4) synthesized by an auto-combustion method have been investigated by magnetic measurements and Mossbauer spectroscopy. The as-synthesized single phase nanosized ferrite powder is annealed at different temperatures in the range 673-1,273 K to obtain nanoparticles of different sizes. The powders are characterized by powder X-ray diffraction, vibrating sample magnetometer, transmission electron microscopy and Mossbauer spectroscopy. The as-synthesized powder with average particle size of similar to 9 nm is superparamagnetic. Magnetic transition temperature increases up to 665 K for the nanosized powder as compared to the transition temperature of 548 K for the bulk ferrite. This has been confirmed as due to the abnormal cation distribution, as evidenced from room temperature Mossbauer spectroscopic studies.

}, keywords = {Ferrite, magnetic properties, Mossbauer spectroscopy, Nanoparticles}, issn = {0304-3843}, doi = {10.1007/s10751-008-9736-3}, author = {Sreeja, V. and Vijayanand, S. and Deka, Sasanka and Joy, Pattayil Alias} } @article { ISI:000253115600026, title = {Morphological study of heavy metal complexes of chitosan and crosslinked chitosans by SEM and WAXRD}, journal = {Carbohydrate Polymers}, volume = {71}, number = {4}, year = {2008}, month = {MAR}, pages = {698-702}, publisher = {ELSEVIER SCI LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Metal complexes of salts of Hg, Cu, Cd, Pb, Zn, and Mn with chitosan and crosslinked chitosans were prepared, and their morphologies were studied using scanning electron microscopy and wide angle X-ray diffraction. The metal ions which were specifically and strongly complexed to the amino functions of chitosans, like Hg, showed smooth surface morphology inspite of large number of ions complexed (372 mg/g of chitosan). The presence of metal ions on the surface of the chitosans could be detected with decrease in metal ion binding, in the following sequence Hg \> Cu \> Cd \> Zn \> Pb \> Mn. Particularly in the case of Pb ions, the presence of these ions is clearly seen on the surface of the polymer by SEM. The number of ions of Mn complexed on the polymers was too few (5 mg/g of chitosan) to be visible. SEM of Hg and Cu complexes do not show the {\textquoteleft}{\textquoteleft}holes{\textquoteright}{\textquoteright} observed in the crosslinked polymers as they bind specifically to amino groups of chitosan, but for Cd, Zn, Mn, and Pb complexes, these {\textquoteleft}{\textquoteleft}holes{\textquoteright}{\textquoteright} are clearly visible. These results are also in agreement with the morphologies studied by WAXRD. The metal complexation data for each of these metal ions was also in the same sequence. (c) 2007 Elsevier Ltd. All rights reserved.

}, keywords = {Chitosan, Crosslinked chitosan, metal complex, Morphology, SEM, WAXRD}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2007.07.010}, author = {Trimukhe, K. D. and Varma, Anjanikumar} } @article {43320, title = {Multiple weak supramolecular interactions stabilize a surprisingly twisted As2L3 assembly}, journal = {Chemical Communications}, year = {2008}, month = {OCT}, pages = {3936 - 3938}, abstract = {A combined crystallographic, DFT and NMR spectroscopic study of a flexible As(2)(3) assembly reveals temperature dependent conformational behavior in solution and a highly asymmetric structure stabilized by As-pi and edge-to-face aromatic interactions.}, doi = {10.1039/b806958a}, author = {Pitt, Melanie A. and Zakharov, Lev N. and Vanka, Kumar and Thompson, Ward H. and Laird, Brian B. and Johnson, Darren W.} } @article {43318, title = {Multipoint anchoring of the [2.2.2.2]metacyclophane motif to a gold surface via self-assembly: coordination chemistry of a cyclic tetraisocyanide revisited}, journal = {Inorganic Chemistry}, volume = {47}, year = {2008}, month = {MAY}, pages = {3284-91}, abstract = {A one-pot transformation of bis(2-isocyano-3-methylphenyl)ethane affords gram quantities of 8,16,24,32-tetraisocyano[2.2.2.2]metacyclophane ( 3). The solid state structure of 3 is remarkably close to the lowest energy conformation found on the potential energy landscape for 3 by DFT. In solution, the structure of metacyclophane 3 is mobile but can be locked in a rectangular gauche- anti- gauche- anti conformation by coordination of the isocyanide substituents to the [W(CO) 5] units to give [M] 4(mu 4-eta (1):eta (1):eta (1):eta (1)- 3) ( 5). The tetranuclear [M] 4(mu 4-eta (1):eta (1):eta (1):eta (1)- 3) motif featured in crystallographically characterized 5 may be present in several insoluble complexes of 3 previously described as mononuclear eta (4) species. A self-assembled monolayer of metacyclophane 3 is formed upon exposing a solution of 3 to the gold(111) surface with no precautions to exclude air or light. The monolayer nature of the film was confirmed by optical ellipsometry. The isocyanide stretching band for 3 shifts from 2119 cm (-1) in solution to 2175 cm (-1) upon chemisorption to metallic gold. The FTIR spectrum of the film indicates interaction of 3 with the gold surface via all four of its isocyanide anchors. No gold-facilitated oxidation of the -NC junctions was detected under ambient conditions. The energy cost associated with accessing the conformations of 3 suitable for mu 4-eta (1):eta (1):eta (1):eta (1) interaction of the molecule with the Au(111) surface is under 8 kcal/mol, a value that can be easily offset by formation of a gold-isocyanide bond. Two different mu 4-eta (1):eta (1):eta (1):eta (1) coordination arrangements of 3 with respect to gold atoms on the (111) face of the fcc Au lattice are suggested.}, doi = {10.1021/ic702401b}, author = {Toriyama, Masaharu and Maher, Tiffany R. and Holovics, Thomas C. and Vanka, Kumar and Day, Victor W. and Berrie, Cindy L. and Thompson, Ward H. and Barybin, Mikhail V.} } @article { ISI:000261275000005, title = {Non-phosgene route for the synthesis of methyl phenyl carbamate using ordered AISBA-15 catalyst}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {295}, number = {1-2}, year = {2008}, month = {NOV}, pages = {29-33}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Methyl phenyl carbamate (MPC) has been synthesized Under liquid phase conditions from dimethyl carbonate and aniline by using mesoporous AISBA-15 catalyst. The catalyst with different Si/Al ratio was synthesized by isomorphous Substitution of aluminium into the framework of siliceous SBA-15. The structural integrity of the catalyst system was diagnosed with the help of various characterization techniques Such as X-ray diffraction, Surface analysis, and the acidity measurement has been done by TPD using ammonia as probe molecule. AISBA-15 (Si/Al = 10) exhibited highest catalytic activity in the synthesis of MPC under the reaction Conditions Studied. The effect of parameters Such as molar ratio of reactants, catalyst concentration. reaction temperature and time on the conversion of aniline was investigated. The results demonstrated that an aniline conversion of 99\% and MPC selectivity of 71\% were achieved when the reaction was carried out at 100 C, DMC to aniline mole ratio of 10 with 5\% of catalyst (wt\% of total reaction mixture) for 3 h. (c) 2008 Elsevier B.V. All rights reserved.

}, keywords = {amines, Dimethyl carbonate, Mesoporous AISBA-15, Methoxycarbonylation, Methyl phenyl carbamate}, issn = {1381-1169}, doi = {10.1016/j.molcata.2008.08.009}, author = {Lucas, Nishita and Amrute, Amol P. and Palraj, K. and Shanbhag, G. V. and Vinu, Ajayan and Halligudi, Shivaraj B.} } @article { ISI:000253625100010, title = {Novel stereoselective synthesis of pachastrissamine (jaspine B) starting from 1-pentadecanol}, journal = {Tetrahedron-Asymmetry}, volume = {19}, number = {2}, year = {2008}, month = {FEB}, pages = {209+}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

A novel stereoselective synthesis of pachastrissamine (jaspine B), starting from commercially available 1-pentadecanol is described. Sharpless asymmetric dihydroxylation and a chelation controlled vinyl Grignard reaction are the key steps in this synthetic strategy. (C) 2007 Elsevier Ltd. All rights reserved.

}, issn = {0957-4166}, doi = {10.1016/j.tetasy.2007.12.001}, author = {Venkatesan, K. and Srinivasan, K. V.} } @article { ISI:000254450600014, title = {Novel three dimensional cubic Fm3m mesoporous aluminosilicates with tailored cage type pore structure and high aluminum content}, journal = {Advanced Functional Materials}, volume = {18}, number = {4}, year = {2008}, month = {FEB}, pages = {640-651}, publisher = {WILEY-V C H VERLAG GMBH}, address = {PO BOX 10 11 61, D-69451 WEINHEIM, GERMANY}, abstract = {

Novel three dimensional cubic Fm3m mesoporous aluminosilicates (AIKIT-5) with very high structural order and unprecedented loadings of Al in the silica framework have been successfully prepared for the first time by using non ionic surfactant as a template in a highly acidic medium. The obtained materials have been unambiguously characterized in detail by several sophisticated techniques such as XRD, N, adsorption, HRTEM, HRSEM, EDS, elemental mapping, Al-27 MAS NMR, and NH3-TPD. We also demonstrate that the nature, and the amount of Al incorporation in the silica framework can easily be controlled by simply varying the n(H2O)/n(HCl) and the n(Si)/n(Al), ratios, and the Al sources in the synthesis gel. Among the Al sources examined, the Al isopropoxide (AiPr) is superior over other Al sources. Al-27 MAS NMR results reveal that the amount of tetrahedral Al in the framework can be controlled by simply adjusting the nSi/nAl ratio in the synthesis gel, which increases with increasing the Al incorporation. One of the interesting findings in the work is the increase of the specific surface area, specific pore volume and the pore diameter of AIKIT-5 with increasing the Al incorporation in the silica framework (up to n(Si)/n(Al), ratio of 10) while retaining the well-ordered three dimensional cage type porous structure, and the mechanism for the unusual behavior has been discussed in detail. Finally, the acidity and the catalytic activity in the acetylation of veratrole of the AIKIT-5 catalysts have been studied and the results have been compared with the several zeolites catalysts. Among the catalysts examined, AIKIT-5(10) is found to be superior over the zeolites catalysts such as mordenite, zeolite H-Y, zeolite H-beta, and ZSM-5.

}, issn = {1616-301X}, doi = {10.1002/adfm.200701027}, author = {Srinivasu, Pavuluri and Alam, Sher and Balasubramanian, Veerappan V. and Velmathi, Sivan and Sawant, Dhanashri P. and Boehlmann, Winfred and Mirajkar, Subhash P. and Ariga, Katsuhiko and Halligudi, Shivappa B. and Vinu, Ajayan} } @article { ISI:000271775108158, title = {ORGN 511-Total synthesis of 7-chloro-10-methoxycamptothecin: an important synthon for commercially important derivatives of camptothecin}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {235}, year = {2008}, note = {235th American-Chemical-Society National Meeting, New Orleans, LA, APR 06-10, 2008}, month = {APR}, publisher = {Amer Chem Soc}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, issn = {0065-7727}, author = {Sharma, Anil and Chavan, Subhash P. and Venkatraman, M. S.} } @article { ISI:000255295700013, title = {Photocatalytic decomposition of methylene nanocrystalline titania prepared by different blue on methods}, journal = {Materials Research Bulletin}, volume = {43}, number = {5}, year = {2008}, month = {MAY}, pages = {1145-1152}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

Nanocrystalline particles of pure anatase titania were prepared by two different methods. One is the sol-gel method at ambient temperature using ultrasonication (TiO2-SG-US) and conventional stirring method (TiO2-SG-S) and the other by surfactant assisted hydrothermal synthesis (TiO2-HT). More uniform distribution/dispersion of the nanoparticles (SEM), marginally higher surface area, better thermal stability and phase purity are some of the advantages of preparation of nanocrystalline titania by sol gel ultrasonication method and hydrothermal synthesis method. The behavior of anatase titania in photocatalytic decomposition of methylene blue in aqueous medium was studied as a function of the method of preparation and the crystallite size. The nanoparticles prepared by ultrasonication method were more effective than both, the sample prepared by conventional stirring method and commercial Degussa P-25. The higher photocatalytic activity of TiO2-SG-US is attributed to the more uniform size of the particles as compared to TiO2-SG-S samples. Both TEM and XRD data on TiO2-HT samples reveal a uniform and nanocrystalline TiO2 particles, which showed photocatalytic activity in both UV and visible region although brookite phase was also present. (C) 2007 Elsevier Ltd. All rights reserved.

}, keywords = {Catalytic properties, Nanostructures, Sol-gel chemistry}, issn = {0025-5408}, doi = {10.1016/j.materresbull.2007.06.003}, author = {Ramaswamy, Veda and Jagtap, Neelam and Vijayanand, S. and Bhange, Deu S. and Awati, Preeti} } @article { ISI:000255612400002, title = {Preparation of ferroelectric CaBi(4)Ti(4)O(15) powders from novel hydroxide precursors}, journal = {Materials Letters}, volume = {62}, number = {12-13}, year = {2008}, month = {APR}, pages = {1751-1753}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Ferroelectric CaBi(4)Ti(4)O(15) (CBT) powders were prepared for the first time from their respective hydroxides. Commercially purchased Ca(OH)(2) is mixed thoroughly with freshly prepared Bi(OH)(3) and Ti(OH)(4) in stoichiometrie ratio and heated at different temperatures ranging from 100 to 600 degrees C. The CBT phase found to be formed at 500 degrees C by the X-ray diffraction studies. This is the lowest temperature so far reported in the literature for the formation of CBT phase. The advantage of this method is that it also avoids the formation of calcium carbonate phase during synthesis. The phase contents and lattice parameters were studied by the powder X-ray diffraction (XRD) method. The average particle size and morphology were studied by scanning electron microscopy (SEM) technique. (c) 2007 Elsevier B.V All rights reserved.

}, keywords = {CaBi(4)Ti(4)O(15), Ceramics, Chemical synthesis, Electron microscopy, Oxides, X-ray methods}, issn = {0167-577X}, doi = {10.1016/j.matlet.2007.09.080}, author = {Deshmukh, Rupali G. and Vaishampayan, Mukta V. and Darshane, Sonali L. and Mulla, Imtiaz S. and Gaikwad, A. B. and Rao, N. Kotaserwara and Ravi, V.} } @article { ISI:000260561800007, title = {Rapid and high biodegradation of phenols catalyzed by Candida tropicalis NCIM 3556 cells}, journal = {Enzyme and Microbial Technology}, volume = {43}, number = {6}, year = {2008}, month = {NOV}, pages = {431-435}, publisher = {ELSEVIER SCIENCE INC}, address = {360 PARK AVE SOUTH, NEW YORK, NY 10010-1710 USA}, abstract = {

Cells of 19 yeast cultures, belonging to genus Candida were screened for biodegradation of phenol. The cultures procured from NCIM culture collection and were selected so as to contain a representative of varied strains of the species. These were grown in MGYP3 medium and tested for biodegradation of phenol. C. tropicalis (CT) nos. 3118, 3556 and C. lipolytica 3472 effectively degraded \>90\% 2 g l(-1) phenol. The C. tropicalis 3556 strain was selected for further studies as it metabolized \>95\% phenol in just 16 h as compared to the other two which took 48 h. The maximum substrate concentration that could be completely degraded was 2 g l(-1). A study of induction, of different concentration of phenol in the growth medium showed that toxicity to cell growth increased with increasing phenol levels in growth media. Biodegradation of phenol derivatives - o-cresol, m-cresol. 2,6-dimethyl phenol, alpha-naphthol, o-chlorophenol and p-nitrophenol, by the selected three strains indicated that the specificity of each culture varied for different substrate. (C) 2008 Elsevier Inc. All rights reserved.

}, keywords = {Biodegradation, Candida lipolytica, Candida tropicalis, phenol, Phenol derivatives}, issn = {0141-0229}, doi = {10.1016/j.enzmictec.2008.07.008}, author = {Varma, Rita J. and Gaikwad, Bhaskar G.} } @article { ISI:000257349100007, title = {Silicate nanoparticles by bioleaching of glass and modification of the glass surface}, journal = {Journal of Non-Crystalline Solids}, volume = {354}, number = {29}, year = {2008}, month = {JUL}, pages = {3433-3437}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Bioleaching is examined as a low temperature (50 degrees C) soft chemical approach to nanosynthesis and surface processing. We demonstrate that fungus based bioleaching of borosilicate glass enables synthesis of nearly monodispersed ultrafine (similar to 5 +/- 0.5 nm) silicate nanoparticles. Using various techniques such as X-ray diffraction, X-ray photoelectron spectroscopy and FTIR we compare the constitution and composition of the nanoparticles with that of the parent glass, and establish the basic similarities between the two. The bioleaching process is shown to enhance the non-bridging oxygen component and correspondingly influence the Si-O-Si network. The root mean square roughness of glass surface is seen to increase from 1.27 nm for bare glass to 2.52 nm for 15 h fungal processed case, this increase being equivalent to that for glass annealed at 500 degrees C. (c) 2008 Elsevier B.V. All rights reserved.

}, keywords = {Bioglass, Biomaterials, borosilicates, narroparticles}, issn = {0022-3093}, doi = {10.1016/j.jnoncrysol.2008.03.025}, author = {Kulkarni, Sneha and Syed, Asad and Singh, Sanjay and Gaikwad, Anil and Patil, Kashinath and Vijayamohanan, K. and Ahmad, Absar and Ogale, Satishchandra} } @article { ISI:000254798300017, title = {Spectrophotometric method for estimation of aliphatic primary amines in biological samples}, journal = {World Journal of Microbiology \& Biotechnology}, volume = {24}, number = {4}, year = {2008}, month = {APR}, pages = {573-576}, publisher = {SPRINGER}, address = {233 SPRING STREET, NEW YORK, NY 10013 USA}, abstract = {

A method based on Rimini test for aliphatic amines was studied and developed for quantitative estimation of aliphatic primary amines. The method involves action of the amine with acetone to form schiff base which complexes with sodium nitroprusside to give violet colour. The absorption maximum in the visible range of the spectrum, for the reaction mixture was found to be 550 nm. The pH (8-11) and reaction time scan for the assay were optimized. A linear relation of concentration (0.2-3 mg/mL) of amine against absorbance at 550 nm was established. Interference due to other reaction components was negligible (+/- 0.02 mg/mL) as compared to the sample in buffer. 1,3-dimethyl butylamine was used as the model amine and the method was applied to other amines; it was observed that when electron-withdrawing substituents are present in the molecule the reaction is retarded, as the incubation time was longer. This method is useful for estimation of aliphatic primary amine in biological samples.

}, keywords = {determination, estimation, primary aliphatic amines, Schiffs base, sodium nitroprusside, spectrophotometric}, issn = {0959-3993}, doi = {10.1007/s11274-007-9499-z}, author = {Varma, Rita J. and Gaikwad, Bhaskar G.} } @article { ISI:000263106900028, title = {Stereoselective synthesis of (S)-dapoxetine starting from trans-cinnamyl alcohol}, journal = {Arkivoc}, year = {2008}, month = {JAN}, pages = {302-310}, publisher = {ARKAT USA INC}, type = {Article}, address = {C/O ALAN R KATRITZKY, UNIV FLORIDA, DEPT CHEMISTRY, PO BOX 117200, GAINESVILLE, FL 32611 USA}, abstract = {

A novel stereoselective synthesis of (S)-dapoxetine starting from commercially available trans-cinnamyl alcohol is described. Sharpless Asymmetric Epoxidation (SAE) is utilized as the key step in this synthetic strategy.

}, keywords = {(S)-dapoxetine, antidepressant, Sharpless asymmetric epoxidation, stereoselective synthesis}, issn = {1424-6376}, author = {Venkatesan, K. and Srinivasan, K. V.} } @article { ISI:000256285600005, title = {Studies on optimization of cultural conditions and effect of media constituents on production of intracellular penicillin V acylase from Erwinia aroideae (DSMZ 30186)}, journal = {Research Journal of Biotechnology}, volume = {3}, number = {2}, year = {2008}, month = {MAY}, pages = {26-30}, publisher = {RESEARCH JOURNAL BIOTECHNOLOGY}, address = {SECTOR A-80, SCHEME NO 54, VIJAY NAGAR, A B ROAD, INDORE, 452 010 MP, INDIA}, abstract = {

Penicillin V acylase (PVA) is a pharmaceutically important enzyme. Erwinia aroideae (DSMZ 30186) produced high levels of intracellular penicillin V acylase. Amongst various carbon sources used (2.0 \%); fructose, galactose, sucrose and mannitol increased enzyme production up to 579, 544, 534 and 504 IU/g dry weight (DW), respectively, compared to minimal media (263 IU/g DW); however maximum PVA productivity (2796 IU/ L) was achieved using fructose. Ammonium ions escalated the enzyme production to 1266.9 IU/g DW; however sodium glutamate was the best nitrogen source for overall productivity of enzyme (2045 IU/ L). Cornsteep liquor and skim milk were used as supplements; 1.0 \% cornsteep liquor and 3.0 \% skim milk were optimum for the production of PVA up to 823 and 93 IU/g DW, respectively. Optimum cultural conditions for the production of PVA from E. aroideae were standardized. Erwinia aroideae produced 1543 IU/g DW penicillin V acylase in Erlenmeyer flasks (250 ml) containing 50 ml of minimal medium with 0.3\% ammonium sulphate, pH 7. 0 at 28 degrees C and 180 rpm when incubated for 56 hr.

}, keywords = {carbon sources, Erwinia aroideae, intracellular, nitrogen sources, Penicillin V acylase}, issn = {0973-6263}, author = {Atul, Kumar and Vivek, Lonkar and Archana, Pundle} } @article { ISI:000257381600004, title = {Sulfur nanoparticles synthesis and characterization from H2S gas, using novel biodegradable iron chelates in w/o microemulsion}, journal = {Nanoscale Research Letters}, volume = {3}, number = {6}, year = {2008}, month = {JUN}, pages = {221-229}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Sulfur nanoparticles were synthesized from hazardous H2S gas using novel biodegradable iron chelates in w/o microemulsion system. Fe3+-malic acid chelate (0.05 M aqueous solution) was studied in w/o microemulsion containing cyclohexane, Triton X-100 and n-hexanol as oil phase, surfactant, co-surfactant, respectively, for catalytic oxidation of H2S gas at ambient conditions of temperature, pressure, and neutral pH. The structural features of sulfur nanoparticles have been characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive spectroscopy (EDS), diffused reflectance infra-red Fourier transform technique, and BET surface area measurements. XRD analysis indicates the presence of alpha-sulfur. TEM analysis shows that the morphology of sulfur nanoparticles synthesized in w/o microemulsion system is nearly uniform in size (average particle size 10 nm) and narrow particle size distribution (in range of 5-15 nm) as compared to that in aqueous surfactant systems. The EDS analysis indicated high purity of sulfur (\> 99\%). Moreover, sulfur nanoparticles synthesized in w/o microemulsion system exhibit higher antimicrobial activity (against bacteria, yeast, and fungi) than that of colloidal sulfur.

}, keywords = {Antimicrobial activity, H2S gas, iron chelates, sulfur nanoparticles, w/o microemulsion}, issn = {1931-7573}, doi = {10.1007/s11671-008-9140-6}, author = {Deshpande, Aniruddha S. and Khomane, Ramdas B. and Vaidya, Bhalchandra K. and Joshi, Renuka M. and Harle, Arti S. and Kulkarni, Bhaskar D.} } @article { ISI:000254180300055, title = {Synthesis and antimicrobial activity of beta-lactam-bile acid conjugates linked via triazole}, journal = {Bioorganic \& Medicinal Chemistry Letters}, volume = {18}, number = {6}, year = {2008}, month = {MAR}, pages = {2043-2047}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

Synthesis of novel 1,2,3-triazole-linked beta-lactam-bile acid conjugates 17-24 using 1,3-dipolar cycloaddition reaction of azido beta-lactam and terminal alkyne of bile acids in the presence of Cu( I) catalyst ( click chemistry) have been realized. These molecules were evaluated in vitro for their antifungal and antibacterial activities. Most of the compounds exhibited significant antifungal and moderate antibacterial activity against all the tested strains. (c) 2008 Elsevier Ltd. All rights reserved.

}, issn = {0960-894X}, doi = {10.1016/j.bmcl.2008.01.102}, author = {Vatmurge, Namdev S. and Hazra, Braja G. and Pore, Vandana S. and Shirazi, Fazal and Chavan, Pradnya S. and Deshpande, Mukund V.} } @article { ISI:000260429100023, title = {Synthesis and biological evaluation of bile acid dimers linked with 1,2,3-triazole and bis-beta-lactam}, journal = {Organic \& Biomolecular Chemistry}, volume = {6}, number = {20}, year = {2008}, month = {OCT}, pages = {3823-3830}, publisher = {ROYAL SOC CHEMISTRY}, type = {Article}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

We report herein the synthesis and biological evaluation of bile acid dimers 11-18 linked through 1,2,3-triazole and bis-beta-lactam. The dimers 11-18 were synthesized using 1,3-dipolar cycloaddition reaction of diazido bis-beta-lactams 3, 4 and terminal alkynes 7-10 derived from cholic acid/deoxycholic acid in the presence of Cu(I) catalyst (click chemistry). These novel molecules were evaluated in vitro for their antifungal and antibacterial activity. Most of the compounds exhibited significant antifungal as well as antibacterial activity against all the tested fungal and bacterial strains. Moreover, their in vitro cytotoxicities towards HEK-293 and MCF-7 cells were also established.

}, issn = {1477-0520}, doi = {10.1039/b809221d}, author = {Vatmurge, Namdev S. and Hazra, Braja G. and Pore, Vandana S. and Shirazi, Fazal and Deshpande, Mukund V. and Kadreppa, Sreenath and Chattopadhyay, Samit and Gonnade, Rajesh G.} } @article { ISI:000258981000008, title = {Synthesis and characterization of novel polybenzimidazoles bearing pendant phenoxyamine groups}, journal = {Journal of Polymer Science Part A-Polymer Chemistry}, volume = {46}, number = {17}, year = {2008}, month = {SEP}, pages = {5776-5793}, publisher = {JOHN WILEY \& SONS INC}, type = {Article}, address = {111 RIVER ST, HOBOKEN, NJ 07030 USA}, abstract = {

A novel aromatic diacid, 3, 5-dicarboxyl-4{\textquoteright}-amino diphenyl ether, containing pendant phenoxy amine group was synthesized. Homo- and co-polybenzimidazoles containing different content of pendant phenoxyamine groups were synthesized by condensation of 3,3{\textquoteright}-diaminobenzidine with this acid and a mixture of this acid and isophthalic acid in different ratio in polyphosphoric acid. Copolybenzimidazoles with structural variations were also synthesized based on this acid and pyridine dicarboxylic acid, terephthalic acid, adipic acid, or sebacic acid. The polymers have good solubility in polar aprotic solvents and strong acids and they form tough flexible films by solution casting. The polymers were characterized by different instrumental techniques (FTIR, TGA, DSC, XRD, etc.) and for solvent solubility, mechanical properties, inherent viscosity, and proton conductivity. The inherent viscosities of the polymers vary in the range of 0.62-1.52 dL/g. They have high thermal stability up to 475506 degrees C (IDT) in nitrogen, high glass transition temperatures (T-g) ranging from 313 to 435 degrees C and good tensile strength ranging from 58 to 125 MPa. Proton conductivity of homo polymer is 3.72 x 10(-3) S/cm at 25 degrees C and 2.45 x 10(-2) S/cm at 200 degrees C (c) 2008 Wiley Periodicals, Inc.

}, keywords = {Characterization, copolybenzimidazoles, High performance polymers, high temperature materials, pendant phenoxyamine group, polybenzimidazoles, synthesis}, issn = {0887-624X}, doi = {10.1002/pola.22892}, author = {Kulkarni, Mahesh and Potrekar, Ravindra and Kulkarni, R. A. and Vernekar, S. P.} } @article { ISI:000259684000003, title = {Synthesis and spectral studies of nitrogen-oxygen donor macrocyclic metal complexes of Mn(II), Cu(II) Zn(II), Pd(II) and Pt(II)}, journal = {Journal of the Indian Chemical Society}, volume = {85}, number = {9}, year = {2008}, month = {SEP}, pages = {896-900}, publisher = {SCIENTIFIC PUBL-INDIA}, type = {Article}, address = {5-A, NEW PALI RD, PO BOX 91, NEAR HOTEL TAJ HARI MAHAL, JODHPUR, 342 003, INDIA}, abstract = {

The complexes of Mn(II), Cu(II), Zn(II), Pd(II) and Pt(II) with a nitrogen-oxygen donor macrocyclic ligand, viz. 5,6,13,14-dibenzo[1,4,8,11]dioxadiaza-5,7,11,13-cyclotetradecin have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, spectral and electrochemical studies. The molar conductance measurements of the complexes in DMF solution correspond to non electrolytic nature for M(L)X(2) complexes and 1 : 2 electrolytes for M {\textquoteleft}(L)X(2) Complexes [where M = Mn(II), Cu(II); M {\textquoteleft} = Zn(II), Pd(II) and Pt(II); X = Cl(-), NO(3)(-), and L = ligand]. Thus, the complexes may be formulated as [M(L)X(2)] and [M {\textquoteleft}(L)]X(2) respectively. Mn(II), Cu(II) complexes were of the high-spin type whereas the complexes of Zn(II), Pd(II) and Pt(II) were diamagnetic. On the basis of spectral studies an octahedral geometry has been assigned for Mull, tetragonal for Cull, tetrahedral for Zn(II) complexes whereas square planar for Pd(II) and Pt(II) complexes.

}, keywords = {Cu(II), macrocyclic, Mu(II), Pd(II), Pt(II), Zn(II)}, issn = {0019-4522}, author = {Chandra, Sulekh and Verma, Shweta and Meera, P.} } @article { ISI:000255339200058, title = {Synthesis, characterization, and gas permeability of aromatic polyimides containing pendant phenoxy group}, journal = {Journal of Applied Polymer Science}, volume = {108}, number = {6}, year = {2008}, month = {JUN}, pages = {3881-3889}, publisher = {JOHN WILEY \& SONS INC}, type = {Article}, address = {111 RIVER ST, HOBOKEN, NJ 07030 USA}, abstract = {

A diamine containing a pendant phenoxy group, 1-phenoxy-2,4-diaminobenzene, was synthesized and condensed with different aromatic dianhydrides [4,4{\textquoteright}-oxydiphthalic dianhydride, 4,4{\textquoteright}-(hexafluoroisopropylidene)diphthalic anhydride, 3,3{\textquoteright},4,4-benzophenone tetracarboxylic dianhydride, 3,3{\textquoteright},4,4{\textquoteright}-biphenyltetracorboxylic dianhydride, and pyromellitic dianhydride] by one-step synthesis at a high temperature in m-cresol to obtain polyimides in high yields. Most of the polyimides exhibited good solvent solubility and could be readily dissolved in chloroform, sym-tetrachloroethane, N,N-dimethylformamide, NN-dimethylacetamide, and nitrobenzene. Their inherent viscosities were in the range of 0.33-1.16 dL/g. Wide-angle X-ray spectra revealed that these polymers were amorphous in nature. All these polyimides were thermally stable, having initial decomposition temperatures above 500 degrees C and glass-transition temperatures in the range of 248-281 degrees C. The gas permeability of 4,4{\textquoteright}-oxydiphthalic dianhydride and 4,4{\textquoteright}-(hexafluoroisopropylidene)diphthalic anhydride based polyimides was investigated with pure gases: He, H-2, O-2, Ar, N-2, CH4, and CO2. A polyimide containing a -C(CF3)(2)- linkage showed a good combination of permeability and selectivity. (C) 2008 Wiley Periodicals, Inc.

}, keywords = {Gas permeation, membranes, polyimides, selectivity, structure-property relations}, issn = {0021-8995}, doi = {10.1002/app.28074}, author = {Kothawade, Sandeep S. and Kulkarni, Mahesh P. and Kharul, Ulhas K. and Patil, Anandrao S. and Vernekar, Subhash P.} } @article { ISI:000253450900027, title = {Synthesis of biodiesel over zirconia-supported isopoly and heteropoly tungstate catalysts}, journal = {Catalysis Communications}, volume = {9}, number = {5}, year = {2008}, month = {MAR}, pages = {696-702}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The liquid-phase synthesis of biodiesel by transesterification of sunflower oil with methanol is carried out by using zirconia-supported isopoly and heteropoly tungstates (HPAs) as catalysts. The isopoly and heteropoly tungstate catalysts were prepared by suspending zirconium oxyhydroxide in water/methanol solution of ammonium metatungstate/silicotungstic acid, phosphotungstic acid (WO3/HPA loading, 15\%,,) followed by drying and calcination at 750 degrees C. The catalysts were characterized by XRD, Raman spectroscopy, IR spectroscopy, NH3-TPD and FTIR pyridine adsorption spectroscopy. XRD results indicate that the presence of isopoly and heteropoly tungstates stabilizes ZrO2 in tetragonal phase. Raman and IR spectra of the catalysts show that tungstate species exist as zirconia-anchored octahedral mono-oxotungstate. The acidity measurements by NH3-TPD and FTIR pyridine adsorption spectroscopy show that zirconia-supported phosphotungstate has the highest total acidity and zirconia-supported isopoly tungstate has the highest Bronsted acidity. The zirconia-supported isopoly tungstate shows superior catalytic performance compared to zirconia-supported heteropoly tungstate catalysts. Under the reaction conditions of 200 degrees C and methanol/oil molar ratio 15, 15\% WO3/ZrO2 calcined at 750 degrees C gave 97\% conversion of oil. This catalyst also efficiently catalyzes methanolysis of other vegetable oils like mustard oil and sesame oil. The deactivated catalyst could be regenerated by calcination without appreciable loss in activity. (c) 2007 Elsevier B.V. All rights reserved.

}, keywords = {Biodiesel, phosphotungstic acids, Silicotungstic acid, transesterification, tungsten oxide, Zirconia}, issn = {1566-7367}, doi = {10.1016/j.catcom.2007.08.007}, author = {Sunita, G. and Devassy, Biju M. and Vinu, Ajayan and Sawant, Dhanashri P. and Balasubramanian, Veerappan V. and Halligudi, Shivappa B.} } @article {Council of Scientific and Industrial Research (CSIR), title = {Synthesis of five and six membered aminocyclitols: stereoselective michael and henry reaction approach with D-glucose derived alpha,beta-unsaturated ester}, journal = {Tetrahedron}, volume = {64}, number = {40}, year = {2008}, month = {SEP}, pages = {9574-9580}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

The stereoselective intermolecular Michael addition of nitromethane to D-glucose derived alpha,beta-unSaturated ester 7 afforded L-ido-configurated nitroester 8 as the only product that on reduction of the ester functionality, cleavage of 1,2-acetonide and the intramolecular Henry reaction afforded exclusively muco-nitroinositol 9. While reduction of the ester functionality in 8, deprotection of 1,2-acetonide, oxidative cleavage with NaIO(4) and the intrarnolecular Henry reaction afforded nitrocyclopentitol 13. Nitrocyclitols 9 and 13 were converted to the hydroxyethyl substituted aminocyclohexitol 5 and aminocyclopentitol 6, respectively. (C) 2008 Elsevier Ltd. All rights reserved.

}, keywords = {aminocyclitols, carbohydrates, Henry reaction, Michael addition, nitroinositol}, issn = {0040-4020}, doi = {10.1016/j.tet.2008.07.049}, author = {Chakraborty, Chaitali and Vyavahare, Vinod P. and Puranik, Vedavati G. and Dhavale, Dilip D.} } @article { ISI:000252482800031, title = {Tuning the hydrophobic properties of silica particles by surface silanization using mixed self-assembled monolayers}, journal = {Journal of Colloid and Interface Science}, volume = {318}, number = {2}, year = {2008}, month = {FEB}, pages = {372-379}, publisher = {ACADEMIC PRESS INC ELSEVIER SCIENCE}, type = {Article}, address = {525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USA}, abstract = {

Here we describe a novel method of preparing hydrophobic silica particles (100-150 nm; water contact angle of dropcasted film ranging from 60 degrees to 168 degrees) by surface functionalization using different alkyltrichlorosilanes. During their preparation, the molecular surface roughness is also concurrently engineered facilitating a change in both the surface chemical composition and the geometrical microstructure to generate hierarchical structures. The water contact angle has been measured on drop-cast film surface. The enhancement in the water contact angle on 3D (curved) SAMs in comparison to that on 2D (planar) surface is discussed using the Cassie-Baxter equation. These silica particles can be utilized for many potential applications including selective adsorbents and catalysts, chromatographic supports and separators in microfluidic devices. (C) 2007 Elsevier Inc. All rights reserved.

}, keywords = {alkyltrichlorosilane, silanization, silica particles, superhydrophobicity}, issn = {0021-9797}, doi = {10.1016/j.jcis.2007.11.012}, author = {Kulkami, Sneha A. and Ogale, Satishchandra B. and Vijayamohanan, Kunjukrishanan P.} } @article { ISI:000257971900057, title = {Use of response surface optimization for the production of biosurfactant from rhodococcus spp. MTCC 2574}, journal = {Bioresource Technology}, volume = {99}, number = {16}, year = {2008}, month = {NOV}, pages = {7875-7880}, publisher = {ELSEVIER SCI LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

The production of biosurfactant from Rhodococcus spp. MTCC 2574 was effectively enhanced by response surface methodology (RSM). Rhodococcus spp. MTCC 2574 was selected through screening of seven different Rhodococcus strains. The preliminary screening experiments (one-factor at a time) suggested that carbon source: mannitol, nitrogen source: yeast extract and meat peptone and inducer: n-hexadecane are the critical medium components. The concentrations of these four media components were optimized by using central composite rotatable design (CCRD) of RSM. The adequately high R-2 value (0.947) and F score 19.11 indicated the statistical significance of the model. The optimum medium composition for biosurfactant production was found to contain mannitol (1.6 g/L), yeast extract (6.92 g/L), meat peptone (19.65 g/L), n-hexadecane (63.8 g/L). The crude biosurfactant was obtained from methyl tert-butyl ether extraction. The yield of biosurfactant before and after optimization was 3.2 g/L of and 10.9 g/L, respectively. Thus, RSM has increased the yield of biosurfactant to 3.4-fold. The crude biosurfactant decreased the surface tension of water from 72 mN/m to 30.8 mN/m (at 120 mg L-1) and achieved a critical, micelle concentration (CMC) value of 120 mg L-1. (C) 2008 Published by Elsevier Ltd.

}, keywords = {Biosurfactant, Medium optimization, Response surface methodology, Rhodococcus spp.}, issn = {0960-8524}, doi = {10.1016/j.biortech.2008.02.027}, author = {Mutalik, Snehal R. and Vaidya, Bhalchandra K. and Joshi, Renuka M. and Desai, Kiran M. and Nene, Sanjay N.} } @article { ISI:000266712800028, title = {Biodegradation and phenol tolerance by recycled cells of candida tropicalis NCIM 3556}, journal = {International Biodeterioration \& Biodegradation}, volume = {63}, number = {4}, year = {2009}, month = {JUN}, pages = {539-542}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Resting cells of Candida tropicalis NCIM 3556 rapidly degraded almost completely 2 g L(-1) phenol in 16h. In this study, we explored the possibility of further increasing the efficiency of the culture by repeatedly reusing the cell for biodegradation. The effect of continuous recycling of whole cells of C. tropicalis, for biodegradation of phenol indicated that though with each recycle of the cell there was steady decline in phenol biodegradation the conversion was appreciable for five recycle (similar to 70\%) and reached half-life of 50\% after eleven recycles. Inhibition due to substrate, recycling of cells and adaptation of residual cell were estimated and an equation derived; which indicated that the cell resilience to phenol increased with each cycle and at the end of eleven recycle adaptation was 68\%. However, when the adapted cells were sub cultured and showed marginal increase \<10\% in biodegradation. (C) 2009 Elsevier Ltd. All rights reserved.

}, keywords = {Biodegradation, Candida tropicalis, Inhibition, phenol, Recycle, Tolerance}, issn = {0964-8305}, doi = {10.1016/j.ibiod.2009.01.001}, author = {Varma, R. J. and Gaikwad, B. G.} } @article { ISI:000271494300030, title = {Cellulases from penicillium janthinellum mutants: solid-state production and their stability in ionic liquids}, journal = {Bioresources}, volume = {4}, number = {4}, year = {2009}, month = {AUG}, pages = {1670-1681}, publisher = {NORTH CAROLINA STATE UNIV DEPT WOOD \& PAPER SCI}, address = {CAMPUS BOX 8005, RALEIGH, NC 27695-8005 USA}, abstract = {

The cellulase production by P. janthinellum mutants on lignocellulosic material such as cellulose or steam exploded bagasse (SEB) in combination with wheat bran was studied in solid state fermentation (SSF). One of the mutants, EU2D21, produced the highest levels of endoglucanase (3710 IU g(-1) carbon source) and beta-glucosidase (155 IU g(-1) carbon source). Ionic liquids are so-called green solvents that have become attractive for biocatalysis. Stability of mutant cellulases was tested in 10-50\% of the ionic liquid 1-butyl-3-methylimidazolium chloride ([bmim]Cl). FPA and CMCase were significantly stable in 10\% ionic liquid after 5h. beta-glucosidase showed 85\% of its original activity after 5 h incubation in 30\% ionic liquid and retained 55\% of its activity after 24 h. This enzyme preparation hydrolyzed ionic-liquid-treated SEB completely in 15 h in the presence of 20\% ionic liquid. These studies revealed that there is no need of regenerating cellulose after ionic liquid treatment, since cellulase of mutant strain was found to be significantly stable in the ionic liquid.

}, keywords = {Cellulase stability, Ionic liquid, Mutant cellulase, Solid state fermentation}, issn = {1930-2126}, author = {Adsul, Mukund G. and Terwadkar, Asawari P. and Varma, Anjanikumar and Gokhale, Digambar V.} } @article { ISI:000268335600001, title = {Challenges associated with metal chelation therapy in alzheimer{\textquoteright}s disease}, journal = {Journal of Alzheimers Disease}, volume = {17}, number = {3}, year = {2009}, month = {JUL}, pages = {457-468}, publisher = {IOS PRESS}, address = {NIEUWE HEMWEG 6B, 1013 BG AMSTERDAM, NETHERLANDS}, abstract = {

A close association between brain metal dishomeostasis and the onset and/or progression of Alzheimer{\textquoteright}s disease ( AD) has been clearly established in a number of studies, although the underlying biochemical mechanisms remain obscure. This observation renders chelation therapy an attractive pharmacological option for the treatment of this disease. However, a number of requirements must be fulfilled in order to adapt chelation therapy to AD so that the term {\textquoteleft}{\textquoteleft}metal targeted strategies{\textquoteright}{\textquoteright} seems now more appropriate. Indeed, brain metal redistribution rather than brain metal scavenging and removal is the major goal of this type of intervention. The most recent developments in metal targeted strategies for AD will be discussed using, as useful examples, clioquinol, curcumin, and epigallocatechin, and the future perspectives will also be outlined.

}, keywords = {Alzheimer{\textquoteright}s disease, clioquinol, cuprizone, metal dishomeostasis, metal ions, nanomedicine, Parkinson{\textquoteright}s disease, polyphenols}, issn = {1387-2877}, doi = {10.3233/JAD-2009-1068}, author = {Hegde, Muralidhar L. and Bharathi, P. and Suram, Anitha and Venugopal, Chitra and Jagannathan, Ramya and Poddar, Pankaj and Srinivas, Pullabhatla and Sambamurti, Kumar and Rao, Kosagisharaf Jagannatha and Scancar, Janez and Messori, Luigi and Zecca, Luigi and Zatta, Paolo} } @article { ISI:000262657300010, title = {Comparative study on liquid phase alkylation of 2-methylnaphthalene with long chain olefins using different solid acid catalysts}, journal = {Applied Catalysis A-General}, volume = {352}, number = {1-2}, year = {2009}, month = {JAN}, pages = {74-80}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

A comparative study has been made over a variety of solid acid catalysts, which include isopoly and heteropoly ions supported on various supports such as zirconia, titania, a large variety of zeolites and a couple of mesoporous materials for liquid phasealkylation of 2-methylnaphthalene with 1-octene.All the catalyst systems were characterized by nitrogen sorption analysis, X-ray diffraction and NH(3)-TPD. Inspite of their high acid amounts zeolites gave poor catalytic performance due to their diffusional constraints; on the other hand mesoporous materials lacked diffusional constraints but due to their low acid amounts resulted in poor conversions. lsopoly and heteropoly ions supported on zirconia and titania were found to be catalytically active for the reaction due to total surface acidity. Among them, isopolytungstate supported on zirconia exhibited the best catalytic activity and was used for further optimization of reaction conditions. Excellent conversions of all olefins (\>92\%) with high selectivity of monoalkylmethylnaphthalene (\>95\%) was obtained under optimized reaction conditions. The catalyst could be recycled for several times without any obvious loss of its activity. (C) 2008 Elsevier B.V. All rights reserved.

}, keywords = {2-Methylnaphthalene, Alkylation, Long chain olefins, Zirconia}, issn = {0926-860X}, doi = {10.1016/j.apcata.2008.09.032}, author = {Lucas, Nishita and Bordoloi, Ankur and Amrute, Amol P. and Kasinathan, Palraj and Vinu, Ajayan and Bohringer, Walter and Fletcher, Jack C. Q. and Halligudi, Shivaraj B.} } @article {42552, title = {Comparison of feature selection and classification combinations for cancer classification using microarray data}, journal = { International Journal of Bioinformatics Research and Applications}, volume = {5}, year = {2009}, month = {JAN}, pages = {417-431 }, doi = {10.1504/IJBRA.2009.027515}, author = {Vijayan, V. and Bulsara, B. and Gadgil, Chetan J. and Gadgil, Mugdha} } @article { ISI:000271552400019, title = {Conformational characterization of human eukaryotic initiation factor 2 alpha: a single tryptophan protein}, journal = {Biochemical and Biophysical Research Communications}, volume = {390}, number = {2}, year = {2009}, month = {DEC}, pages = {273-279}, publisher = {ACADEMIC PRESS INC ELSEVIER SCIENCE}, address = {525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USA}, abstract = {

The alpha-subunit of the human eukaryotic initiation factor 2 (heIF2 alpha), a GTP binding protein, plays a major role in the initiation of protein synthesis. During various cytoplasmic stresses, eIF2 alpha gets phosphorylated by eIF2 alpha-specific kinases resulting in inhibition of protein synthesis. The cloned and over expressed heIF2 alpha, a protein with a single tryptophan (trp) residue was examined for its conformational characteristics using steady-state and time-resolved tryptophan fluorescence, circular dichroism (CD) and hydrophobic dye binding. The steady-state fluorescence spectrum, fluorescence lifetimes (tau(1) = 1.13 ns and tau(2) = 4.74 ns) and solute quenching studies revealed the presence of trp conformers in hydrophobic and differential polar environment at any given time. Estimation of the alpha-helix and beta-sheet content showed: (i) more compact structure at pH 2.0, (ii) distorted alpha-helix and rearranged beta-sheet in presence of 4 M guanidine hydrochloride and (iii) retention of more than 50\% ordered structure at 95 degrees C. Hydrophobic dye binding to the protein with loosened tertiary structure was observed at pH 2.0 indicating the existence of a molten globule-like structure. These observations indicate the inherent structural stability of the protein under various denaturing conditions. (C) 2009 Elsevier Inc. All rights reserved.

}, keywords = {Circular dichroism, heIF2 alpha, K562 cells, Molten globule, Steady-state and time-resolved fluorescence}, issn = {0006-291X}, doi = {10.1016/j.bbrc.2009.09.106}, author = {Sreejith, R. K. and Yadav, Viveka Nand and Varshney, Nishant K. and Berwal, Sunil K. and Suresh, C. G. and Gaikwad, Sushama M. and Pal, Jayanta K.} } @article { ISI:000266821100020, title = {Design of an "allsolid-state{\textquoteright}{\textquoteright} supercapacitor based on phosphoric acid doped polybenzimidazole (PBI) electrolyte}, journal = {Journal of Applied Electrochemistry}, volume = {39}, number = {7}, year = {2009}, month = {JUL}, pages = {1097-1103}, publisher = {SPRINGER}, address = {VAN GODEWIJCKSTRAAT 30, 3311 GZ DORDRECHT, NETHERLANDS}, abstract = {

The effectiveness of phosphoric acid doped polybenzimidazole as a polymer electrolyte membrane to fabricate an all solid-state super capacitor has been explored using hydrous RuO(2)/carbon composite electrodes (20 wt.\%) of surface area 250 m(2) g(-1) with many intrinsic advantages. The electrochemical evaluation of these super capacitors through cyclic voltammetry, charge/discharge and impedance measurements demonstrate the utility of this type of thin, compact and flexible supercapacitor capable of functioning at 150 degrees C to yield a maximum capacitance of about 290 F g(-1) along with a life of more than 1,000 cycles. A power density of 300 W kg(-1) and energy density of 10 Wh kg(-1) have been accomplished although the equivalent series resistance (ESR) of about 3.7 Omega needs to be reduced further for high rated applications.

}, keywords = {Electrochemical characterization, Electrochemical supercapacitor, Energy storage device, PBI electrolyte, RuO(2)/carbon composite}, issn = {0021-891X}, doi = {10.1007/s10800-008-9764-3}, author = {Rathod, Dhanraj and Vijay, Meenu and Islam, Md. Nazrul and Kannan, Ramaiyan and Kharul, Ulhas K. and Kurungot, Sreekumar and Pillai, Vijayamohanan} } @article { ISI:000273067400009, title = {Effect of sintering temperature and thermoelectric power studies of the system MgFe2-xCrxO4}, journal = {Solid State Sciences}, volume = {11}, number = {12}, year = {2009}, month = {DEC}, pages = {2075-2079}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Mixed metal oxides showing the spinel structure exhibit interesting structural and electrical properties. Substances with specific compositions in the system MgFe2-xCrxO4 were synthesized by the simple co-precipitation method and have been investigated by X-ray diffraction (XRD) and scanning electron microscope (SEM) to study the effect of temperature on the size of particles and grains. The infrared spectrum shows, two strong bands around 600 and 500 cm(-1). An elemental composition of one of the samples, MgFeCrO4 was found by energy dispersive X-ray spectroscopy (EDS). The thermoelectric power measurements carried out from room temperature to 500 degrees C, show both n-type and p-type behavior. (C) 2009 Elsevier Masson SAS. All rights reserved.

}, keywords = {synthesis, Temperature effect, Thermoelectric studies}, issn = {1293-2558}, doi = {10.1016/j.solidstatesciences.2009.09.005}, author = {Hankare, P. P. and Vader, V. T. and Sankpal, U. B. and Gavali, L. V. and Sasikala, R. and Mulla, Imtiaz S.} } @article { ISI:000267509500004, title = {Electronic manifestation of cation-vacancy-induced magnetic moments in a transparent oxide semiconductor: anatase Nb:TiO2}, journal = {Advanced Materials}, volume = {21}, number = {22}, year = {2009}, month = {JUN}, pages = {2282+}, publisher = {WILEY-V C H VERLAG GMBH}, type = {Article}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

Nb-doped anatase TiO2 thin films grown by pulsed-laser deposition show Kondo scattering in elctronic-transport measurements, providing evidence for the formation of magnetic moments. The origin of magnetism is attributed to cation (Ti) vacancies, confirmed by X-ray absorption spectroscopy and first-principle calculations. The Ti vacancies are controlled by oxygen partial pressure during growth.

}, issn = {0935-9648}, doi = {10.1002/adma.200803019}, author = {Zhang, Shixiong and Ogale, Satishchandra B. and Yu, Weiqiang and Gao, Xingyu and Liu, Tao and Ghosh, Saurabh and Das, Gour P. and Wee, Andrew T. S. and Greene, Richard L. and Venkatesan, Thirumalai} } @article { ISI:000268138200061, title = {Electronic structure and catalytic study of solid solution of GaN in ZnO}, journal = {Chemistry of Materials}, volume = {21}, number = {13}, year = {2009}, month = {JUL}, pages = {2973-2979}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Solid solutions of GaN in ZnO (Zn1-zGaz)(O1-xNx) (x and z \<= 0.15) have been prepared by simple solution combustion method, Except for minor changes in the lattice contraction, no significant change in the Wurtzite structure was observed. Raman and secondary ion mass spectrometry results show the direct Zn-N and Ga-N bonds in (Zn1-zGaz)(O1-xNx). Visible light absorption and XPS results demonstrate that N 2p states of nitride occupy the states above the O 2p valence band, and hence a change in optical band gap reduction occurs to similar to 2.5 eV from 3.37 eV for ZnO. Significant nitrogen fixation catalytic activity through NH3 formation has been observed at ambient pressure oil virgin (Zn1-zGaz)(O1-xNx) material, indicating its potential as a catalyst.

}, issn = {0897-4756}, doi = {10.1021/cm900682q}, author = {Mapa, Maitri and Thushara, K. S. and Saha, Biswajit and Chakraborty, Purushottam and Janet, C. M. and Viswanath, R. P. and Nair, C. Madhavan and Murty, K. V. G. K. and Gopinath, Chinnakonda S.} } @article { ISI:000270363600029, title = {Enhanced conversion efficiency in dye-sensitized solar cells based on hydrothermally synthesized TiO2-MWCNT nanocomposites}, journal = {ACS Applied Materials \& Interfaces}, volume = {1}, number = {9}, year = {2009}, month = {SEP}, pages = {2030-2035}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

A 50 \% enhancement in the conversion efficiency (4.9-7.37 \%) is realized in dye-sensitized solar cells Using hydrothermally synthesized TiO2-multiwalled carbon nanotube (MWCNT) nanocomposites as compared to hydrothermally synthesized TiO2 without MWCNT and Degussa P25. Several characterizations have been employed to reveal the nature of the modification imparted to the MWCNTs under hydrothermal processing conditions and the resulting TiO2-MWCNT conjugation through -COOH groups. Efficient charge transfer In the nanocomposite and efficient electron transport by MWCNT (significantly higher Incident-photon-to-current conversion efficiency) are suggested to be the possible reasons for the enhancement.

}, keywords = {Carbon nanotubes, charge transfer, Dye-sensitized solar cells, Hybrid composite, hydrothermal}, issn = {1944-8244}, doi = {10.1021/am900396m}, author = {Muduli, Subas and Lee, Wonjoo and Dhas, Vivek V. and Mujawar, Sarfraj and Dubey, Megha and Vijayamohanan, K. and Han, Sung-Hwan and Ogale, Satishchandra} } @article { ISI:000272052200068, title = {Enhanced nonvolatile resistive switching in dilutely cobalt doped TiO2}, journal = {Applied Physics Letters}, volume = {95}, number = {20}, year = {2009}, month = {NOV}, pages = {203502}, publisher = {AMER INST PHYSICS}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

Incorporation of dilute concentration of dopant having a valence state different than that of the host cation enables controlled incorporation proximity vacancy defects for local charge balance. Since nonvolatile resistive switching is a phenomenon tied to such defects, it can be expected to be influenced by dilute doping. In this work, we demonstrate that enhanced nonvolatile resistive switching is realized in dilutely cobalt doped TiO2 films grown at room temperature. We provide essential characterizations and analyses. We suggest that the oxygen vacancies in the proximity of immobile dopants provide well distributed anchors for the development of systematic filamentary tracks.

}, keywords = {cobalt, Doping, magnetic switching, random-access storage, titanium compounds, vacancies (crystal), valency}, issn = {0003-6951}, doi = {10.1063/1.3263713}, author = {Bogle, Kashinath A. and Bachhav, Mukesh N. and Deo, Meenal S. and Valanoor, Nagarajan and Ogale, Satishchandra B.} } @article { ISI:000265398300007, title = {Enhanced production of amidase from Rhodococcus erythropolis MTCC 1526 by medium optimisation using a statistical experimental design}, journal = {Journal of Industrial Microbiology \& Biotechnology}, volume = {36}, number = {5}, year = {2009}, month = {MAY}, pages = {671-678}, publisher = {SPRINGER HEIDELBERG}, address = {TIERGARTENSTRASSE 17, D-69121 HEIDELBERG, GERMANY}, abstract = {

In the present work, statistical experimental methodology was used to enhance the production of amidase from Rhodococcus erythropolis MTCC 1526. R. erythropolis MTCC 1526 was selected through screening of seven strains of Rhodococcus species. The Placket-Burman screening experiments suggested that sorbitol as carbon source, yeast extract and meat peptone as nitrogen sources, and acetamide as amidase inducer are the most influential media components. The concentrations of these four media components were optimised using a face-centred design of response surface methodology (RSM). The optimum medium composition for amidase production was found to contain sorbitol (5 g/L), yeast extract (4 g/L), meat peptone (2.5 g/L), and acetamide (12.25 mM). Amidase activities before and after optimisation were 157.85 units/g dry cells and 1,086.57 units/g dry cells, respectively. Thus, use of RSM increased production of amidase from R. erythropolis MTCC 1526 by 6.88-fold.

}, keywords = {Amidase, Medium optimisation, Plackett-Burman screening, Response surface methodology, Rhodococcus erythropolis}, issn = {1367-5435}, doi = {10.1007/s10295-009-0536-9}, author = {Vaidya, Bhalchandra K. and Mutalik, Snehal R. and Joshi, Renuka M. and Nene, Sanjay N. and Kulkarni, Bhaskar D.} } @article { ISI:000264644800018, title = {Ferromagnetic to spin glass cross over in (La,Tb)(2/3)Ca1/3MnO3}, journal = {Solid State Sciences}, volume = {11}, number = {3}, year = {2009}, month = {MAR}, pages = {714-718}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

In the series La2/3-xTbxCa1/3MnO3, it is known that the compositions are ferromagnetic for smaller values of x and show spin glass characteristics at larger values of x. Our studies on the magnetic properties of various compositions in the La2/3-xTbxCa1/3MnO3 series show that the cross over from ferromagnetic to spin glass region takes place above x approximate to 1/8. Also, a low temperature anomaly at 30 K, observed in the ac susceptibility curves, disappears for compositions above this critical value of x. A mixed phase region coexists in the narrow compositional range 0.1 \<= x \<= 0.125, indicating that the ferromagnetic to spin glass cross over is not abrupt. (C) 2008 Elsevier Masson SAS. All rights reserved.

}, keywords = {Ferromagnetism, Magnetic clusters, Manganites, perovskite, Spin glass}, issn = {1293-2558}, doi = {10.1016/j.solidstatesciences.2008.10.002}, author = {Sankar, C. Raj and Vijayanand, S. and Joy, Pattayil Alias} } @article { ISI:000267983100004, title = {First- and second-order electrical properties computed at the FSMRCCSD level for excited states of closed-shell molecules using the constrained-variational approach}, journal = {Journal of Chemical Physics}, volume = {131}, number = {2}, year = {2009}, month = {JUL}, pages = {024102}, publisher = {AMER INST PHYSICS}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

Fock space multireference coupled-cluster (FSMRCC) method emerged as an efficient tool to describe the electronic structure of nearly degenerate cases. Development of linear response has been one of the challenging problems in FSMRCC due to the multiple-root nature of the effective Hamiltonian. A response from any of the roots would span the space for getting the properties. Hence, all roots perturbed by the external field would proliferate the excited states. We recently developed the FSMRCC method for the efficient evaluation of analytic response properties using a constrained variation approach. In this paper, we present analytic dipole moments and polarizabilities of H2O, O-3, and CH+ molecules in low-lying excited states along with brief discussion of singlet triplet decoupling of (1,1) sector of FSMRCC resulting from spin adaptation. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3167796]

}, issn = {0021-9606}, doi = {10.1063/1.3167796}, author = {Bag, Arijit and Manohar, Prashant Uday and Vaval, Nayana and Pal, Sourav} } @article {42757, title = {Functional delivery of siRNA in mice using dendriworms}, journal = {ACS Nano}, volume = {3}, year = {2009}, month = {SEP}, pages = {2495-2504}, doi = {10.1021/nn900201e}, author = {Agrawal, Amit C. and Min, Dal-Hee and Singh, Neetu and Zhu, Haihao and Birjiniuk, Alona and von Maltzahn, Geoffrey and Harris, Todd J. and Xing, Deyin and Woolfenden, Stephen D. and Sharp, Phillip A. and Charest, Alain and Bhatia, Sangeeta N.} } @article { ISI:000270147700079, title = {Hydrolysis of cellulose derived from steam exploded bagasse by penicillium cellulases: comparison with commercial cellulase}, journal = {Bioresource Technology}, volume = {100}, number = {24}, year = {2009}, month = {DEC}, pages = {6679-6681}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

A complete cellulase from Penicillium pinophilum was evaluated for the hydrolysis of a-cellulose derived from steam exploded sugarcane bagasse and other cellulosic substrates. alpha-Cellulose at 1\% substrate concentration was completely hydrolyzed by Penicillium cellulase within 3 h wherein at 10\% the hydrolysis was 100\% within 24 h with an enzyme loading of 10 FPU/g. The hydrolysate yielded glucose as major end product as analyzed by HPLC. Under similar conditions, hydrolysis of Sigmacell (microcrystalline cellulose), CP-123 (pulverized cellulose powder) and ball milled Solka Floc were 42\%, 56\% and 52\%, respectively. Further the hydrolysis performance of Penicillium sp. cellulase is compared with Trichoderma reesei cellulase (Accellerase (TM) 1000) from Genencore. The kinetics of hydrolysis with respect to enzyme and substrate concentration will be presented. (C) 2009 Elsevier Ltd. All rights reserved.

}, keywords = {Accellerase (TM) 1000, Enzymatic hydrolysis, High beta-glucosidase, Penicillium cellulase, Sugarcane bagasse}, issn = {0960-8524}, doi = {10.1016/j.biortech.2009.07.060}, author = {Singh, Rajkumar and Varma, Anjanikumar and Laxman, Ryali Seeta and Rao, Mala} } @article { ISI:000266197300018, title = {Hypocholesteremic effect of bile salt hydrolase from Lactobacillus buchneri ATCC 4005}, journal = {Food Research International}, volume = {42}, number = {4}, year = {2009}, note = {International Congress on Bioprocesses in Food Industries, Hyderabad, INDIA, NOV 06-08, 2008}, month = {MAY}, pages = {516-520}, publisher = {ICBF Forum; Biotech Res Soc India}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The effect of oral administration of the immobilized bile salt hydrolase enzyme on serum cholesterol. triglyceride, high density lipoprotein levels and its application in the therapeutic treatment of hypercholesteremia was assessed. Culture conditions were optimized for the production of bile salt hydrolase, which resulted in 2.9-fold enhancement in activity. Bile salt hydrolase (BSH; E.C.3.5.1.24) was isolated from Lactobacillus buchneri ATCC 4005 and immobilized in 0.5\% gellan gum gel. The immobilized enzyme was orally delivered in wistar rats, induced with hypercholesteremia by triton X-100. The serum cholesterol and triglycerides were reduced by 50\% and 15\%, respectively, in the group fed with immobilized enzyme 10 IU/kg dose whereas administration of 20 IU/kg immobilized enzyme resulted in reduction of serum cholesterol by 58\% and triglycerides by 45\%, respectively. The results indicate that bile salt hydrolase has potential cholesterol lowering property and oral administration of the immobilized enzyme is an alternative pharmacological approach to reduce serum cholesterol levels. (C) 2009 Elsevier Ltd. All rights reserved.

}, keywords = {Bile salt hydrolase, Gellan gum, Hypocholesteremic effect, Lactobacillus buchneri, Wistar Rats}, issn = {0963-9969}, doi = {10.1016/j.foodres.2009.02.016}, author = {Sridevi, N. and Vishwe, Pradnya and Prabhune, Asmita} } @article { ISI:000270136900080, title = {Intracellular biogenic silver nanoparticles for the generation of carbon supported antiviral and sustained bactericidal agents}, journal = {Langmuir}, volume = {25}, number = {19}, year = {2009}, month = {OCT}, pages = {11741-11747}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Intracellular silver nanoparticles produced by exposing silver ions to the fungus Aspergillus ochraceus were heat-treated in nitrogen environment to yield silver nanoparticles embedded in carbonaceous supports. This carbonaceous matrix embedded silver nanoparticles showed antimicrobial properties against both bacteria (Gram-positive and Gram-negative) and virus (M 13 phage virus). The bactericidal effects were noticed even after washing and repealed exposure of these carbon supported silver nanoparticles to fresh bacterial Cultures, revealing their sustained activity.

}, issn = {0743-7463}, doi = {10.1021/la901024p}, author = {Vijayakumar, P. S. and Bhagavatula L. V. Prasad} } @article { ISI:000269638800052, title = {Magnetic characteristics of nanocrystalline multiferroic BiFeO3 at low temperatures}, journal = {Physical Review B}, volume = {80}, number = {6}, year = {2009}, month = {AUG}, pages = {064423}, publisher = {AMER PHYSICAL SOC}, address = {ONE PHYSICS ELLIPSE, COLLEGE PK, MD 20740-3844 USA}, abstract = {

The magnetic characteristics of nanocrystalline BiFeO3 with average crystallite sizes of similar to 50 and similar to 100 nm are evaluated by studying the temperature and field dependence of magnetization at low temperatures. Different properties such as magnetization, coercivity, and remanence show evidence for changes in the magnetic properties associated with the phase transitions at low temperatures, reported from Raman studies. Detailed field-cooled and zero-field-cooled magnetization measurements show that the likely origin of the changes in the magnetic characteristics is from the changes in the domain structure.

}, keywords = {bismuth compounds, coercive force, crystallites, magnetic domains, magnetic transitions, Multiferroics, Nanostructured materials, Raman spectra, remanence}, issn = {1098-0121}, doi = {10.1103/PhysRevB.80.064423}, author = {Vijayanand, S. and Mahajan, Mangesh B. and Potdar, H. S. and Joy, Pattayil Alias} } @article { ISI:000267086900013, title = {Magnetizability of doublet radicals using fock space multi-reference coupled cluster method}, journal = {International Journal of Quantum Chemistry}, volume = {109}, number = {10, SI}, year = {2009}, month = {AUG}, pages = {2191-2198}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

In this article, we report the first implementation of the recently developed Fock space multi reference Coupled cluster (FSMRCC) response approach for magnetizabilities. The FSM-RCC treats dynamic and static correlation in a very extensive manner. We report pilot application of the diarnagnetizability of NO, NO2, OH, and BH2 radicals. We also report preliminary applications of the paramagnetic magnetizability of the NO radical. Standard atom-centered Gaussian basis functions have been used, and this allowed US to Study the gauge dependence of the magnetizabilities. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 109: 2191-2198, 2009

}, keywords = {Fock space, magnetizability, multireference}, issn = {0020-7608}, doi = {10.1002/qua.22093}, author = {Ravichandran, Lalitha and Vaval, Nayana and Pal, Sourav} } @article { ISI:000265398300016, title = {Media optimization for biosurfactant production by rhodococcus erythropolis MTCC 2794: artificial intelligence versus a statistical approach}, journal = {Journal of Industrial Microbiology \& Biotechnology}, volume = {36}, number = {5}, year = {2009}, month = {MAY}, pages = {747-756}, publisher = {SPRINGER HEIDELBERG}, address = {TIERGARTENSTRASSE 17, D-69121 HEIDELBERG, GERMANY}, abstract = {

This paper entails a comprehensive study on production of a biosurfactant from Rhodococcus erythropolis MTCC 2794. Two optimization techniques-(1) artificial neural network (ANN) coupled with genetic algorithm (GA) and (2) response surface methodology (RSM)-were used for media optimization in order to enhance the biosurfactant yield by Rhodococcus erythropolis MTCC 2794. ANN and RSM models were developed, incorporating the quantity of four medium components (sucrose, yeast extract, meat peptone, and toluene) as independent input variables and biosurfactant yield [calculated in terms of percent emulsification index (\% EI24)] as output variable. ANN-GA and RSM were compared for their predictive and generalization ability using a separate data set of 16 experiments, for which the average quadratic errors were similar to 3 and similar to 6\%, respectively. ANN-GA was found to be more accurate and consistent in predicting optimized conditions and maximum yield than RSM. For the ANN-GA model, the values of correlation coefficient and average quadratic error were similar to 0.99 and similar to 3\%, respectively. It was also shown that ANN-based models could be used accurately for sensitivity analysis. ANN-GA-optimized media gave about a 3.5-fold enhancement in biosurfactant yield.

}, keywords = {Artificial neural network, Biosurfactant, Genetic algorithm, Media optimization, Response surface methodology, Rhodococcus}, issn = {1367-5435}, doi = {10.1007/s10295-009-0547-6}, author = {Pal, Moumita P. and Vaidya, Bhalchandra K. and Desai, Kiran M. and Joshi, Renuka M. and Nene, Sanjay N. and Kulkarni, Bhaskar D.} } @article { ISI:000260148600010, title = {Metal complexes of crosslinked chitosans: correlations between metal ion complexation values and thermal properties}, journal = {Carbohydrate Polymers}, volume = {75}, number = {1}, year = {2009}, month = {JAN}, pages = {63-70}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

A series of heavy metal complexes of crosslinked chitosans were evaluated by thermogravimetric studies. The metal complexes with Cu, Cd and Hg ions exhibiting the highest complexing ability to chitosans (Hg 354-364, Cu 100-112, and Cd 121-160, in mg/g chitosan), had the lowest onset of degradation temperatures (range 194-210 degrees C) and the lowest final degradation temperatures (generally less than 294-304 degrees C for Hg, 296-338 degrees C for Cu, and 305-368 degrees C for Cd complexes). Mn ion, with the lowest binding to chitosans (Mn 5-7 mg/g), showed the reverse behavior, having onset (240-248 degrees C) and final degradation temperatures (range 300-368 degrees C). Zn (binding 74-87 mg/g) and Pb (binding 39-62 mg/g) ions have a binding ability intermediate to Cu/Cd/Hg and Mn extremes, and therefore the effects on onset and final degradation temperatures are intermediate to these values. (C) 2008 Elsevier Ltd. All rights reserved.

}, keywords = {Chitosan, Crosslinked chitosan, Degradation temperature, Metal complexes, Thermal properties, Thermogravimetry}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2008.06.011}, author = {Trimukhe, K. D. and Varma, Anjanikumar} } @article { ISI:000266034600017, title = {Methyl glycosides are identified as glycosyl donors for the synthesis of glycosides, disaccharides and oligosaccharides}, journal = {Chemical Communications}, number = {18}, year = {2009}, month = {MAR}, pages = {2505-2507}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Stable methyl glycosides are identified as glycosyl donors in the presence of AuBr(3) in acetonitrile; a panel of aglycones comprising aliphatic, alicyclic, steroidal and sugar alcohols are examined successfully for the glycosylation reaction and methyl glycosides of di- and tri-saccharides are converted to corresponding tri- and tetra-saccharides exploiting salient features of our novel activation protocol.

}, issn = {1359-7345}, doi = {10.1039/b822526e}, author = {Vidadala, Srinivasa Rao and Hotha, Srinivas} } @article { ISI:000263073800056, title = {N,S-Co-doped TiO2 Nanophotocatalyst: synthesis, electronic structure and photocatalysis}, journal = {Journal of Nanoscience and Nanotechnology}, volume = {9}, number = {1, SI}, year = {2009}, month = {JAN}, pages = {423-432}, publisher = {AMER SCIENTIFIC PUBLISHERS}, address = {26650 THE OLD RD, STE 208, VALENCIA, CA 91381-0751 USA}, abstract = {

N,S-co-doped anatase-phase TiO2 (N,S-TiO2) nanophotocatalysts were prepared from either benzothiazoline or aminothiol with titanium isopropoxide followed by a systematic thermal decomposition. The chemical nature of S and N in N,S-TiO2 have been identified by XPS to be sulfate and NO-like, respectively. A significant band broadening and red-shift in the UV-visible absorption spectrum of N,S-TiO2 suggests a band gap reduction compared to TiO2. A maximum band-gap narrowing of 0.22 +/- 0.02 eV was observed on N,S-TiO2. Higher energy width observed on N,S-TiO2 is in contrast to 0.13 eV from N-doped TiO2 indicating the sulfate-like species might play a major role in narrowing the band-gap to a Higher level. It is confirmed that the oxidation of N and S to NO and SO42- occurs in the final stage of preparation of N,S-TiO2, during calcination in air. It is predicted that the oxygen associated with sulfate and NO structural features could be crucial in bringing down the energy gap and red shift in optical absorption and the role of sulfur is to facilitate the above. Photocatalytic decomposition of methylene blue has been carried out on N,S-TiO2 shows higher activity than the commercial TiO2 in the visible region. However, sulfate species seems to enhance the activity of N,S-TiO2 marginally compared to N-TiO2, and possible suggestions are given to improve the same.

}, keywords = {nitrogen, Photocatalyst, Sulfur, TiO2, Visible Light Absorption}, issn = {1533-4880}, doi = {10.1166/jnn.2009.J095}, author = {Sathish, M. and Viswanath, R. P. and Gopinath, Chinnakonda S.} } @article { ISI:000265933700042, title = {Origin of high room temperature ferromagnetic moment of nanocrystalline multiferroic BiFeO3}, journal = {Applied Physics Letters}, volume = {94}, number = {18}, year = {2009}, month = {MAY}, pages = {182507}, publisher = {AMER INST PHYSICS}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

Single phase nanocrystalline BiFeO3 of average crystallite size similar to 25 nm with very high magnetization at room temperature is synthesized by an autocombustion method. Magnetic measurements above room temperature show deviation between field cooled and zero field cooled magnetization below 645 K, the Neel temperature (T-N) of the bulk material, indicating intrinsic nature of ferromagnetism. However, observation of a broad magnetic transition above T-N of BiFeO3 and extended up to 800 K suggests the presence of Fe3O4 as a possible magnetic impurity phase. Evidence for the presence of Fe3O4 is obtained from detailed analysis of the powder x-ray diffraction pattern.

}, keywords = {bismuth compounds, Combustion synthesis, crystallites, ferromagnetic materials, high-temperature effects, magnetic impurities, Magnetic moments, Magnetisation, Multiferroics, Nanostructured materials, Neel temperature, X-ray diffraction}, issn = {0003-6951}, doi = {10.1063/1.3132586}, author = {Vijayanand, S. and Potdar, H. S. and Joy, Pattayil Alias} } @article { ISI:000272083700044, title = {Orthogonal activation of propargyl and n-pentenyl glycosides and 1,2-orthoesters}, journal = {Journal of Organic Chemistry}, volume = {74}, number = {23}, year = {2009}, month = {DEC}, pages = {9233-9236}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

An orthogonal activation strategy with propargyl and n-pentenyl glycosides has been identified. According to this methodology, n-pentenyl glycosides can be selectively activated with NIS/TMSOTf in the presence of either armed or disarmed propargyl O-glycosides. In addition, we report herein that propargyl 1,2-orthoesters can be selectively activated with AuBr(3) in CH(2)Cl(2) at room temperature in the presence of n-pentenyl glycosides. Similarly, pentenyl 1,2-orthoesters can be selectively activated with NIS/Yb(OTf)(3) in the presence of propargyl glycosides.

}, issn = {0022-3263}, doi = {10.1021/jo901837z}, author = {Vidadala, Srinivasa Rao and Thadke, Shivaji A. and Hotha, Srinivas} } @article { ISI:000265316800007, title = {Polybenzimidazoles tethered with N-Phenyl 1,2,4-triazole units as polymer electrolytes for fuel cells}, journal = {Journal of Polymer Science Part A-Polymer Chemistry}, volume = {47}, number = {9}, year = {2009}, month = {MAY}, pages = {2289-2303}, publisher = {JOHN WILEY \& SONS INC}, address = {111 RIVER ST, HOBOKEN, NJ 07030 USA}, abstract = {

Polybenzimidazole (PBI) polymers tethered with N-phenyl 1,2,4-triazole (NPT) groups were prepared from a newly synthesized aromatic diacid, 3{\textquoteright}-(4-phenyl-4H-1,2,4-triazole-3,5-diyl) dibenzoic acid (PTDBA). The obtained polymers show superior thermal and chemical stability and good solubility in many aprotic solvents. The inherent viscosities of all polymers were around 1 dL/g. They exhibit high thermal stability with initial decomposition temperature ranging from 515 to 530 degrees C, high glass transition temperature ranging from 375 to 410 degrees C, and good mechanical properties with tensile stress in the range of 66-98 MPa and modulus 1897-2600 MPa. XRD analysis indicates that these polymers are amorphous in nature. PhysicochemiCal properties such as water and phosphoric acid-uptake, oxidative stability, and proton conductivity of membranes of these polymers have also been determined. The proton conductivity ranged from 4.7 x 10(-3) to 1.8 x 10(-2) S cm(-1) at 175 degrees C in dry conditions. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2289-2303, 2009

}, keywords = {fuel cells, Polybenzimidazole, synthesis and characterization, Triazole}, issn = {0887-624X}, doi = {10.1002/pola.23310}, author = {Potrekar, R. A. and Kulkarni, M. P. and Kulkarni, R. A. and Vernekar, S. P.} } @article {43344, title = {Process for the preparation of polymeric absorbents }, number = {US 09/537,450}, year = {2009}, month = {JAN}, chapter = {US6794467 B2}, abstract = {The invention discloses a process for the preparation of polymeric absorbents useful for gelling organic liquids. The process comprises mixing one or more monomers with a cross-linking agent, a free radical initiator, an optional solvent, optionally in the presence of a transition metal source and subjecting the mixture so obtained to a conventional polymerisation method. The polymer is removed, crushed to obtain polymer powder, washed with solvent and dried by conventional methods to remove unreacted monomers, followed by swelling in alcohols to obtain the desired product.}, author = {Lele, Ashish Kishor and Varghese, Shyni and Badiger, Manohar V. and Mashelkar, Raghunath Anant} } @article { ISI:000261921400006, title = {Proline-catalyzed simple and efficient synthesis of 1,8-dioxo-decahydroacridines in aqueous ethanol medium}, journal = {Synthetic Communications}, volume = {39}, number = {2}, year = {2009}, month = {DEC}, pages = {PII 907127919}, publisher = {TAYLOR \& FRANCIS INC}, address = {325 CHESTNUT ST, SUITE 800, PHILADELPHIA, PA 19106 USA}, abstract = {

Proline-catalyzed synthesis of 1,8-dioxo-decahydroacridines is achieved via one-pot, three-component condensation of aromatic aldehydes, cyclic diketone, and aryl amines in aqueous ethanol medium. This method offers the advantages of proceeding in neutral and mild conditions, giving high to excellent yields of acridines with easy workup procedure.

}, keywords = {1, 8-dioxodecahydroacridines, aqueous media, one-pot MCR, Proline}, issn = {0039-7911}, doi = {10.1080/00397910802044306}, author = {Venkatesan, K. and Pujari, Suresh S. and Srinivasan, Kumar V.} } @article { ISI:000266545500027, title = {Real-time nanomechanical and topographical mapping on live bacterial cells-brevibacterium casei under stress due to their exposure to Co2+ Ions during microbial synthesis of Co3O4 nanoparticles}, journal = {Journal of Physical Chemistry B}, volume = {113}, number = {22}, year = {2009}, month = {JUN}, pages = {7927-7933}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The study of elastic properties of microbial and mammalian cells using atomic force microscopy, with force-sensitivity as high as pico-Newtons and spatial resolution of a few nanometers, is proving to be a great tool for the real-time observation of the effects of drugs, biomolecules, metal ions, and nanoparticles on cell physiology in their natural environment. It has been shown that the Young{\textquoteright}s modulus of the cell surfaces is extremely sensitive to the surrounding environment. Recently, a broad array of microbes have been used successfully to synthesize nanocrystals of several metal and metal oxides in a controlled manner at room temperature after exposing them to various metal ion precursors. However, so far there is no report on the fate of their elastic properties and cell topography etc. during and after their exposure to the metal ions during the microbial synthesis of nanomaterials. Additionally, this information is also found to be extremely relevant to areas such as bioremediation, bioleaching, and biomineralization, where it is important to study the direct influence on the cell physiology in the presence of metal ions. Here, we report, for the first time, the use of AFM force-distance curves on live cells, to directly monitor (in real time) the changes in the surface-topography, surface-adhesion, indentation-depth, and Young{\textquoteright}s modulus of a metal-tolerant marine bacterium, Brevibacterium casei, isolated from the coast of the Arabian Sea, after its exposure to the Co2+ ions during the process of biosynthesis of nanoparticles. We earlier reported that this bacterium is capable of using the cobalt acetate as a precursor to synthesize protein-functionalized Co3O4 nanoparticles with very high crystallinity. Our study indicates a significant change in the morphology as well as elastic and adhesive properties of the Brevibacterium casei, where we found an increase in the adhesive properties and the indentation depth of the bacterial surfaces and a decrease in the cell stiffness after several hours of exposure to the cobalt acetate. We have discussed both qualitative and quantitative analysis of the force-spectroscopy data in detail.

}, issn = {1520-6106}, doi = {10.1021/jp902698n}, author = {Kumar, Umesh and Vivekanand, K. and Poddar, Pankaj} } @article { ISI:000286307300007, title = {Synthesis of Sb-doped SnO2 nanowires and hyperbranched structures}, journal = {Science of Advanced Materials}, volume = {1}, number = {1}, year = {2009}, month = {APR}, pages = {38-43}, publisher = {AMER SCIENTIFIC PUBLISHERS}, address = {26650 THE OLD RD, STE 208, VALENCIA, CA 91381-0751 USA}, abstract = {

Branched nanostructures of semiconducting materials are of great interest for their potential applications in optoelectronic, photonic devices and sensors. We herein describe a facile single-step chemical vapor deposition route for the synthesis of Sb-SnO2 hyperbranched nanostructures comprised of elongated nanowires with 30-40 nm diameter and 10-20 Am length. The morphology and structure has been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), selective area electron diffraction (SAED), and powder X-ray diffraction (XRD). Also, a possible mechanism is proposed for the growth of nanowires into the hyperbranched form on the basis of the substrate effect, the role of Au nanoparticles, and the effect of Sb doping on specific morphology evolution. Interestingly, electrical conductivity measurements as a function of temperature suggest a semiconducting behavior, despite being governed by different electron-transport mechanisms with activation energies of 0.55 and 0.17 eV, which correspond to pure SnO2 and Sb-SnO2 nanowires, respectively. A precise control over the operating parameters not only envisages custom-designed, branched structures by a simple and economical route but also offers an alternative method to the expensive and tedious nanofabrication techniques for industrial applications.

}, keywords = {Au Nanoparticles, chemical vapor deposition, Sb-SnO2 Hyperbranched Nanostructures}, issn = {1947-2935}, doi = {10.1166/sam.2009.1006}, author = {Sathe, Bhaskar R. and Patil, Mrudula and Walke, Pravin S. and Vivek, J. P. and Lele, Ashish K. and Pillai, Vijayamohanan K. and Mulla, Imtiaz S.} } @article { ISI:000263073800048, title = {Template free synthesis of mesoporous TiO2 with high wall thickness and nanocrystalline framework}, journal = {Journal of Nanoscience and Nanotechnology}, volume = {9}, number = {1, SI}, year = {2009}, month = {JAN}, pages = {371-377}, publisher = {AMER SCIENTIFIC PUBLISHERS}, address = {26650 THE OLD RD, STE 208, VALENCIA, CA 91381-0751 USA}, abstract = {

A simple procedure to prepare nanocrystalline mesoporous titania (meso-TiO2) is reported without any templating agent and it possesses a high BET surface area and a large pore wall thickness (11.3 nm) than that of meso-TiO2 prepared by other methods. Nanocrystalline meso-TiO2 also has been synthesized with hexadecylamine template for comparison through known procedure. The meso-TiO2 materials were characterized by X-ray diffraction, FT-IR, UV-Vis absorbance spectra, thermal analysis, SEM, HRTEM and textural properties through N-2 adsorption-desorption isotherms. Spherical shape particles in a range of few hundred nanometers are obtained in the template free method. Above systematic characterization provides direct indications toward the mechanism of formation of meso-TiO2 in the template free method. A comparison of the physical and textural properties indicates a possibility of coarse-tuning of the textural characteristics of mesoporous TiO2 by adopting different preparation methods.

}, keywords = {Mesopore, Mesopore Formation, Template-Free, Thick Wall, titania}, issn = {1533-4880}, doi = {10.1166/jnn.2009.J019}, author = {Kulkarni, Dhanashree G. and Murugan, A. Vadivel and Viswanath, Annamraju Kasi and Gopinath, Chinnakonda S.} } @article { ISI:000263399700004, title = {Utilization of sugarcane bagasse cellulose for producing cellulose acetates: novel use of residual hemicellulose as plasticizer}, journal = {Carbohydrate Polymers}, volume = {76}, number = {1}, year = {2009}, month = {MAR}, pages = {23-29}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Sugarcane bagasse was fractionated to cellulose, hemicellulose and lignin by a proprietary steam explosion process, followed by downstream purifications, developed in our laboratory. The fractionated cellulose contained similar to 94\% cellulose, about similar to 5\% hemicellulose, traces of lignin (similar to 0.2\%), and similar to 1\% ash. The cellulose was acetylated under heterogeneous conditions to obtain cellulose acetates. These were extensively characterized using FTIR, TGA, DSC, GPC, HPIC, WAXRD, and viscometry. The novel feature of this study was the utilization of the hemicellulose content (5\%) of bagasse cellulose as an internal plasticizer. Through kinetic experimentation, we have demonstrated that the residual hemicellulose need not be considered as an impurity; rather it can be used in acetylated form as a plasticizer as well as a biodegradable additive for cellulose acetates made from slightly impure cellulose produced from non-wood origin. Our results therefore show how lignocellulosic agricultural wastes can be utilized to produce high value plastics. (C) 2008 Elsevier Ltd. All rights reserved.

}, keywords = {Bagasse cellulose, Cellulose acetate, Hemicellulose, Plasticizer, Sugarcane bagasse, Xylan acetate}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2008.09.014}, author = {Shaikh, Hamid M. and Pandare, Kiran V. and Nair, Greeshma and Varma, Anjanikumar} } @conference { ISI:000279938400012, title = {Chemical shielding of closed-shell molecules using extended coupled-cluster theory}, booktitle = {International Conference on Recent Advances in Spectroscopy - Theoretical, Astrophysical and Experimental Perspectives}, series = {Astrophysics and Space Science Proceedings}, year = {2010}, note = {International Conference on Recent Advances in Spectroscopy - Theoretical, Astrophysical and Experimental Perspectives, Indian Inst Astrophys, Kodaikanal Observatory, Bangalore, INDIA, JAN 28-31, 2009}, month = {MAR}, pages = {111-121}, publisher = {Springer}, organization = {Springer}, address = {233 Spring Street, New York, NY 10013, United States}, abstract = {

In this paper we report calculation of the nuclear magnetic shielding constant using extended coupled cluster response approach. We present the results for the HF, BH, CO and N(2) molecules. These results show importance of correlation corrections for the shielding constant.

}, isbn = {978-3-642-10321-6}, issn = {1570-6591}, doi = {10.1007/978-3-642-10322-3_12}, author = {Ravichandran, Lalitha and Joshi, Sayali and Vaval, Nayana}, editor = {Chaudhuri, R. K. and Mekkaden, M. V. and Raveendran, A. V. and Narayanan, A. S.} } @article { ISI:000281868200016, title = {Cobalt nanoparticles doped emaraldine salt of polyaniline: a promising room temperature magnetic semiconductor}, journal = {Journal of Magnetism and Magnetic Materials}, volume = {322}, number = {24}, year = {2010}, month = {DEC}, pages = {3926-3931}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Incorporation of magnetic nanoparticles in polymers with organic functional groups working as semiconducting substrate is of immense interest in the field of dilute magnetic semiconductors (DMS) and spintronics. In this article we report on synthesis and evaluation of dilutely doped (0-10 wt\%) cobalt nanoparticles in emaraldine salt (ES) of polyaniline in the presence of dodecyl benzene sulfonic acid (DBSA) and p-toluene sulfonic acid (p-TSA) using a sonochemical-assisted-reduction approach as a possible DMS candidate. The X-ray diffraction pattern and high resolution transmission electron microscopy (HRTEM) image show the ES to be polycrystalline, in which 10 nm sized Co nanoparticles get embedded in its FCC structural form. From Fourier transform infrared (FT-IR) and UV-visible (UV-vis) spectroscopy studies, it is predicted that cobalt particles get electrostatically bound to the specific SO(3)(-) ion sites of ES, thereby modifying torsional degrees of freedom of the system. The applied field dependent magnetization study shows that the sample exhibits hysteresis loop with a minimal doping of 3 wt\% of Co nanoparticles and increases with the amount of Co nanoparticles in ES due to dipolar interaction. The electron transport data show that with increase in Co wt\% there is a gradual shift from ohmic to non-ohmic response to the sample bias, accompanied by opening of electrical hysteresis and an increased resistance. The non-linear response of higher doped systems has been attributed to the combination of direct and Fowler-Nordheim tunneling phenomena in these systems. Persistence of optical and transport properties of the polymer, with an introduction of magnetic moment in the system, envisages the system to be a fine magnetic semiconductor. (C) 2010 Elsevier B.V. All rights reserved.

}, keywords = {Cobalt nanoparticles, Magnetic semiconductor, polyaniline}, issn = {0304-8853}, doi = {10.1016/j.jmmm.2010.08.022}, author = {Hatamie, Shadie and Kulkarni, M. V. and Kulkarni, S. D. and Ningthoujam, R. S. and Vatsa, R. K. and Kale, Sangeeta N.} } @article { ISI:000284515800005, title = {Combined experimental and density functional theory study on the Pd-mediated cycloisomerization of o-alkynylnitrobenzenes - synthesis of isatogens and their evaluation as modulators of ROS-mediated cell death}, journal = {European Journal of Organic Chemistry}, number = {31}, year = {2010}, month = {NOV}, pages = {5955-5966}, publisher = {WILEY-V C H VERLAG GMBH}, address = {PO BOX 10 11 61, D-69451 WEINHEIM, GERMANY}, abstract = {

Highly selective cycloisomerization of o-alkynylnitrobenzenes, leading to isatogens, has been achieved by employment of a Pd-II complex. This reaction is very general and functional-group-tolerant. The possible mechanism of this reaction was investigated with the help of DFT calculations. Three possible pathways - namely, the addition of the nitro group either in (i) 5-exo-dig or (ii) 6-endo-dig mode and (iii) halopalladation - and subsequent intramolecular events have been considered and studied in detail. These investigations revealed that pathway (i) is the favored route to isatogen formation. A preliminary screening of the available isatogens reveals the 2-alkylisatogens to be novel ROS scavengers capable of inhibiting cellular necroptosis.

}, keywords = {Anthranil, cyclization, Density functional calculations, isatogens, Nitro-alkyne cycloisomerization, Palladium}, issn = {1434-193X}, doi = {10.1002/ejoc.201000769}, author = {Ramana, Chepuri V. and Patel, Pitambar and Vanka, Kumar and Miao, Benchun and Degterev, Alexei} } @article { ISI:000276497600005, title = {Continuous phenol biodegradation in a simple packed bed bioreactor of calcium alginate-immobilized Candida tropicalis (NCIM 3556)}, journal = {World Journal of Microbiology \& Biotechnology}, volume = {26}, number = {5}, year = {2010}, month = {MAY}, pages = {805-809}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Phenol biodegradation in a continuous system of immobilized Candida tropicalis NCIM 3556 was studied. The bioreactor was simple, it had a feed inlet from the bottom and the effluent outlet from top, no supplementary oxygen was supplied, the reactor was operated continuously for 116 days. Initially the column was run continuously with a feed concentration of 2 g l(-1) for 42 days whence a degradation of \> 97\% was achieved. The feed concentration was then increased to 3 g l(-1), for which a similar to 80\% biodegradation was sustained for 90 days after which there was a steady decrease in the performance. When the phenol degradation was reduced to similar to 50\% in 116 days, the reactor was stopped. The efficiency of free cells recycled every 24 h and immobilized cells were compared; it was estimated that repeated reuse of free cells in batch mode gave an overall efficiency of 0.102 g phenol degradation g(-1) cell wet weight in 12 days. In contrast, the immobilized system of the same biomass had a longer working lifetime of similar to 4 months indicating an efficiency of 3.72 g phenol g(-1) cell wet wt.

}, keywords = {Biodegradation, Ca alginate, Candida tropicalis, Immobilization, phenol}, issn = {0959-3993}, doi = {10.1007/s11274-009-0236-7}, author = {Varma, R. J. and Gaikwad, B. G.} } @article { ISI:000280605900013, title = {Coupling growth-factor engineering with nanotechnology for therapeutic angiogenesis}, journal = {Proceedings of the National Academy of Sciences of the United States of America}, volume = {107}, number = {31}, year = {2010}, month = {AUG}, pages = {13608-13613}, publisher = {NATL ACAD SCIENCES}, address = {2101 CONSTITUTION AVE NW, WASHINGTON, DC 20418 USA}, abstract = {

Therapeutic angiogenesis is an emerging paradigm for the management of ischemic pathologies. Proangiogenic Therapy is limited, however, by the current inability to deliver angiogenic factors in a sustained manner at the site of pathology. In this study, we investigated a unique nonglycosylated active fragment of hepatocyte growth factor/scatter factor, 1K1, which acts as a potent angiogenic agent in vitro and in a zebrafish embryo and a murine matrigel implant model. Furthermore, we demonstrate that nanoformulating 1K1 for sustained release temporally alters downstream signaling through the mitogen activated protein kinase pathway, and amplifies the angiogenic outcome. Merging protein engineering and nanotechnology offers exciting possibilities for the treatment of ischemic disease, and furthermore allows the selective targeting of downstream signaling pathways, which translates into discrete phenotypes.

}, keywords = {cardiovascular disease, HGF/SF, ischemic disease, nanoparticle, protein engineering}, issn = {0027-8424}, doi = {10.1073/pnas.1006007107}, author = {Roy, Rituparna Sinha and Soni, Shivani and Harfouche, Rania and Vasudevan, Pooja R. and Holmes, Oliver and de Jonge, Hugo and Rowe, Arthur and Paraskar, Abhimanyu and Hentschel, Dirk M. and Chirgadze, Dimitri and Blundell, Tom L. and Gherardi, Ermanno and Mashelkar, Raghunath Anant and Sengupta, Shiladitya} } @article { ISI:000278165900028, title = {Crystallization and preliminary X-ray diffraction analysis of various enzyme-substrate complexes of isopropylmalate dehydrogenase from thermus thermophilus}, journal = {Acta Crystallographica Section F-Structural Biology and Crystallization Communications}, volume = {66}, number = {6}, year = {2010}, month = {JUN}, pages = {738-743}, publisher = {WILEY-BLACKWELL PUBLISHING, INC}, address = {COMMERCE PLACE, 350 MAIN ST, MALDEN 02148, MA USA}, abstract = {

The Thermus thermophilus 3-isopropylmalate dehydrogenase (Tt-IPMDH) enzyme catalyses the penultimate step of the leucine-biosynthesis pathway. It converts (2R,3S)-3-isopropylmalate to (2S)-2-isopropyl-3-oxosuccinate in the presence of divalent Mg(2+) or Mn(2+) and with the help of NAD(+). In order to elucidate the detailed structural and functional mode of the enzymatic reaction, crystals of Tt-IPMDH were grown in the presence of various combinations of substrate and/or cofactors. Here, the crystallization, data collection and preliminary crystallographic analyses of six such complexes are reported.

}, issn = {1744-3091}, doi = {10.1107/S174430911001626X}, author = {Merli, Angelo and Manikandan, Karuppasamy and Graczer, Eva and Schuldt, Linda and Singh, Rajesh Kumar and Zavodszky, Peter and Vas, Maria and Weiss, Manfred S.} } @article { ISI:000275090400021, title = {Cu:Al Nano catalyst for selective hydrogenolysis of glycerol to 1,2-propanediol}, journal = {Catalysis Letters}, volume = {135}, number = {1-2}, year = {2010}, month = {MAR}, pages = {141-147}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Non-chromium Cu:Al nano catalyst prepared by simultaneous co-precipitation and digestion method without any template or stabilizer, showed three times higher activity than the bulk Cu-Cr catalyst for hydrogenolysis of glycerol in both isopropanol and water solvents, with the selectivity to 1,2-Propanediol (1,2-PDO) as high as 91\% at 493 K and H(2) pressure of 7 MPa in 5 h. XRD pattern showed the presence of Cu(+) species in the activated Cu: Al nano catalyst. Although Cu(+) is catalytically inactive in glycerol hydrogenolysis reaction, the presence of Cu(+) helps to stabilize the particle size in a narrow range of 7-11 nm by inhibiting the sintering of copper particles under reaction conditions.

}, keywords = {1, 2-Propanediol, Cu:Al nano catalyst, Glycerol, Selective hydrogenolysis}, issn = {1011-372X}, doi = {10.1007/s10562-010-0276-5}, author = {Mane, Rasika B. and Hengne, Amol M. and Ghalwadkar, Ajay A. and Vijayanand, Subramanian and Mohite, Pravin H. and Potdar, Hari S. and Rode, Chandrashekhar V.} } @article { ISI:000281754000029, title = {DFT Study of lewis base interactions with the MgCl2 surface in the ziegler-natta catalytic system: expanding the role of the donors}, journal = {Journal of Physical Chemistry C}, volume = {114}, number = {37}, year = {2010}, month = {SEP}, pages = {15771-15781}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We present a computational study, using density functional theory, of the role of internal and external donors in supported heterogeneous Ziegler-Natta polymerization catalyst systems. The focus of the investigation is the ability of the donors to stabilize the MgCl2 support through the zip mode of coordination. Phthalates and alkoxy benzoates have been considered as representative internal and external donors, respectively. Models for the alpha (ccp) and the beta (hcp) phases of the (110) MgCl2 lateral cut have been considered. Studies were first done with a {\textquoteleft}{\textquoteleft}Fully Fixed Model{\textquoteright}{\textquoteright}, where the atoms in the MgCl2 lateral cuts were kept fixed. The studies indicated that the phthalate donors would preferentially stabilize the alpha phase of MgCl2, while the alkoxy benzoate donors would stabilize the beta phase more, corroborating experimental results. A comparison of the zip coordination mode with other modes of coordination (mono, chelate, and bridge) indicates that it would be preferred over the mono and chelate coordination modes and be competitive with the bridge coordination mode. The validity of the Fully Fixed Model was then tested by doing calculations with the Partially Relaxed (some of the magnesium and chlorine atoms unfixed) and the Fully Relaxed (all atoms free) Models. The results from the latter two models corrected some of the discrepancies that had been observed for the Fully Fixed Model in comparison to previous experimental and computational investigations but were in general agreement with the Fully Fixed Model, indicating that the overall conclusions drawn with the earlier model are correct. Insertion studies done on an octahedrally coordinated titanium site flanked by two zip-coordinated phthalate donor molecules indicated that the zip-coordinating donors can confer exceptional regioselectivity to the titanium center. A list of potential donors that could serve as external donors, with di-iso-butyl phthalate (DIBP) as the internal donor, was investigated, and it was found that 1,3-diethers would serve as the best external donors to DIBP.

}, issn = {1932-7447}, doi = {10.1021/jp106673b}, author = {Vanka, Kumar and Singh, Gurmeet and Iyer, Divya and Gupta, Virendra K.} } @article { ISI:000284386100046, title = {Direct transfer of micro-molded electrodes for enhanced mass transport and water management in PEMFC}, journal = {Electrochemistry Communications}, volume = {12}, number = {11}, year = {2010}, month = {NOV}, pages = {1638-1641}, publisher = {ELSEVIER SCIENCE INC}, address = {360 PARK AVE SOUTH, NEW YORK, NY 10010-1710 USA}, abstract = {

Soft lithography technique is used to micropattern the electrodes on the electrolyte membrane of polymer electrolyte fuel cell (PEMFC) in order to alleviate the issues due to poor water management and inadequate reactant distribution in the fuel cell environment. Membrane electrode assembly with the micropatterned electrode has shown an increase in power density at a higher temperature as well as at a higher relative humidity when compared to a flat electrode. Consistency in cell performance is observed in the case of micropatterned electrodes. (C) 2010 Elsevier B.V. All rights reserved.

}, keywords = {Bipolar plate-less PEM fuel cell, Micropatterned electrodes, Microtransfer molding, Soft lithography}, issn = {1388-2481}, doi = {10.1016/j.elecom.2010.09.015}, author = {Deshmukh, Ashvini B. and Kale, Vinayak S. and Dhavale, Vishal M. and Sreekumar, K. and Vijayamohanan, K. and Shelke, Manjusha V.} } @article { ISI:000278534900028, title = {D-(-)-Lactic acid production from cellobiose and cellulose by Lactobacillus lactis mutant RM2-24}, journal = {Green Chemistry}, volume = {12}, number = {6}, year = {2010}, month = {MAY}, pages = {1106-1109}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Lactobacillus lactis mutant RM2-24 utilizes cellobiose efficiently, converting it into D-(-)-lactic acid. Cellobiose-degrading enzyme activities were determined for whole cells, cell extracts and disrupted cells. Aryl-beta-glucosidase activity was detected in whole cells and disrupted cells, suggesting that these activities are confined to the cells. The mutant produced 80 g l(-1) of lactic acid from 100 g l(-1) of cellobiose with 1.66 g l(-1) h(-1) productivity. Production of D-lactic acid from different cellulose samples was also studied. The cellulose samples at high concentration (10\%) were hydrolyzed by cellulase enzyme preparation (10 FPU g(-1) cellulose) derived from Penicillium janthinellum mutant EU1 generated in our own laboratory. We obtained a maximum 72\% hydrolysis, yielding glucose and cellobiose as the main end products. Lactic acid was produced from these cellulose samples by simultaneous sacchari. cation and fermentation (SSF) in a media containing a cellulase enzyme preparation derived from Penicillium janthinellum mutant EU1 and cellobiose utilizing Lactobacillus lactis mutant RM2-24. A maximum lactic acid concentration of 73 g l(-1) was produced from a concentration of 100 g l(-1) of bagasse-derived cellulose, the highest productivity and yield being 1.52 g l(-1) h(-1) and 0.73 g g(-1), respectively. Considering that bagasse is a waste material available in abundance, we propose to use this biomass to produce cellulose and then sugars, which can be fermented to valuable products such as ethanol and lactic acid.

}, issn = {1463-9262}, doi = {10.1039/b925975a}, author = {Singhvi, Mamta and Joshi, Dipti and Adsul, Mukund G. and Varma, Anjanikumar and Gokhale, Digambar V.} } @article { ISI:000274269700021, title = {Effect of reduced particle size on the magnetic properties of chemically synthesized BiFeO3 nanocrystals}, journal = {Journal of Physical Chemistry C}, volume = {114}, number = {5}, year = {2010}, month = {FEB}, pages = {2108-2115}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Here, we report the effect of reduction in particle size on the temperature dependent magnetization of chemically synthesized BiFeO3 nanocrystals with average grain size of 55 nm. The X-ray photoelectron spectroscopy results show a significant broadening of binding energy peaks associated to Fe3+ 2p(3/2) core levels due to the reduced size. Additionally, due to the nanosize effect, the M-H loops show a significant coercivity starting from 390 K with an anomaly located in the vicinity of 150 K in our H-c vs T as well as M-r/M-s(50 kOe) vs T curves. At this temperature, both H-c and M-r/M-s(50 kOe) undergo minima. Additionally, our results for the first time show the evidence of existence of a low temperature anomaly due to spin-glass transition in the range from 40-44 K in the field cooled magnetization curves. In bulk single crystals, this transition is reported to be situated at around 50 K, however, this transition remained so far undiscovered in the recent studies on BiFeO3 nanoparticles due to the insufficient temperature resolution. The significant shift in this transition toward lower temperature can be attributed to size dependent effects. Our results clearly present new information on the size dependent properties of BiFeO3 nanoparticles.

}, issn = {1932-7447}, doi = {10.1021/jp910745g}, author = {Jaiswal, Adhish and Das, Raja and Vivekanand, K. and Abraham, Priya Mary and Adyanthaya, Suguna D. and Poddar, Pankaj} } @article {43206, title = {Efficient synthesis of varenicline}, journal = {Tetrahedron Letters}, volume = {51}, year = {2010}, month = {JAN}, pages = {151-152}, abstract = {Synthesis of varenicline the antismoking drug has been achieved in six steps with 10\% overall yield. A Diels-Alder reaction, oxidative cleavage of an olefin and reductive amination remain as key steps in the synthesis (C) 2009 Elsevier Ltd. All rights reserved.}, doi = {10.1016/j.tetlet.2009.10.107}, author = {Pasikanti, Srinivas and Reddy, D. Srinivasa and Venkatesham, B. and Dubey, P. K. and Iqbal, Javed and Das, Parthasarathi} } @article {43205, title = {Enantiospecific synthesis of sex pheromone of the obscure mealybug from pantolactone via tandem conjugate addition/cyclization}, journal = {Tetrahedron Letters}, volume = {51}, year = {2010}, month = {OCT}, pages = {5291-5293}, abstract = {An efficient synthesis of an enantiomer of insect{\textquoteright}s natural pheromone is reported starting from chiral pool D-(-)-pantolactone. Highly stereoselective tandem conjugate addition/cyclization sequence and hydrogenation of exocyclic double bond are the key steps in the present synthesis. (C) 2010 Elsevier Ltd. All rights reserved.}, doi = {10.1016/j.tetlet.2010.07.166}, author = {Hajare, Atul K. and Datrange, Laxmikant S. and Vyas, Samir and Bhuniya, Debnath and Reddy, D. Srinivasa} } @article { ISI:000274459600009, title = {Evidence for the co-existence of distorted tetrahedral and trigonal bipyramidal aluminium sites in SrAl12O19 from Al-27 NMR studies}, journal = {Solid State Communications}, volume = {150}, number = {5-6}, year = {2010}, month = {JAN}, pages = {262-266}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

Strontium aluminate, SrAl12O19, is a ceramic material having the hexagonal magnetoplumbite-type structure, with multiple Al coordination environments. An earlier low-field Al-27 solid-state NMR study reported five different Al sites in this system: one AlO4, one AlO5, and three AlO6 sites; whereas a later high-field study showed that the AlO5 site is a distorted AlO4 site with a very large quadrupolar coupling constant (similar to 20 MHz). Our magic angle spinning (MAS) and 3-quantum magic angle spinning (3QMAS) NMR studies at 7.05 T unambiguously show evidence for an AlO5 site. However, evidence for the presence of a distorted AlO4 site is obtained from studies at high fields (16.4 and 17.6 T), in addition to the AlO5 site. Thus the present solid-state NMR studies give evidence for the simultaneous presence of both the five-coordinated and distorted four-coordinated sites in this system. (C) 2009 Elsevier Ltd. All rights reserved.

}, keywords = {Local structure, MQMAS, Nuclear magnetic resonance, Strontium aluminate}, issn = {0038-1098}, doi = {10.1016/j.ssc.2009.11.008}, author = {Harindranath, K. and Viswanath, K. Anusree and Chandran, C. Vinod and Braeuniger, Thomas and Madhu, Perunthiruthy K. and Ajithkumar, Thalasseril G. and Joy, Pattayil Alias} } @article { ISI:000284238000010, title = {Fabrication of homogeneous nanoparticle/nanoneedle BaTiO3 and Ba0.8Sr0.2TiO3 smooth thin films by simple dip coating}, journal = {International Journal of Nanotechnology}, volume = {7}, number = {9-12, SI}, year = {2010}, month = {DEC}, pages = {919-931}, publisher = {INDERSCIENCE ENTERPRISES LTD}, address = {WORLD TRADE CENTER BLDG, 29 ROUTE DE PRE-BOIS, CASE POSTALE 896, CH-1215 GENEVA, SWITZERLAND}, abstract = {

Ferroelectric BaTiO3 (BTO) and Ba0.8Sr0.2TiO3 (BSTO) thin film materials have been successfully prepared by sol-gel processing and simple dip coating on glass and silicon supports. Above thin films were characterised by x-ray diffraction (XRD), Raman spectroscopy, photoelectron spectroscopy, thermal analysis, atomic force microscopy (AFM) and spectroscopic ellipsometry. Phase identification of BaTiO3 and Ba0.8Sr0.2TiO3 was performed by XRD. XRD and Raman spectroscopy investigations demonstrate that thc Ba0.8Sr0.2TiO3 film exhibits tetragonal structure. AFM analysis demonstrates the elongated nanospherical particles on glass substrate and nanowires on silicon substrate, which represent a strong influence of the crystallinity of underlying substrate on the grain morphology in this technique. The thin films on both the substrates are uniformly coated without any pinhole to significant area (similar to 2.5 cm(2)), and this method might be extended to large area uniform coating. Spectroscopic ellipsometric measurements reveal the exact thickness, refractive index and extinction coefficient of the thin films.

}, keywords = {barium strontium titanate, barium titanate, dip coating, fabrication, ferroelectric material, large area coating, nanotechnology, thin film}, issn = {1475-7435}, author = {Saini, Mamta and Vivekanand, K. and Poddar, Pankaj and Murty, K. V. G. K. and Thushara, K. S. and Gopinath, Chinnakonda S.} } @article { ISI:000272936000061, title = {Fluconazole analogues containing 2H-1,4-benzothiazin-3(4H)-one or 2H-1,4-benzoxazin-3(4H)-one moieties, a novel class of anti-Candida agents}, journal = {Bioorganic \& Medicinal Chemistry Letters}, volume = {20}, number = {2}, year = {2010}, month = {JAN}, pages = {722-725}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

As a part of our program to develop new antifungal agents, a series of fluconazole analogues was designed and synthesized wherein one of the triazole moieties in fluconazole was replaced with 2H-1,4-benzothiazin-3(4H)-one or 2H-1,4-benzoxazin-3(4H)-one moiety. The new chemical entities thus synthesized were screened against various fungi and it was observed that the compounds 4a and 4i are potent inhibitors of Candida strains. The structure-activity relationship for these compounds is discussed. (C) 2009 Elsevier Ltd. All rights reserved.

}, keywords = {antifungal, Benzothiazinone, Benzoxazinone, Fluconazole}, issn = {0960-894X}, doi = {10.1016/j.bmcl.2009.11.071}, author = {Borate, Hanumant B. and Maujan, Suleman R. and Sawargave, Sangmeshwer P. and Chandavarkar, Mohan A. and Vaiude, Sharangi R. and Joshi, Vinay A. and Wakharkar, Radhika D. and Iyer, Ramki and Kelkar, Ramesh G. and Chavan, Subhash P. and Kunte, Sunita S.} } @article { ISI:000274954400005, title = {Gas-phase oxidant-free oxidation of cyclohexanol over V2O5-MoO3-M2O (M = Na, K, Cs) catalysts}, journal = {Indian Journal of Chemical Technology}, volume = {17}, number = {1}, year = {2010}, month = {JAN}, pages = {43-49}, publisher = {NATL INST SCIENCE COMMUNICATION-NISCAIR}, address = {DR K S KRISHNAN MARG, PUSA CAMPUS, NEW DELHI 110 012, INDIA}, abstract = {

Oxidant-free oxidation (dehydrogenation) of cyclohexanol is carried out in a down-flow integral laboratory scale reactor using different alkali doped catalysts. The effect of reaction temperature, contact time (W/F) and doping of alkali metals is studied to check its effect on nature of prominent products of the reaction (cyclohexanone and cyclohexene). At lower temperature the cyclohexanone prevails whereas at higher temperature cyclohexene is observed in prominence. Acid-modified catalysts (with boron and phosphorous) facilitated cyclohexene selectivity whereas alkali modified catalysts facilitated cyclohexanone selectivity. Calcination of sodium modified catalyst at different temperatures under static condition affect characteristic phase intensity and cyclohexanone selectivity. XRD investigation showed formation of different inorganic phases as the characteristic of dopant. Cesium modified catalyst showed better dehydrogenation activity.

}, keywords = {Cyclohexanol, dehydration, Dehydrogenation, Electronegativity, V2O5-MoO3}, issn = {0971-457X}, author = {Vyawahare, Y. K. and Chumbhale, Vilas R. and Pardhy, S. A. and Samuel, V. and Aswar, A. S.} } @article { ISI:000285370100021, title = {In situ, on-resin synthesis of 8-Br/NH2 adeninyl peptide nucleic acid (PNA) oligomers and complementation studies with DNA}, journal = {Tetrahedron Letters}, volume = {51}, number = {50}, year = {2010}, month = {DEC}, pages = {6560-6564}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

A new, novel and efficient in situ synthesis of 8-aminoadeninyl PNA oligomers from corresponding 8-bromoadeninyl PNA oligomers is reported. The study of hybridisation properties of (8-Br/8-NH2) PNA oligomers with cDNA reveals substitution-site dependent stabilization of derived triplexes and duplexes. (C) 2010 Elsevier Ltd. All rights reserved.

}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2010.10.040}, author = {Vysabhattar, Raman and Ganesh, Krishna N.} } @article { ISI:000273689600061, title = {Magnetic and dielectric properties and Raman spectroscopy of GdCrO3 nanoparticles}, journal = {Journal of Applied Physics}, volume = {107}, number = {1}, year = {2010}, month = {JAN}, pages = {013912}, publisher = {AMER INST PHYSICS}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

The rare earth orthochromites are extremely interesting due to the richness of their optical, dielectric, and magnetic properties as well as due to their multiferroic properties which make them suitable materials to study in the nanoregime. However, the wet-chemical synthesis of these materials in nanosize is nontrivial. Here, we report for the first time, the detailed Raman spectra as well as magnetic and dielectric properties of chemically synthesized GdCrO3 nanoparticles of size ranging from 40 to 60 nm. The magnetic properties are dictated by competing Cr3+-Cr3+, Gd3+-Cr3+, and Gd3+-Gd3+ superexchange interactions in different temperature regions, resulting into an antiferromagnetic ordering at 167 K due to the Cr3+-Cr3+ followed by weak ferromagnetic ordering due to the onset of Cr3+-Gd3+ interactions. At lower temperature, it shows weak antiferromagnetic ordering due to Gd3+-Gd3+ interaction. Below 95 K, GdCrO3 nanoparticles showed the presence of negative magnetization due to Gd3+ and Cr3+ interactions resulting into weak ferromagnetic coupling. The Raman spectroscopy shows the characteristic Raman shifts indicating that below 450 cm(-1), Gd3+ ions play a dominant role in determining the phonon frequencies of GdCrO3, and above 450 cm(-1), the Cr+3 ions dominate. We also present for the first time the low temperature dielectric constant and loss tangent data for GdCrO3 in a broad temperature and frequency range. The dielectric constant shows a decrease in comparison to the bulk values due to the size dependent effects. It also shows a peak centered at around 320 K above which it shows a sharp decrease. The dielectric loss value in GdCrO3 nanoparticles is quite small and shows an interesting frequency dependent anomaly at lower temperature which might be due to the coupling between magnetic and dielectric order parameters.

}, keywords = {dielectric losses, gadolinium compounds, Magnetisation, Multiferroics, nanofabrication, Nanoparticles, permittivity, phonons, Raman spectra, superexchange interactions}, issn = {0021-8979}, doi = {10.1063/1.3275926}, author = {Jaiswal, Adhish and Das, Raja and Vivekanand, K. and Maity, Tuhin and Abraham, Priya Mary and Adyanthaya, Suguna D. and Poddar, Pankaj} } @article { ISI:000277280500019, title = {Measurements and molecular interactions for N,N-dimethylformamide with ionic liquid mixed solvents}, journal = {Journal of Physical Chemistry B}, volume = {114}, number = {18}, year = {2010}, month = {MAY}, pages = {6126-6133}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

To understand the molecular interactions between N,N-dimethylformamide (DMF) with two families of ionic liquids (ILs), we have measured thermophysical properties such as densities (rho) and ultrasonic sound velocities (a) over the whole composition range at 25 degrees C under atmospheric pressure. The excess molar volume (V(E)) and the deviation in isentropic compressibilities (Delta K(s)) were predicted using these properties as a function of the concentration of IL. These results are fitted to the Redlich-Kister polynomials. The materials investigated in the present study included two families of ILs such as ammonium salts and imidazolium salts. Diethylammonium acetate ([Et(2)NH][CH(3)COO], DEAA), triethylammonium actetate ([Et(3)NH][CH(3)COO], TEAA), triethylammonium dihydogen phosphate ([Et(3)NH][H(2)PO(4)], TEAP), and triethylammonium sulfate ([Et(3)NH][HSO(4)], TEAS) are ammonium salts and l-benzy1-3-methylimidazolium chloride (Bmiml[Cl]) belongs to the imidazolium family. The intermolecular interactions and structural effects were analyzed on the basis of the measured and the derived properties. A qualitative analysis of the results is discussed in terms of the ion dipole, ion-pair interactions, and hydrogen bonding between ILs and DMF molecules and their structural factors.

}, issn = {1520-6106}, doi = {10.1021/jp101209}, author = {Attri, Pankaj and Reddy, P. Madhusudan and Venkatesu, P. and Kumar, Anil and Hofman, T.} } @article { ISI:000274375500003, title = {Molecular cloning, over expression, and activity studies of a peptidic HIV-1 protease inhibitor: designed synthetic gene to functional recombinant peptide}, journal = {Peptides}, volume = {31}, number = {1}, year = {2010}, month = {JAN}, pages = {16-21}, publisher = {ELSEVIER SCIENCE INC}, address = {360 PARK AVE SOUTH, NEW YORK, NY 10010-1710 USA}, abstract = {

The aspartic protease inhibitor (ATBI) purified from a Bacillus sp. is a potent inhibitor of several proteases including recombinant HIV-1 protease, pepsin, and fungal aspartic protease. In this study, we report the cloning, and over expression of a synthetic gene coding for ATBI in Escherichia coli and establish a purification Protocol. The ATBI molecule consists of eleven amino acids and is peptidic in nature. We used the peptide sequence data of ATBI to synthesize complementary oligonucleotides, which were annealed and subsequently cloned in-frame with the gene for glutathione-S-transferase (GST). The expression of the resulting fusion protein was induced in E. coli BL21-A1 cells using arabinose. The recombinant peptide was Purified using a reduced glutathione column, and cleaved with Factor Xa to remove the GST tag. The resultant product was further purified to homogeneity using RP-HPLC. Mass spectroscopy analysis revealed that the purified peptide had a molecular weight of 1186 Da which matches the theoretical molecular weight of the amino acids present in the synthetic gene. The recombinant peptide was found to be active in vitro against HIV-1 protease, pepsin, and fungal aspartic protease. The protocol described in this study may be used to clone pharmaceutically important peptide molecules. (C) 2009 Elsevier Inc. All rights reserved.

}, keywords = {Gateway cloning, HIV-1 protease, inhibitor, Proteases, Synthetic gene}, issn = {0196-9781}, doi = {10.1016/j.peptides.2009.09.034}, author = {Vathipadiekal, Vinod and Umasankar, Perunthottathu K. and Patole, Milind S. and Rao, Mala} } @article { ISI:000281058900005, title = {Nanogold-Loaded sharp-edged carbon bullets as plant-gene carriers}, journal = {Advanced Functional Materials}, volume = {20}, number = {15}, year = {2010}, month = {AUG}, pages = {2416-2423}, publisher = {WILEY-V C H VERLAG GMBH}, address = {PO BOX 10 11 61, D-69451 WEINHEIM, GERMANY}, abstract = {

The higher DNA delivery efficiency into plants by gold nanoparticles embedded in sharp carbonaceous carriers is demonstrated. These nanogold-embedded carbon matrices are prepared by heat treatment of biogenic intracellular gold nanoparticles. The DNA-delivery efficiency is tested on a model plant, Nicotiana tabacum, and is further extended to the monocot, Oryza sativa, and a hard dicot tree species, Leucaena leucocephala. These materials reveal good dispersion of the transport material, producing a greater number of GUS foci per unit area. The added advantages of the composite carrier are the lower plasmid and gold requirements. Plant-cell damage with the carbon-supported particles is very minimal and can be, gauged from the increased plant regeneration and transformation efficiency compared with that of the commercial micrometer-sized gold particles. This is ascribed to the sharp edges that the carbon supports possess, which lead to better piercing capabilities with minimum damage.

}, issn = {1616-301X}, doi = {10.1002/adfm.200901883}, author = {Vijayakumar, Periyasamy S. and Othalathara U. Abhilash and Khan, Bashir Mohammad and Bhagavatula L. V. Prasad} } @article { ISI:000279514400059, title = {Nanoscale modulation of electronic states across unit cell steps on the surface of an epitaxial colossal magnetoresistance manganite film}, journal = {Applied Physics Letters}, volume = {96}, number = {26}, year = {2010}, month = {JUN}, pages = {Article No. 263108}, publisher = {AMER INST PHYSICS}, type = {Article}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

The nature of electronic states near the edge of unit cell steps on the surface of epitaxial La(0.7)Sr(0.3)MnO(3) (LSMO) thin films grown by real-time reflection high energy electron diffraction monitored pulsed laser deposition is examined by scanning tunneling microscopy and scanning tunneling spectroscopy techniques. It is observed that the electronic states are strongly modulated near the step edge with considerably high gap at the edge and low gap on the terrace. This modulation weakens at low temperature. The temperature evolution of the density of states and the nature of gap in deep metallic state of LSMO are also discussed. (C) 2010 American Institute of Physics. [doi:10.1063/1.3455886]

}, keywords = {colossal magnetoresistance, electronic density of states, lanthanum compounds, magnetic epitaxial layers, Nanostructured materials, pulsed laser deposition, reflection high energy electron diffraction, scanning tunnelling microscopy, scanning tunnelling spectroscopy, strontium compounds}, issn = {0003-6951}, doi = {10.1063/1.3455886}, author = {Rana, Abhimanyu and Bogle, Kashinath A. and Game, Onkar S. and Patil, Shankar and Valanoor, Nagarajan and Ogale, Satishchandra B.} } @article { ISI:000279958200023, title = {Nitrophenoxy groups containing polybenzimidazoles as polymer electrolytes for fuel cells: synthesis and characterization}, journal = {Journal of Applied Polymer Science}, volume = {117}, number = {6}, year = {2010}, month = {SEP}, pages = {3282-3292}, publisher = {JOHN WILEY \& SONS INC}, address = {111 RIVER ST, HOBOKEN, NJ 07030 USA}, abstract = {

Polybenzimidazoles containing different contents of pendant nitrophenoxy groups were prepared by condensation of 3,3{\textquoteright}-diamino-benzidine with a mixture of 3,5-dicarboxyl-4{\textquoteright}-nitro diphenyl ether and isophthalic acid (IPA) in different ratios in polyphosphoric acid. The polymers are soluble in polar aprotic solvents, they have inherent viscosities in the range of 0.75-1.10 dL g(-1) and they form tough and transparent films on solution casting. They have good thermal stability with initial decomposition temperature ranging from 380 to 416 degrees C in nitrogen, good tensile strength ranging from 56 to 65 MPa and reasonably good oxidative stability. Phosphoric acid uptake of these polymers is low compared with PBI and membranes doped with phosphoric acid exhibit good proton conductivity in the range of 6.6x 10(-3) to 1.9x 10(-2) S/cm at 25 degrees C and 1.2x 10(-2) to 4.9x 10(-2) S/cm at 175 degrees C, compared with 3.9x 10(-3) S/cm at 25 degrees C and 3.2x 10(-2) S/cm at 175 degrees C for PBI. These membranes are suitable for applications as polymer electrolyte for fuel cell and presumably for gas separation at high temperature. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117: 3282-3292, 2010

}, keywords = {Characterization, membranes, pendant nitrophenoxy group, polybenzimidazoles, proton conductivity, synthesis}, issn = {0021-8995}, doi = {10.1002/app.30279}, author = {Kulkarni, Mahesh and Potrekar, Ravindra and Kulkarni, R. A. and Vernekar, S. P.} } @article {43241, title = {Non-covalent interactions in extended systems described by the effective fragment potential method: theory and application to nucleobase oligomers}, journal = {Journal of Physical Chemistry A}, volume = {114}, year = {2010}, month = {NOV}, abstract = {The implementation of the effective fragment potential (EFP) method within the Q-CHEM electronic structure package is presented. The EFP method is used to study noncovalent π-π and hydrogen-bonding interactions in DNA strands. Since EFP is a computationally inexpensive alternative to high-level ab initio calculations, it is possible to go beyond the dimers of nucleic acid bases and to investigate the asymptotic behavior of different components of the total interaction energy. The calculations demonstrated that the dispersion energy is a leading component in π-stacked oligomers of all sizes. Exchange-repulsion energy also plays an important role. The contribution of polarization is small in these systems, whereas the magnitude of electrostatics varies. Pairwise fragment interactions (i.e., the sum of dimer binding energies) were found to be a good approximation for the oligomer energy.}, author = {Ghosh, Debashree and Kosenkov, Dmytro and Vanovschi, Vitalii and Williams, Christopher F. and Herbert, John M. and Gordon, Mark S. and Schmidt, Michael W. and Slipchenko, Lyudmila V. and Krylov, Anna I.} } @article { ISI:000274292700015, title = {Polymer-supported palladium-imidazole complex catalyst for hydrogenation of substituted benzylideneanilines}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {317}, number = {1-2}, year = {2010}, month = {FEB}, pages = {111-117}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The polymer-supported palladium-imidazole complex catalyst was synthesized and characterized by various techniques Such as elemental analysis, IR spectroscopy and TG analysis. The physico-chemical properties such as bulk density, Surface studies by BET method and swelling studies of catalyst in different solvents were investigated. XPS Studies were carried out to identify the oxidation state of palladium in the catalyst. The morphology of the support and the catalyst was studied using scanning electron microscope. Using the synthesized catalyst, hydrogenation of benzylideneaniline and a few of its para Substituted derivatives was carried out at ambient conditions. The influence of variation in temperature, concentration of the catalyst as well as the substrate on the rate of reaction Was Studied. The catalyst showed an excellent recycling efficiency over six cycles without leaching of metal from the polymer support. (C) 2009 Elsevier B.V. All rights reserved.

}, keywords = {Benzylideneaniline, Hydrogenation, kinetics, Polymer-supported palladium-imidazole complex catalyst}, issn = {1381-1169}, doi = {10.1016/j.molcata.2009.10.030}, author = {Udayakumar, V. and Alexander, S. and Gayathri, V. and Shivakumaraiah and Patil, K. R. and Viswanathan, B.} } @article { ISI:000282444000036, title = {Production of single cell protein, essential amino acids, and xylanase by penicillium janthinellum}, journal = {Bioresources}, volume = {5}, number = {4}, year = {2010}, month = {OCT}, pages = {2470-2477}, publisher = {NORTH CAROLINA STATE UNIV DEPT WOOD \& PAPER SCI}, address = {CAMPUS BOX 8005, RALEIGH, NC 27695-8005 USA}, abstract = {

Microbial biomass having 46\% crude protein content and enriched with essential amino acids as well as extracellular xylanase activity (100-150 IU/ml) was produced by an efficient fungal strain, Penicillium janthinellum (NCIM St-F-3b). Optimization studies for maximum xylanase and biomass production showed that the fungus required a simple medium containing bagasse hemicellulose as carbon source and ammonium sulphate as the nitrogen source. Therefore bagasse, which is a waste product of the sugar industry, can be efficiently used in microbioal biomass protein preparation for animal feed.

}, keywords = {Bagasse hydrolysate, Crude protein, Microbial biomass production, Penicillium janthinellum, Xylanase}, issn = {1930-2126}, author = {Rao, Mala and Varma, Anjanikumar and Deshmukh, Sumedha S.} } @article { ISI:000275985700041, title = {Pt-MoOx-carbon nanotube redox couple based electrocatalyst as a potential partner with polybenzimidazole membrane for high temperature polymer electrolyte membrane fuel cell applications}, journal = {Electrochimica Acta}, volume = {55}, number = {8}, year = {2010}, month = {MAR}, pages = {2878-2887}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

A redox couple based electrocatalyst comprising of Pt-Multi Wall Carbon NanoTube (Pt-MWCNT) promoted with molybdenum oxide (MoOx, 2 \< x \< 3) nanoparticles was prepared. The objective was to effectively organize the Pt-MoOx interface on the smooth MWCNT surface to overcome the practical difficulties associated with establishing such interface with Pt dispersed on carbon morphologies possessing surface irregularities. The present study revealed the importance of stringent controlling of the additive level for maintaining a balanced bifunctional behavior of the catalyst combination through the synergistic effects by the components and the need of a proton conducting membrane operable at high temperature to get better output from the Polymer Electrolyte Membrane Fuel Cell (PEMFC) systems. An indigenously developed polybenzimidazole (PBI) membrane was used to fabricate a membrane electrode assembly (MEA) as it can be operated at higher temperatures compared to that of Nafion membranes. MoOx additive level was carefully controlled by monitoring the active Pt area by cyclic voltammetry. All prepared electrocatalysts were characterized by using HRTEM, XRD and XPS to get information on dispersion and morphology, crystalinity and oxidation state of different elements, respectively. The system prepared with 5\% MoOx addition with respect to Pt (hereafter Pt-MoOx(5\%)-MWCNT) displayed balanced active Pt area and excellent oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) activities. Rotating Disk Electrode (ROE) system was extensively utilized to understand the ORR kinetics and the favorable role of MoOx as the promoter in the reaction. The kinetic current (j(k)) measured at 0.02 V vs. Hg/Hg2SO4 electrode from the Koutecky-Levich plots was 9 times higher and the apparent activation energy during single cell evaluation was 27 kJ/mol lower for the MoOx promoted system, compared to the system without the additive. A higher operating temperature significantly favored the cell performance by a combined effect of enhancement in proton conductivity of the PBI membrane and possible kinetic benefit by the well postulated oxygen spill over effect by the MoOx type systems in some combinations involving such systems. (C) 2010 Elsevier Ltd. All rights reserved.

}, keywords = {Methanol oxidation reaction, MWCNT, oxygen reduction reaction, PBI membrane, PEMFC}, issn = {0013-4686}, doi = {10.1016/j.electacta.2010.01.012}, author = {Vellacheri, Ranjith and Unni, SreeKuttan M. and Nahire, Sandip and Kharul, Ulhas K. and Kurungot, Sreekumar} } @article { ISI:000281175500059, title = {Simple chemical co-precipitation/calcination route for the synthesis of simulated synroc-B and synroc-C powders}, journal = {Materials Chemistry and Physics}, volume = {123}, number = {2-3}, year = {2010}, month = {OCT}, pages = {695-699}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

A simple chemical co-precipitation/calcination route was developed for the synthesis of simulated synroc-B and synroc-C powders using mostly nitrate salts as starting chemicals and 20\% ammonia solution as precipitant. In this route, a mixed solution containing Al-nitrate, Ca-nitrate, Ba-nitrate, zirconyl nitrate and titanyl nitrate in the molar proportion required for synroc-B is added to dilute ammonia solution to precipitate these cations in the form of their hydroxides at room temperature by maintaining pH approximate to 10.5 during precipitation. Formation of a major fluorite phase with minor amounts of anatase, rutile and hollandite phases is observed in the powder obtained after calcination in air at 750 degrees C. Multiphase crystalline synroc-B matrix containing hollandite, perovskite, zirconolite, and rutile phases is obtained after sintering the heat treated powder in the form of pellets at 1230 degrees C for 4h in air. Similarly, pure synroc-C phases with 14 and 20\% simulated waste loadings were synthesized following the same synthesis protocol. These pre-treated powders with a high surface area of similar to 25 m(2) g(-1) gave sintered ceramics having density of similar to 90\% for 14 and 20\% waste loadings. (C) 2010 Elsevier B.V. All rights reserved.

}, keywords = {Ceramics, Chemical synthesis, Oxides, Sintering}, issn = {0254-0584}, doi = {10.1016/j.matchemphys.2010.05.039}, author = {Potdar, H. S. and Vijayanand, S. and Mohaideen, Kamal Khaja and Patil, K. R. and Joy, Pattayil Alias and Madhavan, R. Raja and Kutty, K. V. G. and Ambashta, Ritu D. and Wattal, P. K.} } @proceedings {42678, title = {On some aspects of fock-space multi-reference coupled-cluster singles and doubles energies and optical properties}, volume = {11}, year = {2010}, month = {APR}, pages = {375-393}, publisher = {Springer}, address = {Netherlands}, author = {Manohar, Prashant Uday and Shamasundar, K. R. and Bag, Arijit and Vaval, Nayana and Pal, Sourav} } @article { ISI:000275049800051, title = {Structural diversity in partially fluorinated metal organic frameworks (F-MOFs) composed of divalent transition metals, 1,10-phenanthroline, and fluorinated carboxylic acid}, journal = {Crystal Growth \& Design}, volume = {10}, number = {3}, year = {2010}, month = {MAR}, pages = {1351-1363}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Seven new partially fluorinated metal-organic frameworks (F-MOFs) have been synthesized under different solvothermal conditions (H(2)O or N,N-dimethylformamide (DMF)) from transition metal cations [Zn(II), Co(II), and Mn(II)], 1,10-phenanthroline (phen), and 4,4{\textquoteright}-(hexafluoroisopropylidene) bis(benzoic acid) (C(17)H(10)F(6)O(4), H(2)hfbba) to determine the influence of reaction conditions on the formation of metal-organic frameworks. This family of materials displays a striking degree of structural similarity depending on the solvent of synthesis. Of the seven materials, two contain three-dimensional connectivity: Co(3)(hfbba)(6)(phen)(2) (F-MOF-6) and Mn(3)(hfbba)(6)(Phen)(2) (F-MOF-10). Three materials are one-dimensional structures: Zn(hfbba)(0.5)(phen)(HCO(2)) (F-MOF-8), Mn(Hhfbba)(2)(Phen) (F-MOF-11), and [Mn(hfbba)(2)(dm-phen)]center dot(H(2)O) (F-MOF-11A). Lastly, Co(hfbba)(phell)(2)center dot 2(H(2)hfbba)(H(2)O)(HCO(2)) (F-MOF-7) and Zn(hfbba)(phen)(2)center dot 2(H(2)hfbba) (H(2)O)-(HCO(2)) (F-MOF-9) are discrete zero-dimensional molecular complexes. F-MOF-6 and -10, which feature it three-dimensional (3D) framework with pcu topolgy are formed in DMF like F-MOF-8 and at 85 degrees C. The remaining F-MOFs are formed by a solvothermal reaction at 120 degrees C in water. F-MOF-7 and -9 are isostructural discrete zero-dimensional molecular complexes (a similar to 19.5; b similar to 13.7; c similar to 26.2/29.6 angstrom; beta similar to 99.9/120.04; V similar to 6840 angstrom(3)). All these F-MOFs were structurally determined by single-crystal X-ray diffraction. Solid-state properties such its UV-vis and the thermal stability of F-MOF-6 to -11A have also been studied. Insight into the factors influencing the preferred crystallization of a specific complex over others has been obtained from full quantum chemical (QM) calculations using density functional theory (DFT).

}, issn = {1528-7483}, doi = {10.1021/cg9013812}, author = {Pachfule, Pradip and Dey, Chandan and Panda, Tamas and Vanka, Kumar and Banerjee, Rahul} } @article { ISI:000273580700038, title = {Structure, electronic structure, optical, and dehydrogenation catalytic study of (Zn1-zInz)(O1-xNx) solid solution}, journal = {Chemistry of Materials}, volume = {22}, number = {2}, year = {2010}, month = {JAN}, pages = {565-578}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Indium and nitrogen codoping in ZnO leads to a solid solution of InN in ZnO with I composition of(Zn1-zInz)(O1-xNx). A simple solution combustion method has been adopted to prepare the above materials in less than 10 min with metal nitrates as the metal loll source and urea as fuel. With reference to ZnO, significant increase in lattice parameters was observed with increasing In-content. However, the In2O3 phase was Observed along with InN for]it content \>= 10\%. Optical absorption extended into the Visible region, at least LIP to 550 nm, demonstrates an effective reduction of optical band gap due to the formation of solid Solution. A new feature observed just above O2p valence band in X-ray photoelectron spectroscopy (XPS) suggests the creation of N 2p states from InN; the N Is core level XPS result too confirms nitride contribution. Raman spectroscopy and secondary ion mass spectrometry results show direct In-N, Zn-N. and In-N-Zn fragments in (Zn1-zInz)(O1-x,N-x). Catalytic activity explored for Oxidation of 2-butanol to ethyl methyl ketone demonstrates a high selectivity at 350 and 400 degrees C. All of the above characteristics suggest the multifunctional nature of (Zn1-zInz)(O1-xNx) and its potential for other applications.

}, issn = {0897-4756}, doi = {10.1021/cm903368r}, author = {Mapa, Maitri and Sivaranjani, Kumarsrinivasan and Bhange, Deu S. and Saha, Biswajit and Chakraborty, Purushottam and Viswanath, Annamraju Kasi and Gopinath, Chinnakonda S.} } @article { ISI:000276562300063, title = {Synthesis and characterization of poly-L-lysine-grafted silica nanoparticles synthesized via NCA polymerization and click chemistry}, journal = {Langmuir}, volume = {26}, number = {8}, year = {2010}, month = {APR}, pages = {5772-5781}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Polypeptide polymer-grafted silica nanoparticles are of considerable interest because the ordered secondary structure of the polypeptide grafts imparts novel functional properties onto the nanoparticle composite. The synthesis of poly-L-lysine-grafted nanoparticles would be of particular interest because the high density of cationic charges on the surface could lead to many applications such as gene delivery and antimicrobial agents. In this work, we have developed a {\textquoteleft}{\textquoteleft}grafting-to{\textquoteright}{\textquoteright} approach using a combination of NCA polymerization and {\textquoteleft}{\textquoteleft}click chemistry{\textquoteright}{\textquoteright} to synthesize poly-L-lysine-grafted silica nanoparticles with a high graft density of 1 chain/nm(2). The covalent attachment of poly-L-lysine to silica nanoparticles (PLL-silica) was confirmed using a variety of techniques such as C-13 CP MAS NMR, TGA, and IR. This methodology was then extended to graft poly-L-lysine-b-poly-L-leucine copolymer (PLL-b-PLLeu-silica) and poly-L-benzylglutamate (PLUG silica) onto silica nanoparticles. All of these polypeptide-grafted nanoparticles show interesting aggregation properties in solution. The efficacy of PLL-silica and PLL-h-PLLeu-silica as antimicrobial agents was tested on both gram-negative B. cull and grain-positive Bacillus subtilis.

}, issn = {0743-7463}, doi = {10.1021/la903595x}, author = {Kar, Mrityunjov and Vijayakumar, P. S. and Bhagavatula L. V. Prasad and Sen Gupta, Sayam} } @article { ISI:000283110500021, title = {Temperature effect on the molecular interactions between ammonium ionic liquids and N,N-dimethylformamide}, journal = {Journal of Physical Chemistry B}, volume = {114}, number = {42}, year = {2010}, month = {OCT}, pages = {13415-13425}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

In view of the wide scope of molecular interactions between the highly polar compound of N,N-dimethylformamide (DMF) and ammonium ionic liquids (ILs), we have measured thermophysical properties such as densities (rho) and ultrasonic sound velocities (u) over the whole composition range at temperatures ranging from 25 to 50 degrees C under atmospheric pressure. To gain some insight into the several aggregations of molecular interactions present in these mixed solvents, we predicted the excess molar volume (V(E)) and the deviations in isentropic compressibilities (Delta K(s)) as a function of the concentration of IL. These results are fitted to the Redlich-Kister polynomials. The materials investigated in the present study included the hydroxide series of ammonium ILs of tetramethylammonium hydroxide [(CH(3))(4)N][OH] (TMAH), tetraethylammonium hydroxide [(C(2)H(5))(4)N][OH] (TEAH), and tetrapropylammonium hydroxide [(C(2)H(7))(4)N][OH] (TPAH). The intermolecular interactions and structural effects were analyzed on the basis of the measured and the derived properties. A qualitative analysis of the results is discussed in terms of the ion-dipole and ion-pair interactions, and hydrogen bonding between ILs and DMF molecules and their structural factors.

}, issn = {1520-6106}, doi = {10.1021/jp108003x}, author = {Attri, Pankaj and Venkatesu, Pannuru and Kumar, Anil} } @article { ISI:000280070900009, title = {Temperature-dependent raman and dielectric spectroscopy of BiFeO3 nanoparticles: signatures of spin-phonon and magnetoelectric coupling}, journal = {Journal of Physical Chemistry C}, volume = {114}, number = {29}, year = {2010}, month = {JUL}, pages = {12432-12439}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We report the temperature-dependent Raman and dielectric spectroscopy of chemically synthesized BiFeO3 nanoparticles (average size similar to 50-60 nm). The Raman spectra (90-700 K) show two sets of transitions in the lowest Raman E mode, associated with Bi-O bond motion situated in close proximity to the spin reorientation transitions reported for BiFeO3, thereby indicating the existence of possible coupling between magnons and phonons for particle size below the helical order parameter (62 nm). These transitions are slightly shifted in temperature in comparison to the bulk single crystals. We also observe a step-like behavior in Raman peak position around the Neel temperature, suggesting that the phonons are influenced by the magnetic ordering in nanosized BiFeO3. The heat-flow measurements show two sharp endothermic peaks at 1094 and 1223 K representing rhombohedral to orthorhombic or monoclinic transition followed by transition into the cubic phase above 1200K. The low temperature (20-325 K), frequency-dependent (1-10(6) Hz) dielectric constant and loss tangent measurements show that the loss tangent (similar to 10(-3)) and ac conductivity values (similar to 10(-8) Ohm(-1)-cm(-1)) are orders of magnitude lower than the reported values for BiFeO3 ceramics, indicating high levels of ionic purity of our samples. The real part of the permittivity shows a slight reduction in its value (similar to 30) in comparison to the bulk single crystals. Similar to the Stokes Raman shift, its temperature-dependent dielectric constant also shows four weak anomalies at similar to 85, 168, 205, and 230 K situated in close proximity to the spin reorientation transitions, indicating magnetoelectric coupling.

}, issn = {1932-7447}, doi = {10.1021/jp102450z}, author = {Jaiswal, Adhish and Das, Raja and Maity, Tuhin and Vivekanand, K. and Adyanthaya, Suguna D. and Poddar, Pankaj} } @article { ISI:000273709900033, title = {Vice to virtue: intracellular biogenic nanoparticles for the generation of carbon supported catalysts}, journal = {Journal of Nanoscience and Nanotechnology}, volume = {10}, number = {2}, year = {2010}, month = {FEB}, pages = {905-911}, publisher = {AMER SCIENTIFIC PUBLISHERS}, address = {25650 NORTH LEWIS WAY, STEVENSON RANCH, CA 91381-1439 USA}, abstract = {

Intracellular biogenic nanoparticles are considered disadvantageous as the separation of the nanoparticles from the biomass becomes intricate. However realizing the importance of carbon supported catalyst for many important organic reactions we envisaged these nanoparticles as a source for carbon supported catalyst. Herein we demonstrate the heat treatment of intracellular biogenic nanoparticles under inert atmosphere as an efficient method for the preparation of carbon supported metal oxide catalysts. Aspergillus ochraceus, a fungus isolated from foundries, on incubation with K(2)TiF(6) led to the synthesis of intracellular titanium oxide nanoparticles. The nanoparticles embedded biomass upon heat treatment at 600 degrees C in a nitrogen environment gave titanium oxide nanoparticles implanted in a carbonaceous matrix. The material thus formed was characterized using FTIR spectroscopy, Raman spectroscopy, HRTEM and X-ray diffraction. Appreciable benzaldehyde selectivity was observed when styrene oxidation was carried out over such immobilized catalysts. The conversion rate was determined to be 76\% and the benzaldehyde selectivity was greater than 80\%.

}, keywords = {Benzaldehyde Selectivity, Biosynthesis, Carbon Supported Titania, Nanoparticles, Styrene Oxidation}, issn = {1533-4880}, doi = {10.1166/jnn.2010.1894}, author = {Vijayakumar, P. S. and Selvakumar, S. and Gholap, Ramkrishna S. and Singh, A. P. and Bhagavatula L. V. Prasad} } @article { ISI:000276917900011, title = {ZnO-beta zeolite: as an effective and eco-friendly heterogeneous catalyst for the synthesis of benzothiazole derivatives}, journal = {Chinese Chemical Letters}, volume = {21}, number = {4}, year = {2010}, month = {APR}, pages = {421-425}, publisher = {ELSEVIER SCIENCE INC}, address = {360 PARK AVE SOUTH, NEW YORK, NY 10010-1710 USA}, abstract = {

A cheap and recyclable ZnO-beta zeolite was used as catalyst for the synthesis of benzothiazole derivatives. This method provides several advantages such as environmental friendliness, short reaction times, high yields, simple work-up procedure and catalyst was successfully reused for four cycles without significant loss of activity. (C) 2009 Machhindra K. Lande. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

}, keywords = {Benzothiazole, cyclocondensation, heterogeneous catalyst, ZnO-beta zeolite}, issn = {1001-8417}, doi = {10.1016/j.cclet.2009.10.020}, author = {Katkar, Santosh S. and Mohite, Pravinkumar H. and Gadekar, Lakshman S. and Vidhate, Kaluram N. and Lande, Machhindra K.} } @article { ISI:000286890500041, title = {Activity and stability of alpha-chymotrypsin in biocompatible ionic liquids: enzyme refolding by triethyl ammonium acetate}, journal = {Physical Chemistry Chemical Physics}, volume = {13}, number = {7}, year = {2011}, month = {FEB}, pages = {2788-2796}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

In view the of wide scope of structural information of biomolecules in biocompatible ionic liquids (ILs) in various applications including chemical and biochemical, it is essential to study the productive preferential interactions between biological macromolecules and biocompatible ILs. We have therefore explored the stability and activity of alpha-chymotrypsin (CT) in the presence of five ILs from different families, such as triethyl ammonium acetate (TEAA), triethyl ammonium phosphate (TEAP) from ammonium salts, 1-benzyl-3-methylimidazolium chloride ([Bzmim][Cl]), 1-benzyl-3-methylimidazolium tetrafluoroborate ([Bzmim][BF(4)]) from imidazolium salts and tetra-butyl phosphonium bromide (TBPBr) from phosphonium families. Circular dichroism (CD) and UV-vis spectrophotometer experiments were used to study CT stabilization by ILs, related to the associated structural changes and enzyme activity studies, respectively. We observed that all ILs have a dominant contribution to the stabilization of CT. The stability and activity of CT depends on the structural arrangement of the ions of ILs. Our experimental results explicitly elucidate that more hydrophobic imidazolium and phosphonium cations carrying longer alkyl chains of ILs ([Bzmim][Cl], [Bzmim][BF(4)] and TBPBr) were weak stabilizers for CT, while small alkyl chain molecules of triethyl ammonium salts (TEAA and TEAP) are strong stabilizers and therefore more biocompatible for CT stability. Our CD and NMR measurements reveal that TEAA is a refolding additive for CT from a quenched thermal unfolded enzyme structure.

}, issn = {1463-9076}, doi = {10.1039/c0cp01291b}, author = {Attri, Pankaj and Venkatesu, Pannuru and Kumar, Anil} } @article { ISI:000288274200014, title = {Adsorption of cresols on zinc-aluminium hydroxides - a comparison with zeolite-X}, journal = {Separation Science and Technology}, volume = {46}, number = {3}, year = {2011}, month = {JAN}, pages = {PII 934305034}, publisher = {TAYLOR \& FRANCIS INC}, address = {530 WALNUT STREET, STE 850, PHILADELPHIA, PA 19106 USA}, abstract = {

Liquid phase adsorption of m-cresol on Zn-Al hydroxide adsorbents with three different Zn/Al molar ratios was studied in different solvents and compared with commercial zeolite 13X. Among the three adsorbents, ZA-16 showed adsorption capacity similar to commercial zeolite 13X. Solvents used for the preparation of m-cresol solution were found to influence the adsorption capacity. The adsorption capacity was maximum for the solution of m-cresol in n-hexane. Conventional Langmuir and Freundlich adsorption isotherm equations were used to explain the adsorption behavior. The kinetics of m-cresol adsorption followed the first-order Lagergren kinetic model. p-Cresol/m-cresol separation factor was the highest when toluene was used as the organic medium.

}, keywords = {Adsorption, cresol, zeolite, zinc-aluminium hydroxide}, issn = {0149-6395}, doi = {10.1080/01496395.2010.510494}, author = {Vijayakumar, J. and Chikkala, Suresh K. and Mandal, Sujata and Mayadevi, S.} } @article { ISI:000292333103041, title = {Atomic level description of the domain closure in a dimeric enzyme: thermus thermophilus 3-isopropylmalate dehydrogenase (IPMDH)}, journal = {FEBS Journal}, volume = {278}, number = {1, SI}, year = {2011}, note = {36th FEBS Congress of the Biochemistry for Tomorrows Medicine, Torino, ITALY, JUN 25-30, 2011}, month = {JUN}, pages = {458}, publisher = {Federat Soc Biochem \& Mol Biol}, address = {COMMERCE PLACE, 350 MAIN ST, MALDEN 02148, MA USA}, issn = {1742-464X}, author = {Graczer, E. and Merli, Angelo and Singh, R. K. and Karuppasamy, Manikandan and Zavodszky, P. and Weiss, M. S. and Vas, M.} } @article { ISI:000289367200026, title = {Atomic level description of the domain closure in a dimeric enzyme: thermus thermophilus 3-isopropylmalate dehydrogenase}, journal = {Molecular Biosystems}, volume = {7}, number = {5}, year = {2011}, month = {MAR}, pages = {1646-1659}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

The domain closure associated with the catalytic cycle is described at an atomic level, based on pairwise comparison of the X-ray structures of homodimeric Thermus thermophilus isopropylmalate dehydrogenase (IPMDH), and on their detailed molecular graphical analysis. The structures of the apo-form without substrate and in complex with the divalent metal-ion to 1.8 angstrom resolution, in complexes with both Mn(2+) and 3-isopropylmalate (IPM), as well as with both Mn(2+) and NADH, were determined at resolutions ranging from 2.0 to 2.5 angstrom. Single crystal microspectrophotometric measurements demonstrated the presence of a functionally competent protein conformation in the crystal grown in the presence of Mn(2+) and IPM. Structural comparison of the various complexes clearly revealed the relative movement of the two domains within each subunit and allowed the identification of two hinges at the interdomain region: hinge 1 between alpha d and beta F as well as hinge 2 between alpha h and beta E. A detailed analysis of the atomic contacts of the conserved amino acid side-chains suggests a possible operational mechanism of these molecular hinges upon the action of the substrates. The interactions of the protein with Mn(2+) and IPM are mainly responsible for the domain closure: upon binding into the cleft of the interdomain region, the substrate IPM induces a relative movement of the secondary structural elements beta E, beta F, beta G, alpha d and alpha h. A further special feature of the conformational change is the movement of the loop bearing the amino acid Tyr139 that precedes the interacting arm of the subunit. The tyrosyl ring rotates and moves by at least 5 angstrom upon IPM-binding. Thereby, new hydrophobic interactions are formed above the buried isopropyl-group of IPM. Domain closure is then completed only through subunit interactions: a loop of one subunit that is inserted into the interdomain cavity of the other subunit extends the area with the hydrophobic interactions, providing an example of the cooperativity between interdomain and intersubunit interactions.

}, issn = {1742-206X}, doi = {10.1039/c0mb00346h}, author = {Graczer, Eva and Merli, Angelo and Singh, Rajesh Kumar and Karuppasamy, Manikandan and Zavodszky, Peter and Weiss, Manfred S. and Vas, Maria} } @article { ISI:000292722900032, title = {Comparative behavior of CdS and CdSe quantum dots in poly (3-hexylthiophene) based nanocomposites (vol 41, pg 198, 2006)}, journal = {Materials Research Bulletin}, volume = {46}, number = {8}, year = {2011}, month = {AUG}, pages = {1321}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, issn = {0025-5408}, doi = {10.1016/j.materresbull.2011.04.020}, author = {Sonar, Prashant and Sreenivasan, K. P. and Maddanimath, Trupti and Vijayamohanan, K.} } @article {43255, title = {Comparative genomics of the pathogenic ciliate Ichthyophthirius multifiliis, its free-living relatives and a host species provide insights into adoption of a parasitic lifestyle and prospects for disease control}, journal = {Genome Biology}, volume = {12}, year = {2011}, month = {OCT}, pages = {Article Number: R100}, abstract = {Background: Ichthyophthirius multifiliis, commonly known as Ich, is a highly pathogenic ciliate responsible for {\textquoteright}white spot{\textquoteright}, a disease causing significant economic losses to the global aquaculture industry. Options for disease control are extremely limited, and Ich{\textquoteright}s obligate parasitic lifestyle makes experimental studies challenging. Unlike most well-studied protozoan parasites, Ich belongs to a phylum composed primarily of free-living members. Indeed, it is closely related to the model organism Tetrahymena thermophila. Genomic studies represent a promising strategy to reduce the impact of this disease and to understand the evolutionary transition to parasitism. Results: We report the sequencing, assembly and annotation of the Ich macronuclear genome. Compared with its free-living relative T. thermophila, the Ich genome is reduced approximately two-fold in length and gene density and three-fold in gene content. We analyzed in detail several gene classes with diverse functions in behavior, cellular function and host immunogenicity, including protein kinases, membrane transporters, proteases, surface antigens and cytoskeletal components and regulators. We also mapped by orthology Ich{\textquoteright}s metabolic pathways in comparison with other ciliates and a potential host organism, the zebrafish Danio rerio. Conclusions: Knowledge of the complete protein-coding and metabolic potential of Ich opens avenues for rational testing of therapeutic drugs that target functions essential to this parasite but not to its fish hosts. Also, a catalog of surface protein-encoding genes will facilitate development of more effective vaccines. The potential to use T. thermophila as a surrogate model offers promise toward controlling {\textquoteright}white spot{\textquoteright} disease and understanding the adaptation to a parasitic lifestyle.}, doi = {10.1186/gb-2011-12-10-r100}, author = {Coyne, Robert S. and Hannick, Linda and Shanmugam, Dhanasekaran and Hostetler, Jessica B. and Brami, Daniel and Joardar, Vinita S. and Johnson, Justin and Radune, Diana and Singh, Irtisha and Badger, Jonathan H. and Kumar, Ujjwal and Saier, Milton and Wang, Yufeng and Cai, Hong and Gu, Jianying and Mather, Michael W. and Vaidya, Akhil B. and Wilkes, David E. and Rajagopalan, Vidyalakshmi and Asai, David J. and Pearson, Chad G. and Findly, Robert C. and Dickerson, Harry W. and Wu, Martin and Martens, Cindy and Van de Peer, Yves and Roos, David S. and Cassidy-Hanley, Donna M. and Clark, Theodore G.} } @article { ISI:000293230300022, title = {Concurrent display of both alpha- and beta-turns in a model peptide}, journal = {Organic \& Biomolecular Chemistry}, volume = {9}, number = {16}, year = {2011}, month = {MAY}, pages = {5762-5765}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

This article describes a model peptide that concurrently displays both alpha- and beta-turns, as demonstrated by structural investigations using single crystal X-ray crystallography and solution-state NMR studies. The motif reported herein has the potential for the design of novel conformationally ordered synthetic oligomers with structural architectures distinct from those classically observed.

}, issn = {1477-0520}, doi = {10.1039/c1ob05553d}, author = {Srinivas, Deekonda and Vijayadas, Kuruppanthara N. and Gonnade, Rajesh G. and Phalgune, Usha D. and Rajamohanan, Pattuparambil R. and Sanjayan, Gangadhar J.} } @article { ISI:000285749800008, title = {Conformationally rigid aromatic amino acids as potential building blocks for abiotic foldamers}, journal = {Organic \& Biomolecular Chemistry}, volume = {9}, number = {2}, year = {2011}, month = {NOV}, pages = {367-369}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

This communication describes the development of conformationally constrained unnatural aromatic amino acids, constructed on rigid backbone wherein the carboxyl and amino groups project in two dimensions (planes) on the aromatic framework. Such a feature offers the possibility of design and development of conformationally ordered synthetic oligomers with intriguing structural architectures distinct from those classically observed. Furthermore, such amino acids will have the potential to extend the conformational space available for foldamer design with diverse backbone conformation and structural architectures.

}, issn = {1477-0520}, doi = {10.1039/c0ob00593b}, author = {Ramesh, Veera V. E. and Roy, Arup and Vijayadas, Kuruppanthara N. and Kendhale, Amol M. and Prabhakaran, Panchami and Gonnade, Rajesh G. and Puranik, Vedavati G. and Sanjayan, Gangadhar J.} } @article { ISI:000295696300005, title = {DFT investigation of the potential of porous cages for the catalysis of ammonia borane dehydrogenation}, journal = {Chemical Communications}, volume = {47}, number = {41}, year = {2011}, month = {SEP}, pages = {11417-11419}, publisher = {ROYAL SOC CHEMISTRY}, type = {Article}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Full DFT based quantum mechanical studies reveal that zero dimensional porous structures, especially the newly proposed phosphorus incorporated organic cages, can be excellent catalysts for the dehydrogenation of ammonia borane.

}, issn = {1359-7345}, doi = {10.1039/c1cc13285g}, author = {Pal, Amrita and Vanka, Kumar} } @article { ISI:000289315700010, title = {Effect of triples to dipole moments in fock-space multireference coupled cluster method}, journal = {Journal of Chemical Theory and Computation}, volume = {7}, number = {4}, year = {2011}, month = {APR}, pages = {876-883}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

In this paper, we present the new implementation of partial triples for the dipole moment of doublet radicals in Lagrangian formulation of Fock-space multireference coupled cluster (A-FSMRCC) response method. We have implemented a specific scheme of noniterative triples, in addition to singles and doubles schemes, which accounts for the effects appearing at least at the third order in dipole moments. The method is applied to the ground states of OH, OOH, HCOO, CN, CH, and PO radicals.

}, issn = {1549-9618}, doi = {10.1021/ct1007263}, author = {Ravichandran, Lalitha and Vaval, Nayana and Pal, Sourav} } @article { ISI:000294187400078, title = {Enhanced enzymatic hydrolysis of cellulose by partial modification of its chemical structure}, journal = {Carbohydrate Polymers}, volume = {86}, number = {2}, year = {2011}, month = {AUG}, pages = {962-968}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

A series of 2,3-dialdehyde celluloses with different degrees of oxidation were used for deriving corresponding dicarboxylate, dicarboxy, and Schiff{\textquoteright}s base cellulose derivatives. The dialdehyde cellulose was hydrolyzed by cellulase to a lower extent than the starting cellulose, except at high levels of aldehyde content (above 50\%). For dicarboxylate and dicarboxy celluloses, the highest level of oxidized NaDCC and DCC hydrolysed up to 70 and 60\% respectively which was 3-4 times more than cellulose. The 2,3-dioxime cellulose derivative hydrolyzes only up to 16.3\% for the highest level of oxidized dioxime. In the case of 2,3-diethylimine cellulose, all derivatives hydrolyse faster than the native cellulose. Up to 75\% hydrolysis was observed for 2,3-diethyimine cellulose-50, 2,3-dipropylimine and 2,3-dibutylimine cellulose. The 2,3-dibenzylimine cellulose hydrolyses a little slower than the alkylimine derivatives. The 2,3-dihydrazone cellulose derivatives with all level of oxidation showed resistance towards enzymatic hydrolysis. (C) 2011 Elsevier Ltd. All rights reserved.

}, keywords = {2, 3-Dialdehyde celluloses, 3-Dibenzylimine cellulose, 3-Dibutylimine cellulose, 3-Dicarboxy celluloses, 3-Diethyimine cellulose, 3-Dihydrazone cellulose, 3-Dipropylimine cellulose, Cellulase, Enzymatic hydrolysis}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2011.05.067}, author = {Shaikh, H. M. and Adsul, Mukund G. and Gokhale, D. V. and Varma, Anjanikumar} } @article { ISI:000294359100090, title = {Evidence of lateral heat transfer during laser assisted atom probe tomography analysis of large band gap materials}, journal = {Applied Physics Letters}, volume = {99}, number = {8}, year = {2011}, month = {AUG}, pages = {Article No. 084101}, publisher = {AMER INST PHYSICS}, type = {Article}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

Investigation of wustite (FeO), iron (Fe), and silicon (Si) specimens by infrared laser assisted three dimensional atom probe tomography shows evidence of confined surface absorption of the laser energy as the mechanism of laser assisted field evaporation for high band gap materials. The absorption region is shown to be located on the laser illumination side, close to the specimen apex. A simple model based on thermal diffusivity and spatial extent of the absorption region is derived and applied to the experimental results. The values of thermal diffusivity thus obtained are in good agreement with the published data. (C) 2011 American Institute of Physics. [doi:10.1063/1.3622647]

}, issn = {0003-6951}, doi = {10.1063/1.3622647}, author = {Bachhav, Mukesh N. and Danoix, R. and Vurpillot, F. and Hannoyer, Beatrice and Ogale, Satishchandra B. and Danoix, F.} } @article {42524, title = {Exciton-coupled charge-transfer dynamics in a porphyrin J-aggregate/TiO 2 complex}, journal = {Chemistry a European Journal}, volume = {17}, year = {2011}, month = {MAR}, pages = {3458{\textendash}3464}, abstract = {

Exciton-coupled charge-transfer (CT) dynamics in TiO2 nanoparticles (NP) sensitized with porphyrin J-aggregates has been studied by femtosecond time-resolved transient absorption spectroscopy. J-aggregates of 5,10,15-triphenyl-20-(3,4-dihydroxyphenyl) porphyrin (TPPcat) form CT complexes on TiO2 NP surfaces. Catechol-mediated strong CT coupling between J-aggregate and TiO2 NP facilitates interfacial exciton dissociation for electron injection into the conduction band of the TiO2 nanoparticle in pulse width limited time (\<80 fs). Here, the electron-transfer (\<80 fs) process dominates over the intrinsic exciton-relaxation process (J-aggregates: ca. 200 fs) on account of exciton-coupled CT interaction. The parent hole on J-aggregates is delocalized through J-aggregate excitonic coherence. As a result, holes immobilized on J-aggregates are spatially less accessible to electrons injected into TiO2, and thus the back electron transfer (BET) process is slower than that of the monomer/TiO2 system. The J-aggregate/porphyrin system shows exciton spectral and temporal properties for better charge separation in strongly coupled composite systems.

}, doi = {10.1002/chem.201002537}, author = {Verma, Sandeep and Ghosh, Amrita and Das, Amitava and Ghosh, Hirendra Nath} } @article { ISI:000287716400004, title = {Expression analysis of cinnamoyl-CoA reductase (CCR) gene in developing seedlings of Leucaena leucocephala: A pulp yielding tree species}, journal = {Plant Physiology and Biochemistry}, volume = {49}, number = {2}, year = {2011}, month = {FEB}, pages = {138-145}, publisher = {ELSEVIER FRANCE-EDITIONS SCIENTIFIQUES MEDICALES ELSEVIER}, address = {23 RUE LINOIS, 75724 PARIS, FRANCE}, abstract = {

Removal of lignin is a major hurdle for obtaining good quality pulp. Leucaena leucocephala (subabul) is extensively used in paper industry in India; therefore, as a first step to generate transgenic plants with low lignin content, cDNA and genomic clones of CCR gene were isolated and characterized. The cDNA encoding CCR (EC 1.2.1.44) was designated as LI-CCR; the sequence analysis revealed an Open Reading Frame (ORF) of 1005 bp. Phylogenetic analysis showed that LI-CCR sequence is highly homologous to CCRs from other dicot plants. The 2992 bp genomic clone of Leucaena CCR consists of 5 exons and 4 introns. The haploid genome of L leucocephala contains two copies as revealed by DNA blot hybridization. LI-CCR gene was over-expressed in Escherichia coli, which showed a molecular mass of approximately 38 kDa. Protein blot analysis revealed that LI-CCR protein is expressed at higher levels in root and in stem, but undetectable in leaf tissues. Expression of CCR gene in Leucaena increased up to 15 d in case of roots and stem as revealed by QRT-PcR studies in 0-15 d old seedlings. ELISA based studies of extractable CCR protein corroborated with QRT-PCR data. CCR protein was immuno-cytolocalized around xylem tissue. Lignin estimation and expression studies of 5,10 and 15 d old stem and root suggest that CCR expression correlates with quantity of lignin produced, which makes it a good target for antisense down regulation for producing designer species for paper industry. (C) 2010 Elsevier Masson SAS. All rights reserved.

}, keywords = {Cinnamoyl-CoA reductase, Developing seedling, Leucaena leucocephala, Lignin biosynthesis}, issn = {0981-9428}, doi = {10.1016/j.plaphy.2010.11.001}, author = {Srivastava, Sameer and Gupta, Ranadheer K. and Arha, Manish and Vishwakarma, Rishi K. and Rawal, Shuban K. and Kishor, P. B. Kavi and Khan, Bashir Mohammad} } @article { ISI:000299031600049, title = {Ferroelectric and electrical characterization of multiferroic BiFeO3 at the single nanoparticle level}, journal = {Applied Physics Letters}, volume = {99}, number = {25}, year = {2011}, month = {DEC}, pages = {Article No. 252905}, publisher = {AMER INST PHYSICS}, type = {Article}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

Ferroelectric BiFeO3 (BFO) nanoparticles deposited on epitaxial substrates of SrRuO3 (SRO) and La1-xSrxMnO3 (LSMO) were studied using band excitation piezoresponse spectroscopy (BEPS), piezoresponse force microscopy (PFM), and ferromagnetic resonance (FMR). BEPS confirms that the nanoparticles are ferroelectric in nature. Switching behavior of nanoparticle clusters were studied and showed evidence for inhomogeneous switching. The dimensionality of domains within nanoparticles was found to be fractal in nature, with a dimensionality constant of similar to 1.4, on par with ferroelectric BFO thin-films under 100 nm in thickness. Ferromagnetic resonance studies indicate BFO nanoparticles only weakly affect the magnetic response of LSMO. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3671392]

}, issn = {0003-6951}, doi = {10.1063/1.3671392}, author = {Vasudevan, R. K. and Bogle, Kashinath A. and Kumar, A. and Jesse, S. and Magaraggia, R. and Stamps, R. and Ogale, Satishchandra B. and Potdar, H. S. and Nagarajan, V.} } @article { ISI:000291709500006, title = {Identification of sublattice damages in swift heavy ion irradiated N-doped 6H-SiC polytype studied by solid state NMR}, journal = {Journal of Physical Chemistry B}, volume = {115}, number = {24}, year = {2011}, month = {JUN}, pages = {7766-7772}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We have studied N-doped 6H-SiC in its pristine and Swift Heavy Ion (SHI) irradiated (150 MeV Ag12+ ions) forms by solid state Nuclear Magnetic Resonance (NMR) at 7.01 T using C-13 and Si-29 as probe nuclei under magic angle spinning. We show that increased levels of nitrogen doping, than used before, lead to the observation of Knight shifts emanating from an increase in electron density in the conduction band, which in C-13 far exceed those in Si-29 MAS spectra. We have rationalized the differential effects in the MAS spectra and site-dependent paramagnetic shifts in terms of the nitrogen doping at the A, B, and C lattice sites. N-doping has a profound effect on Si-29 spin-lattice relaxation, and the site-dependent relaxation behavior is attributed to a difference in conduction electron properties at the different lattice sites. Si-29 T-1 measurements serve to identify the sublattice damages in SHI irradiated 6H-SiC. By determining the spin-lattice relaxation rates as a function of the SHI irradiation ion fluences, the change in relaxation behavior is correlated to the damage production mechanism. The sublattice damage leads to discernable changes in the interaction between the mobile unpaired electrons in the conduction band and the nuclear site, which profoundly influence the NMR relaxation properties. Our relaxation studies also provide evidence for site-dependent localized effects and a decrease in carrier spin density in the conduction band for the SHI irradiated 6H-SiC.

}, issn = {1520-6106}, doi = {10.1021/jp201367b}, author = {Viswanathan, E. and Kanjilal, D. and Sivaji, K. and Ganapathy, Subramanian} } @article { ISI:000300460900038, title = {Investigation of wustite (Fe1-xO) by femtosecond laser assisted atom probe tomography}, journal = {Ultramicroscopy}, volume = {111}, number = {6}, year = {2011}, month = {MAY}, pages = {584-588}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

In this paper, we report results obtained from laser assisted three-dimensional (3-D) atom probe tomography (APT) on wustite (Fe1-xO). Oxides are generally insulating and hence hard to analyse in conventional electrical assisted APT. To overcome this problem, femtosecond laser pulses are used instead of voltage pulses. Here we discuss some aspects of pulsed laser field evaporation and optimization of parameters to achieve better chemical accuracy. (C) 2010 Elsevier B.V. All rights reserved.

}, keywords = {Atom probe tomography, Laser assisted field evaporation, Wustite}, issn = {0304-3991}, doi = {10.1016/j.ultramic.2010.11.023}, author = {Bachhav, Mukesh N. and Danoix, R. and Danoix, F. and Hannoyer, Beatrice and Ogale, Satishchandra B. and Vurpillot, F.} } @article { ISI:000292962900073, title = {Ligand dynamics controlled reverse spin cross over in bis pyrazolyl pyridine based Fe(II) complex cation with metallodithiolato anions with an example of a ferromagnetic 2:1 cocrystal of mixed Ni(III)/Ni(II) oxidation states}, journal = {Inorganica Chimica Acta}, volume = {374}, number = {1, SI}, year = {2011}, month = {AUG}, pages = {586-600}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

We report here the crystal and molecular structures of three compounds [FeL(2)] [Ni(mnt)(2)] (1), [FeL(2)](2) [Ni(mnt)(2)](3)center dot 2H(2)O (2) and [FeL(2)] [Cu(mnt)(2)]center dot 2CH(3)CN (3) where L = 2,6-bis(3,5-dimethylpyrazol-1-ylmethyl) pyridine and mnt = maleonitriledithiolate, and their detailed spectroscopic and magnetic properties using variable temperature Mssbauer, EPR, susceptibility studies, along with room temperature electron spectroscopy for chemical analysis (ESCA) studies. The observed temperature dependant high spin/low spin (HS/LS) ratios of [FeL(2)](2+) cations in these lattices, exhibiting {\textquoteleft}reverse spin cross-over{\textquoteright} measured unequivocally by Mssbauer, have been interpreted as resulting from differing amount of {\textquoteleft}void space{\textquoteright} in the lattice, a measure of the ease of lattice dynamics originating from ligand L. Differential scanning calorimetric data points this HS/LS transition to order-disorder type of second order phase transitions. While trying to test this lattice dynamics controlled property of [FeL(2)](2+) cations an unusual behavior of cocrystallization of two planar complex anions of the same type in two different oxidation states, viz. [Ni(mnt)(2)](2) and [Ni(mnt)(2)] , was observed in [FeL(2)](2+) [Ni(mnt(2))](3), supported by crystallography, ESCA chemical shifts of Ni 2p(3/2) and EPR. The susceptibility data in combination with ESCA chemical shifts of S 2p(3/2) and Ni 2p(3/2) on all the compounds reveal the importance of charge transfer between the two counter ions. (C) 2011 Elsevier B.V. All rights reserved.

}, keywords = {Iron complexes, Magnetism, Reverse-spin crossover, X-ray crystal structures}, issn = {0020-1693}, doi = {10.1016/j.ica.2011.02.081}, author = {Manoharan, Periakaruppan T. and Sambandam, Balaji and Amsarani, Ramamoorthy and Varghese, Babu and Gopinath, Chinnakonda S. and Nomura, Kiyoshi} } @article { ISI:000289763700026, title = {Low temperature pH dependent synthesis of flower-like ZnO nanostructures with enhanced photocatalytic activity}, journal = {Materials Research Bulletin}, volume = {46}, number = {5}, year = {2011}, month = {MAY}, pages = {771-778}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

In the present study we have synthesized flower-like ZnO nanostructures comprising of nanobelts of 20 nm width by template and surfactant free low-temperature (4 degrees C) aqueous solution route. The ZnO nanostructures exhibit flower-like morphology, having crystalline hexagonal wurtzite structure with (001) orientation. The flowers with size between 600 and 700 nm consist of ZnO units having crystallite size of similar to 40 nm. Chemical and structural characterization reveals a significant role of precursor: ligand molar ratio, pH, and temperature in the formation of single-step flower-like ZnO at low temperature. Plausible growth mechanism for the formation of flower-like structure has been discussed in detail. Photoluminescence studies confirm formation of ZnO with the defects in crystal structure. The flower-like ZnO nanostructures exhibit enhanced photochemical degradation of methylene blue (MB) with the increased concentration of ligand, indicating attribution of structural features in the photocatalytic properties. (C) 2010 Elsevier Ltd. All rights reserved.

}, keywords = {Catalytic properties, Defects, Nanostructures, Optical properties, Semiconductor}, issn = {0025-5408}, doi = {10.1016/j.materresbull.2010.11.007}, author = {Vaishampayan, Mukta V. and Mulla, Imtiaz S. and Joshi, Satyawati S.} } @article { ISI:000293741800076, title = {Magnetic and electric responsive hydrogel-magnetic nanocomposites for drug-delivery application}, journal = {Journal of Applied Polymer Science}, volume = {122}, number = {2}, year = {2011}, month = {OCT}, pages = {1364-1375}, publisher = {WILEY-BLACKWELL}, address = {COMMERCE PLACE, 350 MAIN ST, MALDEN 02148, MA USA}, abstract = {

Magnetic and electrically responsive hydrogel networks were developed for drug-delivery applications. The hydrogel matrices were synthesized by the polymerization of acrylamide monomer in the presence of carboxymethylcellulose (CMC) or methylcellulose (MC) with N,N-methylenebisacrylamide, a crosslinker with the redox initiating system ammonium persulfate/tetramethylethylenediamine. The magnetic nanoparticles were generated throughout these hydrogel matrices by an in situ method by the incorporation of iron ions and their subsequent reduction with ammonia. A series of hydrogel-magnetic nanocomposites (HGMNCs) were developed with various CMC and MC compositions. The synthesized HGMNCs were characterized with spectral (Fourier transform infrared and ultraviolet-visible spectroscopy), X-ray diffraction, thermal, and microscopy methods. These HGMNCs contained iron oxide (Fe3O4) nanoparticles with an average particle size of about 22 nm, as observed by transmission electron microscopy. The dielectrical properties of the pure hydrogel (HG); the hydrogel loaded with iron ions, or the hydrogel iron-ion composite (HGIC); and the HGMNCs were measured. These results suggest that HGMNCs exhibited higher dielectric constants compared to HG and HGICs. The curcumin loading and release characteristics were also measured for HG, HGIC, and HGMNC systems. These data revealed that there was a sustained release of curcumin from HGMNCs because of the presence of magnetic nanoparticles in the hydrogel networks. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 122: 1364-1375, 2011

}, keywords = {hydrogels, magnetic polymers, Nanocomposites, nanoparticle, nanotechnology}, issn = {0021-8995}, doi = {10.1002/app.34016}, author = {Reddy, N. Narayana and Mohan, Y. Murali and Varaprasad, K. and Ravindra, S. and Joy, Pattayil Alias and Raju, K. Mohana} } @article { ISI:000286904500164, title = {Microbial production of xylitol from D-xylose and sugarcane bagasse hemicellulose using newly isolated thermotolerant yeast Debaryomyces hansenii}, journal = {Bioresource Technology}, volume = {102}, number = {3}, year = {2011}, month = {FEB}, pages = {3304-3308}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

A thermotolerant yeast capable of fermenting xylose to xylitol at 40 C was isolated and identified as a strain of Debaryomyces hansenii by ITS sequencing. This paper reports the production of xylitol from D-xylose and sugarcane bagasse hemicellulose by free and Ca-alginate immobilized cells of D. hansenii. The efficiency of free and immobilized cells were compared for xylitol production from D-xylose and hemicellulose in batch culture at 40 degrees C. The maximum xylitol produced by free cells was 68.6 g/L from 100 g/L of xylose, with a yield of 0.76 g/g and volumetric productivity 0.44 g/L/h. The yield of xylitol and volumetric productivity were 0.69 g/g and 0.28 g/L/h respectively from hemicellulosic hydrolysate of sugarcane bagasse after detoxification with activated charcoal and ion exchange resins. The Ca-alginate immobilized D. hansenii cells produced 73.8 g of xylitol from 100 g/L of xylose with a yield of 0.82 g/g and volumetric productivity of 0.46 g/L/h and were reused for five batches with steady bioconversion rates and yields. (C) 2010 Elsevier Ltd. All rights reserved.

}, keywords = {Immobilization, Sugarcane bagasse hemicellulose, Thermotolerant Debaryomyces hansenii, xylitol, Xylose}, issn = {0960-8524}, doi = {10.1016/j.biortech.2010.10.074}, author = {Prakash, Gyan and Varma, Anjanikumar and Prabhune, Asmita and Shouche, Yogesh and Rao, Mala} } @article {42766, title = {Nanoparticles that communicate in vivo to amplify tumour targeting}, journal = {Nature Materials}, volume = {10}, year = {2011}, month = {JUL}, pages = {545-552}, doi = {10.1038/NMAT3049}, author = {von Maltzahn, Geoffrey and Park, Ji-Ho and Lin, Kevin Y. and Singh, Neetu and Schwoeppe, Christian and Mesters, Rolf and Berdel, Wolfgang E. and Ruoslahti, Erkki and Sailor, Michael J. and Bhatia, Sangeeta N.} } @article { ISI:000288189100018, title = {Nanostructured spinet ZnCo2O4 for the detection of LPG}, journal = {Sensors and Actuators B-Chemical}, volume = {152}, number = {1}, year = {2011}, month = {FEB}, pages = {121-129}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

Nanostrucutred spinel ZnCo2O4 (similar to 26-30 nm) was synthesized by calcining the mixed precursor (consisting of cobalt hydroxyl carbonate and zinc hydroxyl carbonate) in air at 600 degrees C for 5 h. The mixed precursor was prepared through a low cost and simple co-precipitation/digestion method. The transformation of the mixed precursor into nanostructured spinel ZnCO2O4 upon calcinations was confirmed by X-ray diffraction (XRD) measurement, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). To demonstrate the potential applicability of ZnCo2O4 spinel in the fabrication of gas sensors, its LPG sensing characteristics were systematically investigated. The ZnCo2O4 spinel exhibited outstanding gas sensing characteristics such as, higher gas response (similar to 72-50 ppm LPG gas at 350 degrees C), response time (similar to 85-90 s), recovery time (similar to 75-80 s), excellent repeatability, good selectivity and relatively lower operating temperature (similar to 350 degrees C). The experimental results demonstrated that the nanostructured spinel ZnCo2O4 is a very promising material for the fabrication of LPG sensors with good sensing characteristics. Plausible LPG sensing mechanism is also discussed. (c) 2010 Elsevier B.V. All rights reserved.

}, keywords = {HRTEM, LPG sensor, Nanostructured ZnCo2O4, Semiconductor gas sensors, XPS}, issn = {0925-4005}, doi = {10.1016/j.snb.2010.09.001}, author = {Vijayanand, Subramanian and Joy, Pattayil Alias and Potdar, Hari S. and Patil, Dewyani and Patil, Pradip} } @article {43203, title = {Novel pyrazole-3-carboxamide derivatives as cannabinoid-1 (CB1) antagonists: journey from non-polar to polar amides}, journal = {Bioorganic \& Medicinal Chemistry Letters}, volume = {21}, year = {2011}, month = {JAN}, pages = {562-568}, abstract = {The synthesis and biological evaluation of novel pyrazole-3-carboxamide derivatives as CB1 antagonists are described. As a part of eastern amide SAR, various chemically diverse motifs were introduced. In general, a range of modifications were well tolerated. Several molecules with high polar surface area were also indentified as potent CB1 receptor antagonists. The in vivo proof of principle for weight loss is exemplified with a lead compound from this series. (C) 2010 Elsevier Ltd. All rights reserved.}, doi = {10.1016/j.bmcl.2010.10.055}, author = {Sasmal, Pradip K. and Reddy, D. Srinivasa and Talwar, Rashmi and Venkatesham, B. and Balasubrahmanyam, D. and Kannan, M. and Srinivas, P. and Kumar, K. Shiva and Devi, B. Neelima and Jadhav, Vikram P. and Khan, Sanjoy K. and Mohan, Priya and Chaudhury, Hira and Bhuniya, Debnath and Iqbal, Javed and Chakrabarti, Ranjan} } @article { ISI:000295665400063, title = {Optical and photocatalytic properties of single crystalline ZnO at the air-liquid interface by an aminolytic reaction}, journal = {Langmuir}, volume = {27}, number = {20}, year = {2011}, month = {OCT}, pages = {12751-12759}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Crystalline flowerlike ZnO was synthesized by an aminolytic reaction at the air-liquid interface in an aqueous media at an alkaline pH. A thin visible film was formed at the air-liquid interface by self-assembly of flowerlike ZnO. Diffraction studies show rearrangement of the single crystalline units at the air-liquid interface leading to the formation of nanobelts. These nanobelts overlap systematically to form petals of the flowerlike structure; individual petals get curved with time. Each nanobelt is found to be single crystalline and can be indexed as the hexagonal ZnO phase. The organic product formed in the aminolytic reaction and dissolution-reprecipitation mechanism is the driving force for the formation of flowerlike ZnO at the air-liquid interface. A clear relationship between the surface, photocatalytic, and photoluminescent properties of ZnO is observed. The flowerlike structure exhibits a blue shift (3.56 eV) in the band emission as compared to bulk ZnO (3.37 eV). The photodegradation of methylene blue over the flowerlike ZnO catalyst formed at the air-liquid interface and in the sediments shows enhanced photocatalytic activity. The sub-bands formed due to surface defects facilitate separation of charge carriers increasing their lifetime, leading to enhanced photocatalytic activity of flowerlike ZnO.

}, issn = {0743-7463}, doi = {10.1021/la203006n}, author = {Vaishampayan, Mukta V. and Mulla, Imtiaz S. and Joshi, Satyawati S.} } @article { ISI:000293662800019, title = {Phase behavior of lipid-based lyotropic liquid crystals in presence of colloidal nanoparticles}, journal = {Langmuir}, volume = {27}, number = {16}, year = {2011}, month = {AUG}, pages = {9792-9800}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We have investigated the microstructure and phase behavior of monoglyceride-based lyotropic liquid crystals in the presence of hydrophilic silica colloidal particles of size comparable to or slightly exceeding the repeat units of the different liquid crystalline phases. Using small angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC), we compare the structural properties of the neat mesophases with those of the systems containing silica colloidal particles. It is found that the colloidal particles always macrophase separate in inverse bicontinuous cubic phases of gyroid (Ia3d) and double diamond (Pn3m) symmetries. SAXS data for the inverse columnar hexagonal phase (H(II)) and lamellar phase (L(alpha)) suggest that a low volume fraction of the nanoparticles can be accommodated within the mesophases, but that at concentrations above a given threshold, the particles do macrophase separate also in these systems. The behavior is interpreted in terms of the enthalpic and entropic interactions of the nanoparticles with the lamellar and hexagonal phases, and we propose that, in the low concentration limit, the nanoparticles are acting as point defects within the mesophases and, upon further increase in concentration, initiate nucleation of nanoparticles dusters, leading to a macroscopic phase separation.

}, issn = {0743-7463}, doi = {10.1021/la201767p}, author = {Venugopal, Edakkal and Bhat, Suresh K. and Vallooran, Jijo J. and Mezzenga, Raffaele} } @article {42541, title = {Photophysical properties of ligand localized excited state in ruthenium(ii) polypyridyl complexes: a combined effect of electron donor-acceptor ligand}, journal = {Dalton Trans}, volume = {40}, year = {2011}, month = {AUG}, pages = {9765-9773}, abstract = {

We have synthesized ruthenium(II) polypyridyl complexes (1) Ru(II)(bpy)2(L1), (2) Ru(II)(bpy)2(L2) and (3) Ru(II)(bpy)(L1)(L2), where bpy = 2,2'-bipyridyl, L1 = 4-[2-(4'-methyl-2,2'-bipyridinyl-4-yl)vinyl]benzene-1,2-diol) and L2 = 4-(N,N-dimethylamino-phenyl)-(2,2'-bipyridine) and investigated the intra-ligand charge transfer (ILCT) and ligand{\textendash}ligand charge transfer (LLCT) states by optical absorption and emission studies. Our studies show that the presence of electron donating {\textendash}NMe2 functionality in L2 and electron withdrawing catechol fragment in L1 ligands of complex 3 introduces low energy LLCT excited states to aboriginal MLCT states. The superimposed LLCT and MLCT state produces redshift and broadening in the optical absorption spectra of complex 3 in comparison to complexes 1 and 2. The emission quantum yield of complex 3 is observed to be extremely low in comparison to that of complex 1 and 2 at room temperature. This is attributed to quenching of the 3MLCT state by the low-emissive 3LLCT state. The emission due to ligand localized CT state (ILCT and LLCT) of complexes 2 and 3 is revealed at 77 K in the form of a new luminescence band which appeared in the 670{\textendash}760 nm region. The LLCT excited state of complex 3 is populated either via direct photoexcitation in the LLCT absorption band (350{\textendash}700 nm) or through internal conversion from the photoexcited 3MLCT (400{\textendash}600 nm) states. The internal conversion rate is determined by quenching of the 3MLCT state in a time resolved emission study. The internal conversion to LLCT and ILCT excited states are observed to be as fast as \~{}200 ps and \~{}700 ps for complexes 3 and 2, respectively. The present study illustrates the photophysical property of the ligand localized excited state of newly synthesized heteroleptic ruthenium(II) polypyridyl complexes.

}, doi = {10.1039/C1DT10266D}, author = {Verma, Sandeep and Kar, Prasenjit and Das, Amitava and Ghosh, Hirendra Nath} } @article { ISI:000294122000044, title = {Propargyl/methyl furanosides as potential glycosyl donors}, journal = {Chemical Communications}, volume = {47}, number = {35}, year = {2011}, month = {AUG}, pages = {9906-9908}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Transfuranosylations are not well studied though many similar studies exist for transpyranosylation; herein, we report that propargyl/methyl D-ribf- and D-lyxf- give only 1,2-trans glycosides whereas D-araf- and D-xylf- result in a mixture of 1,2-trans and 1,2-cis glycosides; observed facts are rationalised by computational studies.

}, issn = {1359-7345}, doi = {10.1039/c1cc13134f}, author = {Vidadala, Srinivasa Rao and Gayatri, Gaddamannugu and Sastry, G. Narahari and Hotha, Srinivas} } @article { ISI:000295128000013, title = {Protic ionic liquid attenuates the deleterious actions of urea on alpha-chymotrypsin}, journal = {Physical Chemistry Chemical Physics}, volume = {13}, number = {38}, year = {2011}, month = {SEP}, pages = {17023-17026}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

We present a biocompatible ionic liquid, triethyl ammonium acetate (TEAA), that attenuates the denaturation action of a non-ionic chaotrope, urea, on the industrially relevant proteolytic enzyme alpha-chymotrypsin.

}, issn = {1463-9076}, doi = {10.1039/c1cp22195g}, author = {Attri, Pankaj and Venkatesu, Pannuru and Kumar, Anil and Byrne, Nolene} } @article { ISI:000293119900005, title = {Robust synthesis of enantiopure cyclohexenyl analogues of 2/3-deoxyribose sugars as carbocyclic nucleoside precursors}, journal = {Tetrahedron}, volume = {67}, number = {32}, year = {2011}, month = {AUG}, pages = {5744-5749}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

An expedient synthesis of 2-deoxy (10) and 3-deoxy (11) cyclohexenyl analogues of 2-deoxy and 3-deoxy-D-ribose sugar from commercially available starting materials is reported. Highly efficient enzymatic resolution of the key compound 10 is described using lipase under hydrolytic conditions. The robust methodology applied here will be useful to synthesize cyclohexenyl nucleosides, which possess potent antiviral activity and are capable of gene silencing via RNAi or antisense applications. (C) 2011 Elsevier Ltd. All rights reserved.

}, keywords = {Carbocyclic mimics of 2-deoxy-D-ribose and 3-deoxy-D-ribose Enzymatic resolution, CeNA, DA reaction}, issn = {0040-4020}, doi = {10.1016/j.tet.2011.06.003}, author = {Varada, Manojkumar and Kotikam, Venubabu and Kumar, Vaijayanti A.} } @article { ISI:000291903100003, title = {Strain improvement and statistical media optimization for enhanced erythritol production with minimal by-products from candida magnoliae mutant R23}, journal = {Biochemical Engineering Journal}, volume = {55}, number = {2}, year = {2011}, month = {JUL}, pages = {92-100}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

Mutants of Candida magnoliae NCIM 3470 were generated by ultra-violet and chemical mutagenesis to enhance erythritol production. The mutants were screened for higher reductase activity on agar plates containing high concentration of glucose and 2,3,5-triphenyl tetrazolium chloride (TTC). One of the mutants named as R23 gave maximum erythritol production, 60.3 g L(-1), compared to 14 g L(-1) of the parent strain. Glucose and yeast extract were identified as critical medium components which decide the ratio of polyols produced, mainly erythritol, mannitol and glycerol. In order to enhance the production of erythritol and to minimize the production of mannitol and glycerol, a four component-five level-three response central-composite-rotatable-design (CCRD) of response surface methodology (RSM) model was used. The optimum medium composition for erythritol production was found to contain (g L(-1)) glucose 238, yeast extract 9.2, KH(2)PO(4), 5.16 and MgSO(4) 0.23. Moreover, erythritol production was studied in a 10 L fermentor in batch and fed-batch mode using RSM optimized medium. In fed-batch fermentation, 87.8 g L(-1) erythritol was produced with 31.1\% yield, without formation of any other polyols. Thus present study involving strain improvement followed by media and process optimization resulted in 6.2-fold increase in erythritol production and 3.4-fold increase in the yield. (C) 2011 Elsevier B.V. All rights reserved.

}, keywords = {Candida magnoliae, Erythritol, Fermentation, Metabolite over-production, Modelling, Optimization}, issn = {1369-703X}, doi = {10.1016/j.bej.2011.03.009}, author = {Savergave, Laxman S. and Gadre, Ramchandra V. and Vaidya, Bhalchandra K. and Narayanan, Karthik} } @article { ISI:000293826800006, title = {Structural, magnetic and mossbauer spectral studies of nanocrystalline Ni0.5Zn0.5Fe2O4 ferrite powders}, journal = {Journal of Alloys and Compounds}, volume = {509}, number = {37}, year = {2011}, month = {SEP}, pages = {8999-9004}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

Nanocrystalline Ni0.5Zn0.5Fe2O4 powders, synthesized by a combustion method are investigated by X-ray diffraction, vibrating sample magnetometry and Mossbauer spectroscopic techniques. We adopt a strategy to systematically control the particle sizes between 4 and 45 nm simply by changing the elemental stoichiometric coefficient, Phi(e), of the combustion mixture. Curie temperature of the superparamagnetic particles of size 4 nm is higher than that of the bulk particles. Interestingly, bigger particles (45 nm) show a comparable room temperature saturation magnetization and exceptionally very high Curie temperature of 833 K, when compared to that of the bulk Ni0.5Zn0.5Fe2O4 material (563 K). (C) 2011 Elsevier B. V. All rights reserved.

}, keywords = {Chemical synthesis, Magnetisation, Mossbauer spectroscopy, Nanostructured materials}, issn = {0925-8388}, doi = {10.1016/j.jallcom.2011.06.047}, author = {Verma, Seema and Joy, Pattayil Alias and Kurian, Sajith} } @article { ISI:000292555200034, title = {Synthesis and characterization of cobalt substituted zinc ferri-chromites prepared by sol-gel auto-combustion method}, journal = {Journal of Materials Science-Materials in Electronics}, volume = {22}, number = {8}, year = {2011}, month = {AUG}, pages = {1109-1115}, publisher = {SPRINGER}, address = {VAN GODEWIJCKSTRAAT 30, 3311 GZ DORDRECHT, NETHERLANDS}, abstract = {

Mixed metal oxides having spinel structure shows interesting structural properties. In the present investigation, cobalt substituted zinc ferri-chromites were prepared by sol-gel auto-combustion method. The completion of solid state reaction and the formation of spinel phase were identified using X-ray diffraction technique. All the compounds exhibit cubic spinel symmetry and lattice constant shows an irregular trend with substitution of Co. Infra-red spectral studies shows an two strong bands, one around 600 cm(-1) which is attributed to the intrinsic vibrations of tetrahedral complexes and the other at 400 cm(-1) is due to octahedral one. The morphology and size of the particles was found out by scanning electron microscopy while the elemental compositions by elemental dispersive X-ray spectroscopy. The various compounds of the present system Zn1-xCoxFeCrO4 were also investigated for their thermal and electronic studies.

}, issn = {0957-4522}, doi = {10.1007/s10854-010-0268-7}, author = {Hankare, P. P. and Vader, V. T. and Sankpal, U. B. and Patil, R. P. and Jadhav, A. V. and Mulla, Imtiaz S.} } @article { ISI:000288141700012, title = {Synthesis, characterisation of polymer-supported palladium-2-methylimidazole complex catalyst for the hydrogenation of aromatic nitro compounds}, journal = {Journal of Chemical Research}, number = {2}, year = {2011}, month = {FEB}, pages = {112-115}, publisher = {SCIENCE REVIEWS 2000 LTD}, address = {PO BOX 314, ST ALBANS AL1 4ZG, HERTS, ENGLAND}, abstract = {

A polymer-supported palladium-2-methylimidazole complex was synthesised and characterised by various physicochemical methods. The complex was successfully used as a catalyst for the hydrogenation of nitrobenzene and a few of its derivatives under ambient conditions. Results reveal that the electronic as well as the steric effects of the substitutent control the rate of hydrogenation of the nitro group in the studied nitro compounds. The kinetics of hydrogenation and the reusability of the catalyst were also studied.

}, keywords = {aromatic nitro compounds, Hydrogenation, polymer-supported complex catalyst, transition metal complexes}, issn = {1747-5198}, doi = {10.3184/174751911X556855}, author = {Velua, Udayakumar and Stanislaus, Alexander and Virupaiah, Gayathri and Shivakumaraiah and Patil, Kashinath Rangu and Balasubramanian, Viswanathan} } @article { ISI:000294593400012, title = {Thermal epimerization of inositol 1,3-benzylidene acetals in the molten state}, journal = {Tetrahedron}, volume = {67}, number = {38}, year = {2011}, month = {SEP}, pages = {7280-7288}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

1,3-O-Benzylidene-2,4,5,6-tetra-O-substituted-myo-inositol derivatives obtained by the DIBAL-H reduction of the corresponding myo-inositol 1,3,5-orthobenzoate derivatives undergo epimerization at the acetal carbon on heating, in the molten state, just above their melting point. The same epimerization reaction does not proceed either in the crystalline state or in solution. DFT calculations suggest that the epimeric acetal obtained by this thermal process is relatively more stable than the starting acetal. Either of these acetals could not be obtained by the reaction of the corresponding inositol derived diol with benzaldehyde. These observations constitute a novel reaction solely in the molten state, which are rarely encountered in the literature. X-ray crystal structures of the epimeric acetals as well as their radical deoxygenation reaction are also reported. (C) 2011 Elsevier Ltd. All rights reserved.

}, keywords = {cyclitols, Deoxygenation, Epimerization, Melt, Xanthate}, issn = {0040-4020}, doi = {10.1016/j.tet.2011.07.044}, author = {Gurale, Bharat P. and Krishnaswamy, Shobhana and Vanka, Kumar and Shashidhar, Mysore S.} } @article { ISI:000307209400005, title = {Alkylation of benzene to cumene over mor zeolite catalysts}, journal = {Revue Roumaine De Chimie}, volume = {57}, number = {2}, year = {2012}, month = {FEB}, pages = {107-113}, publisher = {EDITURA ACAD ROMANE}, address = {CALEA 13 SEPTEMBRIE NR 13, SECTOR 5, BUCURESTI 050711, ROMANIA}, abstract = {

The vapor phase alkylation of benzene to cumene (isopropyl benzene) is studied over MOR (mordenite) type zeolite at different process parameters. The reaction was also studied by adopting different methodologies (pyridine poisoning, passing of moist propylene, alkali dominant mordenite, use of coked catalyst and metal impregnated zeolite) to check the nature of product distribution and the extent of activity and selectivity to alkylated product IPB, DIPB (isopropyl benzene and diisopropyl benzene) and n-PB (n-propyl benzene). It is revealed that the adoption of different methodologies affects the activity and selectivity significantly by suppressing of alkylation / isomerisation reactions.

}, keywords = {Alkylation, cumene, isopropanol, MOR zeolite, propylene}, issn = {0035-3930}, author = {Vyawahare, Yogesh K. and Chumbhale, Vilas R. and Aswar, Anand S.} } @article { ISI:000305764600011, title = {Antituberculosis agent diaportheone B: synthesis, absolute configuration assignment, and anti-TB activity of its analogues}, journal = {Organic \& Biomolecular Chemistry}, volume = {10}, number = {28}, year = {2012}, month = {MAY}, pages = {5385-5394}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

First synthesis of diaportheone B, an antituberculosis agent isolated from endophytic fungus Diaporthe sp. P133 is reported using two complementary routes, a one step and a three-step sequence. The absolute configuration of diaportheone B was determined by using X-ray crystal structure analysis of its dibromo derivative. In addition, we have prepared several close analogues of diaportheone B and determined their anti-TB potential using Alamar-blue assay (H(37)Rv).

}, issn = {1477-0520}, doi = {10.1039/c2ob25831e}, author = {Swaroop, Pandrangi Siva and Raut, Gajanan N. and Gonnade, Rajesh G. and Verma, Priyanka and Gokhale, Rajesh S. and Reddy, D. Srinivasa} } @article { ISI:000300299500001, title = {Biomimetic synthesis of selenium nanoparticles using cell-free extract of microbacterium sp ARB05}, journal = {Micro \& Nano Letters}, volume = {7}, number = {1}, year = {2012}, month = {JAN}, pages = {1-4}, publisher = {INST ENGINEERING TECHNOLOGY-IET}, address = {MICHAEL FARADAY HOUSE SIX HILLS WAY STEVENAGE, HERTFORD SG1 2AY, ENGLAND}, abstract = {

This Letter is a novel approach to synthesise a bio-functionalised selenium nanoparticles using cell-free extract of selenium-resistant bacterial isolate. Phylogenetic analysis of isolate suggested its close similarity with Microbacterium luteolum (Y17235.1) and Microbacterium oxydans str. TPL09 (EU373379.1) while it was distantly related to Microbacterium dextranolyticum (Y17230.1). Selenium colloidal solution exhibited an absorption maximum at 300 nm and gave emission maximum at 590 nm. Transmission electron microscopy followed by selected area electron diffraction pattern analysis indicated the formation of spherical, polydispersed, crystalline, Se nanoparticles of diameter ranging from similar to 30 to 150 nm. X-ray diffraction results showed 111, 200 and 220 planes of face-centred cubic selenium. Energy dispersive analysis of X-rays confirmed the presence of selenium in nanosphere. Selenium nanoparticles synthesised in this manner can be studied for chemo-prevention as well as its fluorescent property can be utilised for molecular diagnostics in cancer research.

}, issn = {1750-0443}, doi = {10.1049/mnl.2011.0498}, author = {Prasad, K. S. and Vyas, P. and Prajapati, V. and Patel, P. and Selvaraj, K.} } @article { ISI:000303153800009, title = {Characterization of biocompatible NiCo2O4 nanoparticles for applications in hyperthermia and drug delivery}, journal = {Nanomedicine-Nanotechnology Biology and Medicine}, volume = {8}, number = {4}, year = {2012}, month = {MAY}, pages = {452-459}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Monodispersed, superparamagnetic nickel cobaltite (NCO) nanoparticles were functionalized using mercaptopropionic acid (MPA). MPA conjugates with NCO forming a metal-carboxylate linkage, with the MPA-MPA interaction occurring via formation of disulfide bonds, leaving another carboxyl end free for additional conjugation. The cytotoxicity studies on NCO-MPA show cell viability of similar to 100\% up to a dosage of 40 mu g/mL on SiHa, MCF7, and B16F10 cell lines, and on mouse primary fibroblasts. Time-dependent cell viability studies done for a duration of 72 hours showed the cell lines{\textquoteright} viability up to 80\% for dosages as high as 80 mu g/mL. Negligible leaching (\<5 ppm) of ionic Co or Ni was noted into the delivery medium. Upon subjecting the NCO-MPA dispersion (0.1 mg/mL) to radiofrequency absorption, the nanoparticles were heated to 75 degrees C within 2 minutes, suggesting its promise as a magnetic hyperthermia agent. Furthermore, the amino acid lysine and the drug cephalexin were successfully adducted to the NCO system, suggesting its potential for drug delivery. From the Clinical Editor: NCO-MPA nanopartciles were found to be promising magnetic hyperthermia agents, suggesting potential future clinical applications. (C) 2012 Elsevier Inc. All rights reserved.

}, keywords = {Cytotoxicity, drug delivery, Magnetic hyperthermia, Magnetic nanoparticles}, issn = {1549-9634}, doi = {10.1016/j.nano.2011.07.010}, author = {Kale, Sangeeta N. and Jadhav, Anil D. and Verma, Seema and Koppikar, Soumya J. and Kaul-Ghanekar, Ruchika and Dhole, Sanjay D. and Ogale, Satishchandra B.} } @article {43249, title = {Comparative genomics of the apicomplexan parasites toxoplasma gondii and neospora caninum: coccidia differing in host range and transmission strategy}, journal = {Plos Pathogens}, volume = {8}, year = {2012}, month = {MAR}, abstract = {Toxoplasma gondii is a zoonotic protozoan parasite which infects nearly one third of the human population and is found in an extraordinary range of vertebrate hosts. Its epidemiology depends heavily on horizontal transmission, especially between rodents and its definitive host, the cat. Neospora caninum is a recently discovered close relative of Toxoplasma, whose definitive host is the dog. Both species are tissue-dwelling Coccidia and members of the phylum Apicomplexa; they share many common features, but Neospora neither infects humans nor shares the same wide host range as Toxoplasma, rather it shows a striking preference for highly efficient vertical transmission in cattle. These species therefore provide a remarkable opportunity to investigate mechanisms of host restriction, transmission strategies, virulence and zoonotic potential. We sequenced the genome of N. caninum and transcriptomes of the invasive stage of both species, undertaking an extensive comparative genomics and transcriptomics analysis. We estimate that these organisms diverged from their common ancestor around 28 million years ago and find that both genomes and gene expression are remarkably conserved. However, in N. caninum we identified an unexpected expansion of surface antigen gene families and the divergence of secreted virulence factors, including rhoptry kinases. Specifically we show that the rhoptry kinase ROP18 is pseudogenised in N. caninum and that, as a possible consequence, Neospora is unable to phosphorylate host immunity-related GTPases, as Toxoplasma does. This defense strategy is thought to be key to virulence in Toxoplasma. We conclude that the ecological niches occupied by these species are influenced by a relatively small number of gene products which operate at the host-parasite interface and that the dominance of vertical transmission in N. caninum may be associated with the evolution of reduced virulence in this species.}, doi = {10.1371/journal.ppat.1002567}, author = {Reid, Adam James and Vermont, Sarah J. and Cotton, James A. and Harris, David and Hill-Cawthorne, Grant A. and Koenen-Waisman, Stephanie and Latham, Sophia M. and Mourier, Tobias and Norton, Rebecca and Quail, Michael A. and Sanders, Mandy and Shanmugam, Dhanasekaran and Sohal, Amandeep and Wasmuth, James D. and Brunk, Brian and Grigg, Michael E. and Howard, Jonathan C. and Parkinson, John and Roos, David S. and Trees, Alexander J. and Berriman, Matthew and Pain, Arnab and Wastling, Jonathan M.} } @article { ISI:000307128500003, title = {Computational investigation of the role of the iridium dihydrogen pincer complex in the formation of the cyclic pentamer (NH2BH2)(5)}, journal = {Computational and Theoretical Chemistry}, volume = {992}, year = {2012}, month = {JUL}, pages = {18-29}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Computational studies with density functional theory (DFT) and MP2 have been done to investigate the interaction between the iridium dihydrogen pincer complex: (POCOP)IrH2 (where POCOP = eta(3)-1,3(OPt-Bu-2)(2)C6H3) and NH2BH2, the immediate product of ammonia borane (NH3BH3) dehydrogenation. A mechanism has been proposed for an oligomerisation process at the metal centre that involves competition between (i) insertion of an NH2BH2 molecule into the (NH2BH2)(n) chain and (ii) termination of the chain leading to the formation of the cyclic (NH2BH2)(n) oligomer. The calculated Delta G values show that the competition favours insertion over termination for the cases n = 1 to n = 4 but favours termination for n = 5. The computational studies therefore indicate that the cyclic pentamer (NH2BH2)(5) would be formed during NH3BH3 dehydrogenation by the (POCOP)IrH2 catalyst, agreeing with experimental findings. The mechanistic understanding gained has implications for the facile regeneration of ammonia borane. (C) 2012 Elsevier B.V. All rights reserved.

}, keywords = {Ammonia borane, Hydrogen storage, Iridium pincer ligand catalyst, Mechanistic studies, Oligomerisation cycle}, issn = {2210-271X}, doi = {10.1016/j.comptc.2012.04.020}, author = {Ghatak, Kamalika and Vanka, Kumar} } @article { ISI:000313298000007, title = {Conducting polyanilline based paints on hot dip galvanized low carbon steel for corrosion protection}, journal = {Bulgarian Chemical Communications}, volume = {44}, number = {4}, year = {2012}, month = {JAN}, pages = {318-323}, publisher = {BULGARIAN ACAD SCIENCE}, type = {Article}, address = {CENTRAL LIBRARY 7 NOEMVRI NO 1, SOFIA, 00000, BULGARIA}, abstract = {

Conducting polyaniline based paints have been applied on hot dip galvanized low carbon steel samples. The corrosion protection performance of these paint coatings was evaluated by using Tafel plots and impedance spectroscopy. It was found that the paint coatings offered significant corrosion protection to hot dip galvanized low carbon steel in aqueous 3.5 wt \% NaCl solution.

}, keywords = {Conducting polyaniline based paints, corrosion prevention, hot dip galvanized low carbon steel}, issn = {0324-1130}, author = {Deshpande, P. and Vagge, S. and Jagtap, Sharmili and Khiarnar, R. and Kelkar, Sarika A. and More, Minal} } @article { ISI:000303281500046, title = {Confinement of zinc oxide nanoparticles in ordered mesoporous silica MCM-41}, journal = {Materials Chemistry and Physics}, volume = {133}, number = {2-3}, year = {2012}, month = {APR}, pages = {850-856}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

Mesoporous silica (MS) and zinc loaded MS composites have been synthesized and characterized using high resolution transmission electron microscopy, X-ray diffraction, UV-visible spectroscopy, photoluminescence spectroscopy, N-2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Thermal treatment of the zinc loaded MS composite lead to the formation of ZnO-MS composite. The well ordered uniform pore structure of MS (pore size similar to 3.4 nm) is found to remain stable even after 30\% Zn loading albeit decrease in the pore size 1.2 nm indicates the formation of ZnO inside the pores. (C) 2012 Elsevier B.V. All rights reserved.

}, keywords = {Defect, Energy spectroscopy for chemical analysis (ESCA), Mesoporous, Photoluminescence spectroscopy, Surface properties}, issn = {0254-0584}, doi = {10.1016/j.matchemphys.2012.01.106}, author = {Lihitkar, P. B. and Violet, Samuel and Shirolkar, Mandar and Singh, Jai and Srivastava, O. N. and Naik, R. H. and Kulkarni, S. K.} } @article { ISI:000304915100006, title = {Constrained variational approach for energy derivatives in Intermediate hamiltonian fock-space coupled-cluster theory}, journal = {Chemical Physics}, volume = {401}, year = {2012}, month = {JUN}, pages = {45-49}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Fock-space multi-reference coupled cluster theory is an efficient method for electronic structure of nearly degenerate cases. However, it suffers from the intruder state problem for large model space. The intermediate Hamiltonian formulation eliminates intruder state problem and helps in the convergence of equations. In this paper we have implemented intermediate Hamiltonian approach in Fock-space coupled cluster method for the response properties. We test our method for the dipole moments of doublet radicals. We report dipole moments of CN, SF and NS radicals. (C) 2011 Elsevier B. V. All rights reserved.

}, keywords = {Constrained variational approach, Fock-space multi-reference coupled cluster, Intermediate Hamiltonian theory, Response approach}, issn = {0301-0104}, doi = {10.1016/j.chemphys.2011.10.018}, author = {Ghosh, Aryya and Gupta, Jitendra and Pal, Sourav and Vaval, Nayana} } @article { ISI:000309372100015, title = {Critical review of membrane bioreactor models - Part 2: Hydrodynamic and integrated models}, journal = {Bioresource Technology}, volume = {122}, number = {SI}, year = {2012}, month = {OCT}, pages = {107-118}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Membrane bioreactor technology exists for a couple of decades, but has not yet overwhelmed the market due to some serious drawbacks of which operational cost due to fouling is the major contributor. Knowledge buildup and optimisation for such complex systems can heavily benefit from mathematical modelling. In this paper, the vast literature on hydrodynamic and integrated MBR modelling is critically reviewed. Hydrodynamic models are used at different scales and focus mainly on fouling and only little on system design/optimisation. Integrated models also focus on fouling although the ones including costs are leaning towards optimisation. Trends are discussed, knowledge gaps identified and interesting routes for further research suggested. (C) 2012 Elsevier Ltd. All rights reserved.

}, keywords = {CFD, Costs, hydrodynamics, Integrated model, Modelling}, issn = {0960-8524}, doi = {10.1016/j.biortech.2012.05.071}, author = {Naessens, W. and Maere, T. and Ratkovich, N. and Vedantam, S. and Nopens, I.} } @article { ISI:000301921300006, title = {Crystallization and X-ray structure analysis of a thermostable penicillin G acylase from alcaligenes faecalis}, journal = {Acta Crystallographica Section F-Structural Biology and Crystallization Communications}, volume = {68}, number = {3}, year = {2012}, month = {MAR}, pages = {273-277}, publisher = {WILEY-BLACKWELL}, address = {COMMERCE PLACE, 350 MAIN ST, MALDEN 02148, MA USA}, abstract = {

{The enzyme penicillin G acylase (EC 3.5.1.11) catalyzes amide-bond cleavage in benzylpenicillin (penicillin G) to yield 6-aminopenicillanic acid, an intermediate chemical used in the production of semisynthetic penicillins. A thermostable penicillin G acylase from Alcaligenes faecalis (AfPGA) has been crystallized using the hanging-drop vapour-diffusion method in two different space groups: C2221, with unit-cell parameters a = 72.9

}, keywords = {calcium binding, disulfide bridges, Ntn hydrolases, orthorhombic form, tetragonal form, Thermostability}, issn = {1744-3091}, doi = {10.1107/S1744309111053930}, author = {Varshney, Nishant Kumar and Kumar, R. Suresh and Ignatova, Zoya and Prabhune, Asmita and Pundle, Archana and Dodson, Eleanor J. and Suresh, C. G.} } @article { ISI:000302902200024, title = {Effect of the surface roughness of conducting polypyrrole thin-film electrodes on the electrocatalytic reduction of nitrobenzene}, journal = {Journal of Applied Polymer Science}, volume = {125}, number = {3}, year = {2012}, month = {AUG}, pages = {1875-1881}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

Conducting polypyrrole (PPy) thin-film electrodes were prepared by the electropolymerization of pyrrole on gold-coated glass plates. Films of various roughnesses were obtained by the variation of the scan rates during electropolymerization. These thin films were modified by doping with 6mM of the dopant NiCl2. The surface morphology of the films was studied by scanning electron microscopy and atomic force microscopy (AFM), which suggested films prepared with a high scan rate were rougher in nature than the films produced with a low scan rate. The electrocatalytic reduction of nitrobenzene was carried out with these electrodes with the cyclic voltammetry technique in acetonitrile containing 0.1M HClO4 as a supporting electrolyte. The various results obtained show that the conducting PPy thin-film electrodes were catalytically active toward the electroreduction process. The modified PPy film electrodes doped with NiCl2 were more active toward nitrobenzene electroreduction than the PPy film alone. The results indicate that the roughness of the films played a very important role in determining their catalytic activity. The PPy films that were more rough in nature were catalytically more active than the smooth films; this may have been due to the availability of more reactive sites in the case of rough films. The apparent diffusion coefficients of the PPy film electrodes were also calculated. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

}, keywords = {atomic force microscopy (AFM), conducting polymers, Diffusion, surface modification, Thin films}, issn = {0021-8995}, doi = {10.1002/app.34880}, author = {Adhikari, Arindam and Radhakrishnan, S. and Vijayan, M.} } @article { ISI:000312301800017, title = {Epitaxial magnetic oxide nanocrystals via phase decomposition of bismuth perovskite precursors}, journal = {Advanced Functional Materials}, volume = {22}, number = {24}, year = {2012}, month = {DEC}, pages = {5224-5230}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

The phase instability of bismuth perovskite (BiMO3), where M is a ferromagnetic cation, is exploited to create self-assembled magnetic oxide nanocrystal arrays on oxide supports. Conditions during pulsed laser deposition are tuned so as to induce complete breakdown of the perovskite precursor into bismuth oxide (Bi2O3) and metal oxide (M-Ox) pockets. Subsequent cooling in vacuum volatizes the Bi2O3 leaving behind an array of monodisperse nanocrystals. In situ reflective high energy electron diffraction beam is exploited to monitor the synthesis in real-time. Analysis of the patterns confirms the phase separation and volatization process. Successful synthesis of M-Ox, where M = Mn, Fe, Co, and Cr, is shown using this template-free facile approach. Detailed magnetic characterization of nanocrystals is carried out to reveal the functionalities such as magnetic anisotropy as well as larger than bulk moments, as expected in these oxide nanostructures.

}, keywords = {Bi2O3 evaporation, bismuth perovskites, epitaxial nanostructures, magnetic oxides, phase separation}, issn = {1616-301X}, doi = {10.1002/adfm.201201066}, author = {Bogle, Kashinath A. and Cheung, Jeffrey and Chen, Yong-Lun and Liao, Sheng-Chieh and Lai, Chih-Hung and Chu, Ying-Hao and Gregg, John M. and Ogale, Satishchandra B. and Valanoor, Nagarajan} } @article { ISI:000306066600010, title = {Equation-of-motion coupled-cluster method for the study of shape resonance}, journal = {Journal of Chemical Physics}, volume = {136}, number = {23}, year = {2012}, month = {JUN}, pages = {234110}, publisher = {AMER INST PHYSICS}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

The equation-of-motion coupled-cluster method (EOM-CC) is applied for the first time to calculate the energy and width of a shape resonance in an electron-molecule scattering. The procedure is based on inclusion of complex absorbing potential with EOM-CC theory. We have applied this method to investigate the shape resonance in e(-)N(2), e(-)CO, and e(-)C(2)H(2). (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4729464]

}, issn = {0021-9606}, doi = {10.1063/1.4729464}, author = {Ghosh, Aryya and Vaval, Nayana and Pal, Sourav} } @article { ISI:000307494500027, title = {Exploring the potential of doped zero-dimensional cages for proton transfer in fuel cells: a computational study}, journal = {Journal of Physical Chemistry B}, volume = {116}, number = {32}, year = {2012}, month = {AUG}, pages = {9803-9811}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Calculations with density functional theory (DFT) and MP2 have been done to investigate the potential of recently synthesized durable zero-dimensional (OD) nitrogen-based cage structures to perform as efficient proton-exchange membranes (PEMs) in fuel cells. Our calculations suggest that the hydrogenated 0-D cages, in combination with hydrogen-bonding 1,2,3- and 1,2,4-triazole molecules, would perform as highly efficient PEMs. The results are important in the context of the need for efficient PEMs for fuel cells, especially at higher temperatures (greater than 120 degrees C) where conventional water-based PEMs such as Nafion have been found to be ineffective.

}, issn = {1520-6106}, doi = {10.1021/jp303884p}, author = {Mane, Manoj V. and Venkatnathan, Arun and Ghatak, Kamalika and Vanka, Kumar} } @article { ISI:000306111900003, title = {Extended coupled cluster for Raman and infrared spectra of small molecules}, journal = {Chemical Physics}, volume = {403}, year = {2012}, month = {JUL}, pages = {25-32}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

In this paper we study the harmonic vibrational frequencies, infrared (IR) intensities, Raman intensities and depolarization ratio using extended coupled cluster method. Raman and IR intensities are mixed derivatives of energy with respect to the electric field and geometric perturbation whereas vibrational frequencies are derivatives of energy with respect to geometry. We use semi-numerical approach to obtain these derivatives. We have studied the effect of electron correlation and basis set for the above properties. We compare our results with non-variational coupled cluster and experimental values, wherever available. We have studied HF, BH, CH+, CO and H2CO molecules in different basis sets. For HF molecule, benchmarking is done with full CI values and basis set convergence is studied for this molecule. Effect of triples is studied for all the molecules. (C) 2012 Elsevier B.V. All rights reserved.

}, keywords = {Extended coupled cluster, IR and Raman spectroscopy, Mixed derivatives}, issn = {0301-0104}, doi = {10.1016/j.chemphys.2012.04.017}, author = {Joshi, Sayali P. and Dutta, Achintya Kumar and Pal, Sourav and Vaval, Nayana} } @article {42666, title = {Fock-space multi-reference coupled-cluster response with the effect of triples on dipole moment of ClO and SF radicals}, journal = {Journal of Chemical Sciences}, volume = {124}, year = {2012}, month = {JAN}, pages = {223-232}, doi = {10.1007/s12039-012-0220-x}, author = {Ravichandran, Lalitha and Bhattacharya, Debarati and Vaval, Nayana and Pal, Sourav} } @article { ISI:000306799700029, title = {Functional characterization and differential expression studies of squalene synthase from Withania somnifera}, journal = {Molecular Biology Reports}, volume = {39}, number = {9}, year = {2012}, month = {SEP}, pages = {8803-8812}, publisher = {SPRINGER}, address = {VAN GODEWIJCKSTRAAT 30, 3311 GZ DORDRECHT, NETHERLANDS}, abstract = {

Squalene synthase (SQS: EC 2.5.1.21) is a potential branch point regulatory enzyme and represents the first committed step to diverge the carbon flux from the main isoprenoid pathway towards sterol biosynthesis. In the present study, cloning and characterization of Withania somnifera squalene synthase (WsSQS) cDNA was investigated subsequently followed by its heterologous expression and preliminary enzyme activity. Two different types of WsSQS cDNA clones (WsSQS1and WsSQS2) were identified that contained an open reading frames of 1,236 and 1,242 bp encoding polypeptides of 412 and 414 amino acids respectively. Both WsSQS isoforms share 99 \% similarity and identity with each other. WsSQS deduced amino acids sequences, when compared with SQS of other plant species, showed maximum similarity and identity with Capsicum annuum followed by Solanum tuberosum and Nicotiana tabacum. To obtain soluble recombinant enzymes, 24 hydrophobic amino acids were deleted from the carboxy terminus and expressed as 6X His-Tag fusion protein in Escherichia coli. Approximately 43 kDa recombinant protein was purified using Ni-NTA affinity chromatography and checked on SDS-PAGE. Preliminary activity of the purified enzymes was determined and the products were analyzed by gas chromatograph-mass spectrometer (GC-MS). Quantitative real-time PCR (qRT-PCR) analysis showed that WsSQS expresses more in young leaves than mature leaves, stem and root.

}, keywords = {Gas chromatograph-Mass Spectrometer (GC-MS), qRT-PCR, Squalene synthase, Withania somnifera}, issn = {0301-4851}, doi = {10.1007/s11033-012-1743-4}, author = {Gupta, Neha and Sharma, Poonam and Kumar, R. J. Santosh and Vishwakarma, Rishi K. and Khan, Bashir Mohammad} } @article { ISI:000299292600030, title = {Hydrous RuO2-carbon nanofiber electrodes with high mass and electrode-specific capacitance for efficient energy storage}, journal = {Nanoscale}, volume = {4}, number = {3}, year = {2012}, month = {DEC}, pages = {890-896}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

We demonstrate a new strategy for the fabrication of supercapacitor electrodes possessing high mass and area-specific capacitance for efficient charge storage, which can be extremely useful for the development of light, compact and high performance supercapacitors for a variety of high power demanding applications. High mass and electrode area specific capacitances were attained by using Hydrous Ruthenium Oxide (HRO)-Carbon Nanofiber (CNF) hybrid electrodes prepared by the deposition of HRO (similar to 31\% Ru content) on both the outer and inner surfaces of a cylindrical hollow CNF having open tips. Electrochemical studies of the uniformly deposited HRO nanoparticles on the CNF surface showed a mass specific capacitance of 645 F g(-1) and an electrode specific capacitance of 1.29 F cm(-2) with a HRO-CNF material loading of 2 mg cm(-2) in the supercapacitor electrodes. The mass specific capacitance of pure HRO is 301 F g(-1), whereas the mass specific capacitance of HRO in the HRO-CNF electrode is similar to 1300 F g(-1), which is very close to the theoretical capacitance of HRO. This enhanced charge storage ability, high rate capability, better cyclic stability and low ESR of the HRO-CNF will be useful for the development of high performance supercapacitors.

}, issn = {2040-3364}, doi = {10.1039/c2nr11479h}, author = {Vellacheri, Ranjith and Pillai, Vijayamohanan K. and Kurungot, Sreekumar} } @article { ISI:000306547300013, title = {Microstructural elucidation of self-emulsifying system: effect of chemical structure}, journal = {Pharmaceutical Research}, volume = {29}, number = {8}, year = {2012}, month = {AUG}, pages = {2180-2188}, publisher = {SPRINGER/PLENUM PUBLISHERS}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Self-emulsifying systems (SES) emulsify spontaneously to produce fine oil-in-water emulsion when introduced into aqueous phase. The self-emulsification process plays an important role during formation of emulsion. The objective of current work was to understand and explore the inner structuration of SES through controlled hydration and further to study the influence of additive on the same which ultimately governs performance of final formulation in terms of droplet size. Droplet size of final formulations containing structural analogues of ibuprofen was determined. Microstructural properties of intermediate hydrated regimes of SES were investigated using techniques such as small angle X-ray scattering, differential scanning calorimetry and rheology. The current work established inverse relationship between droplet size of the formulations containing structural analogues of ibuprofen and their Log P values. Microstructural analysis of intermediate hydrated regimes of the prepared samples showed formation of local lamellar structure. Structural analogues of ibuprofen significantly altered microstructure of lamellae which was well correlated with the droplet size of final formulations. In vitro drug release study showed increase in dissolution rate of lipophillic drugs when formulated as SES. The current work emphasizes the fact that tailor-made formulations can be prepared by controlling the properties of intermediate regimes.

}, keywords = {emulsion, flurbiprofen, ibuprofen, ketoprofen, lamellar structure, self-emulsifying system, structural analogues}, issn = {0724-8741}, doi = {10.1007/s11095-012-0746-0}, author = {Patil, Sharvil S. and Venugopal, Edakkal and Bhat, Suresh K. and Mahadik, Kakasaheb R. and Paradkar, Anant R.} } @article { ISI:000305444200038, title = {Molecular dynamics simulation of phosphoric acid doped monomer of polybenzimidazole: a potential component polymer electrolyte membrane of fuel cell}, journal = {Journal of Physical Chemistry B}, volume = {116}, number = {24}, year = {2012}, month = {JUN}, pages = {7357-7366}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Phosphoric acid doped polybenzimidazole is promising electrolyte membranes for high temperature (100 degrees C and above) fuel cells. Proton conduction is governed by the amount of phosphoric acid content in the polymer membrane. In this present work, we perform molecular dynamics simulations on phosphoric acid doped 2-phenyl-1H,1{\textquoteright}H-5,5{\textquoteright}-bibenzo[d]imidazole (monomer unit of polybenzimidazole) to characterize the structural and dynamical properties at varying phosphoric acid content and temperature. From the structural analysis, we have predicted the arrangement of the phosphoric acids, formation of H-bonds in the system, and the contribution of different atoms toward H-bonding. We have also examined the stacking of 2-phenyl-1H,1{\textquoteright}H-5,5{\textquoteright}-bibenzo[d]imidazole molecules and how their arrangement changes with the increasing amount of PA in the system with the help of cluster analysis. From the molecular dynamics simulation conducted at different temperatures and phosphoric acid doping level, we have predicted the diffusion of phosphoric acid and monomer. As a dynamic quantity, we have also calculated ring flipping of the imidazole ring of the monomer.

}, issn = {1520-6106}, doi = {10.1021/jp301117m}, author = {Pahari, Swagata and Choudhury, Chandan Kumar and Pandey, Prithvi Raj and More, Minal and Venkatnathan, Arun and Roy, Sudip} } @article { ISI:000300041700030, title = {Molecular oxygen-assisted oxidative dehydrogenation of ethylbenzene to styrene with nanocrystalline Ti1-xVxO2}, journal = {Green Chemistry}, volume = {14}, number = {2}, year = {2012}, month = {DEC}, pages = {461-471}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Oxidative dehydrogenation of ethylbenzene to styrene has been studied with vanadium-incorporated mesoporous nanocrystalline titania (Ti1-xVxO2) and molecular oxygen between 440 and 530 degrees C. Incorporation of V in TiO2 lattice framework has been achieved by simple solution combustion method. Incorporation of V in TiO2 lattice has been confirmed by X-ray diffraction, XPS and Raman spectra and other physicochemical analysis. High ethyl benzene conversion and stable styrene yield has been observed with 10\% V-containing rutile phase titania at 500 degrees C. However, stable but relatively lower styrene yield has been observed with 2 and 5\% V-containing catalysts between 440 and 500 degrees C. Highest selectivity is observed with lower vanadium content. Comparable activity has been observed under similar experimental conditions with four times higher air-flow than that of O-2. In order to understand the structure activity relationship, spent catalysts were analyzed by all physico-chemical methods. Although there is a phase change from anatase to rutile Ti1-xVxO2 within 1 h of reaction, higher activity is primarily attributed to the ionic V5+ in Ti1-xVxO2 lattice, which prevents agglomeration to V2O5. It is to be underscored the reactivity is retained at the cost of textural properties and phase change from anatase to rutile, which is essential for the reaction.

}, issn = {1463-9262}, doi = {10.1039/c1gc15907k}, author = {Sivaranjani, Kumarsrinivasan and Verma, Akrati and Gopinath, Chinnakonda S.} } @article { ISI:000299291900033, title = {Nanocomposite silica surfactant microcapsules by evaporation induced self assembly: tuning the morphological buckling by modifying viscosity and surface charge}, journal = {Soft Matter}, volume = {8}, number = {6}, year = {2012}, month = {DEC}, pages = {1955-1963}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Nanocomposite microcapsules of silica and surfactants have been synthesized using evaporation induced self-assembly through spray drying. It was established using electron microscopy and small-angle neutron/X-ray scattering experiments that the viscosity of the virgin dispersion and surface charge of colloidal components play a significant role in the buckling of spray droplets during drying. Hollow spherical grains are realized at relatively low viscosity and higher surface charge while mushroom like grains manifest at higher viscosity and lower surface charge. In the intermediate conditions, deformed doughnut shaped microcapsules are obtained. Scattering experiments establish the presence of the organization of micelle like aggregates of surfactants in the dried grains and also corroborate with the observations from electron microscopy. A plausible mechanism regarding the chronological pathways of morphological transformation is illustrated. Computer simulation, based on buckling of an elastic shell using a surface evolver, has been attempted in order to corroborate the experimental results.

}, issn = {1744-683X}, doi = {10.1039/c1sm06964k}, author = {Sen, D. and Bahadur, Jitendra and Mazumder, S. and Verma, G. and Hassan, P. A. and Bhattacharya, S. and Vijai, K. and Doshi, Pankaj} } @article { ISI:000298058400005, title = {New approximate method for the stochastic simulation of chemical systems: the representative reaction approach}, journal = {Journal of Computational Chemistry}, volume = {33}, number = {3}, year = {2012}, month = {JAN}, pages = {276-285}, publisher = {WILEY-BLACKWELL}, address = {COMMERCE PLACE, 350 MAIN ST, MALDEN 02148, MA USA}, abstract = {

We have developed two new approximate methods for stochastically simulating chemical systems. The methods are based on the idea of representing all the reactions in the chemical system by a single reaction, i.e., by the representative reaction approach (RRA). Discussed in the article are the concepts underlying the new methods along with flowchart with all the steps required for their implementation. It is shown that the two RRA methods {with the reaction \$ 2A \textbackslashrightarrow B \$ as the representative reaction (RR)} perform creditably with regard to accuracy and computational efficiency, in comparison to the exact stochastic simulation algorithm (SSA) developed by Gillespie and are able to successfully reproduce at least the first two moments of the probability distribution of each species in the systems studied. As such, the RRA methods represent a promising new approach for stochastically simulating chemical systems. (C) 2011 Wiley Periodicals, Inc. J Comput Chem, 2012

}, keywords = {approximate algorithm, Stochastic simulations}, issn = {0192-8651}, doi = {10.1002/jcc.21971}, author = {Kadam, Shantanu and Vanka, Kumar} } @article { ISI:000307814000728, title = {Novel mechanism involved in temporal regulation of skin pigmentation homeostasis}, journal = {Journal of Investigative Dermatology}, volume = {132}, number = {2}, year = {2012}, note = {42nd Annual Meeting of the European-Society-for-Dermatological-Research (ESDR), Venice, ITALY, SEP 07-10, 2012}, month = {SEP}, pages = {S128}, publisher = {European Soc Dermatol Res (ESDR)}, address = {75 VARICK ST, 9TH FLR, NEW YORK, NY 10013-1917 USA}, issn = {0022-202X}, author = {Ganju, Parul and Natarajan, V. T. and Singh, A. and Vijayan, V. and Dani, Prachi P. and Kar, H. K. and Natarajan, K. and Gadgil, Chetan J. and Rani, R. and Gokhale, R. S.} } @article { ISI:000305092400004, title = {NOx catalyzed pathway of stratospheric ozone depletion: a coupled cluster investigation}, journal = {Journal of Chemical Theory and Computation}, volume = {8}, number = {6}, year = {2012}, month = {MAY}, pages = {1895-1901}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We report a theoretical investigation on the NOx catalyzed pathways of stratospheric ozone depletion using highly accurate coupled cluster methods. These catalytic reactions represent a great challenge to state-of-the-art ab initio methods, while their mechanisms remain unclear to both experimentalists and theoreticians. In this work, we have used the so-called {\textquoteleft}{\textquoteleft}gold standard of quantum chemistry,{\textquoteright}{\textquoteright} the CCSD(T) method, to identify the saddle points on NOx-based reaction pathways of ozone hole formation. Energies of the saddle points are calculated using the multireference variants of coupled cluster methods. The calculated activation energies and rate constants show good agreement with available experimental results. Tropospheric precursors to stratospheric NOx radicals have been identified, and their potential importance in stratospheric chemistry has been discussed. Our calculations resolve previous conflicts between ab initio and experimental results for a trans nitro peroxide intermediate, in the NOx catalyzed pathway of ozone depletion.

}, issn = {1549-9618}, doi = {10.1021/ct300209s}, author = {Dutta, Achintya Kumar and Vaval, Nayana and Pal, Sourav} } @article { ISI:000304129000011, title = {Organocatalytic sequential alpha-amination/corey-chaykovsky reaction of aldehydes: a high yield synthesis of 4-hydroxypyrazolidine derivatives}, journal = {Organic Letters}, volume = {14}, number = {10}, year = {2012}, month = {MAY}, pages = {2468-2471}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

A tandem reaction of in situ generated a-amino aldehydes with dimethyloxosulfonium methylide under Corey-Chaykovsky reaction conditions proceeds efficiently to give 4-hydroxypyrazolidine derivatives in high yields with excellent enantio- and diastereoselectivities. This organocatalytic sequential method provides for the efficient synthesis of anti-1,2-aminoalcohols, structural subunits present in several bioactive molecules as well.

}, issn = {1523-7060}, doi = {10.1021/ol300739b}, author = {Kumar, B. Senthil and Venkataramasubramanian, V. and Sudalai, Arumugam} } @article {42516, title = {Photosensitization of nanoparticulate TiO2 using a Re(I)-polypyridyl complex: studies on interfacial electron transfer in the ultrafast time domain}, journal = {Physical Chemistry Chemical Physics}, volume = {14}, year = {2012}, month = {APR}, pages = {8192-8198}, abstract = {

We have synthesized a new photoactive rhenium(I)-complex having a pendant catechol functionality [Re(CO)3Cl(L)] (1) (L is 4-[2-(4'-methyl-2,2'-bipyridinyl-4-yl)vinyl]benzene-1,2-diol) for studying the dynamics of the interfacial electron transfer between nanoparticulate TiO2 and the photoexcited states of this Re(I)-complex using femtosecond transient absorption spectroscopy. Our steady state absorption studies revealed that complex 1 can bind strongly to TiO2 surfaces through the catechol functionality with the formation of a charge transfer (CT) complex, which has been confirmed by the appearance of a new red-shifted CT band. The longer wavelength absorption band for 1, bound to TiO2 through the proposed catecholate functionality, could also be explained based on the DFT calculations. Dynamics of the interfacial electron transfer between 1 and TiO2 nanoparticles was investigated by studying kinetics at various wavelengths in the visible and near infrared regions. Electron injection into the conduction band of the nanoparticulate TiO2 was confirmed by detection of the conduction band electron in TiO2 (Image ID:c2cp24105f-t1.gif) and the cation radical of the adsorbed dye (1˙+) in real time as monitored by transient absorption spectroscopy. A single exponential and pulse-width limited (\<100 fs) electron injection was observed. Back electron transfer dynamics was determined by monitoring the decay kinetics of 1˙+ and Image ID:c2cp24105f-t2.gif.

}, doi = {10.1039/C2CP24105F}, author = {Kar, Prasenjit and Banerjee, Tanmay and Verma, Sandeep and Sen, Anik and Das, Amitava and Ganguly, Bishwajit and Ghosh, Hirendra N.} } @article { ISI:000309096400004, title = {Poly(allyl glycidyl ether-co-ethylene glycol dimethacrylate) copolymer beads as support for covalent immobilization of L-aminoacylase}, journal = {Reactive \& Functional Polymers}, volume = {72}, number = {10}, year = {2012}, month = {OCT}, pages = {687-694}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Porous epoxy-activated copolymer beads were synthesized as support for the covalent immobilization of Aspergillus melleus L-aminoacylase. Here, a series of copolymer bead were synthesized using either glycidyl methacrylate (GMA) or ally] glycidyl ether (AGE) as monomer units and ethylene glycol dimethacrylate (EGDM) as cross-linking agent. The effect of monomer used and the effect of amount of cross-linking agent on covalent immobilization of aminoacylase were studied. Furthermore, the effect of porogen on immobilization of aminoacylase was also evaluated. AGE-co-EGDM copolymer beads gave higher binding of aminoacylase than GMA-co-EGDM copolymer beads. AGE-co-EGDM copolymer beads synthesized with lauryl alcohol as porogen and having 150\% cross-linked density (i.e. AGE-(L)-150) gave maximum enzyme binding. Under optimum conditions, AGE-(L)-150 copolymer beads gave about 130 U/g of aminoacylase activity which corresponds to 72.24\% of activity yield. Immobilized aminoacylase showed a broader pH, higher temperature and extended storage stability. (C) 2012 Elsevier Ltd. All rights reserved.

}, keywords = {Enzyme immobilization, Epoxy-activated support, L-Aminoacylase}, issn = {1381-5148}, doi = {10.1016/j.reactfunctpolym.2012.06.012}, author = {Vaidya, Bhalchandra K. and Ingavle, Ganesh C. and Ponrathnam, S. and Nene, Sanjay N.} } @article { ISI:000303366000001, title = {Polymorphs, salts, and cocrystals: what{\textquoteright}s in a name?}, journal = {Crystal Growth \& Design}, volume = {12}, number = {5}, year = {2012}, month = {MAY}, pages = {2147-2152}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The December 2011 release of a draft United States Food and Drug Administration (FDA) guidance concerning regulatory classification of pharmaceutical cocrystals of active pharmaceutical ingredients (APIs) addressed two matters of topical interest to the crystal engineering and pharmaceutical science communities: (1) a proposed definition of cocrystals; (2) a proposed classification of pharmaceutical cocrystals as dissociable {\textquoteleft}{\textquoteleft}API-excipient{\textquoteright}{\textquoteright} molecular complexes. The Indo U.S. Bilateral Meeting sponsored by the Indo-U.S. Science and Technology Forum titled The Evolving Role of Solid State Chemistry in Pharmaceutical Science was held in Manesar near Delhi, India, from February 2-4, 2012. A session of the meeting was devoted to discussion of the FDA guidance draft. The debate generated strong consensus on the need to define cocrystals more broadly and to classify them like salts. It was also concluded that the diversity of API crystal forms makes it difficult to classify solid forms into three categories that are mutually exclusive. This perspective summarizes the discussion in the Indo-U.S. Bilateral Meeting and includes contributions from researchers who were not participants in the meeting.

}, issn = {1528-7483}, doi = {10.1021/cg3002948}, author = {Aitipamula, Srinivasulu and Banerjee, Rahul and Bansal, Arvind K. and Biradha, Kumar and Cheney, Miranda L. and Choudhury, Angshuman Roy and Desiraju, Gautam R. and Dikundwar, Amol G. and Dubey, Ritesh and Duggirala, Nagakiran and Ghogale, Preetam P. and Ghosh, Soumyajit and Goswami, Pramod Kumar and Goud, N. Rajesh and Jetti, Ram R. K. R. and Karpinski, Piotr and Kaushik, Poonam and Kumar, Dinesh and Kumar, Vineet and Moulton, Brian and Mukherjee, Arijit and Mukherjee, Gargi and Myerson, Allan S. and Puri, Vibha and Ramanan, Arunachalam and Rajamannar, T. and Reddy, C. Malla and Rodriguez-Hornedo, Nair and Rogers, Robin D. and Row, T. N. Guru and Sanphui, Palash and Shan, Ning and Shete, Ganesh and Singh, Amit and Sun, Changquan C. and Swift, Jennifer A. and Thaimattam, Ram and Thakur, Tejender S. and Thaper, Rajesh Kumar and Thomas, Sajesh P. and Tothadi, Srinu and Vangala, Venu R. and Variankaval, Narayan and Vishweshwar, Peddy and Weyna, David R. and Zaworotko, Michael J.} } @article { ISI:000306942300059, title = {Polymorphs, salts and cocrystals: what{\textquoteright}s in a name? (vol 12, pg 2147, 2012)}, journal = {Crystal Growth \& Design}, volume = {12}, number = {8}, year = {2012}, month = {AUG}, pages = {4290-4291}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, issn = {1528-7483}, doi = {10.1021/cg300704b}, author = {Aitipamula, Srinivasulu and Banerjee, Rahul and Bansal, Arvind K. and Biradha, Kumar and Cheney, Miranda L. and Choudhury, Angshuman Roy and Desiraju, Gautam R. and Dikundwar, Amol G. and Dubey, Ritesh and Duggirala, Nagakiran and Ghogale, Preetam P. and Ghosh, Soumyajit and Goswami, Pramod Kumar and Goud, N. Rajesh and Jetti, Ram R. K. R. and Karpinski, Piotr and Kaushik, Poonam and Kumar, Dinesh and Kumar, Vineet and Moulton, Brian and Mukherjee, Arijit and Mukherjee, Gargi and Myerson, Allan S. and Puri, Vibha and Ramanan, Arunachalam and Rajamannar, T. and Reddy, C. Malla and Rodriguez-Hornedo, Nair and Rogers, Robin D. and Row, T. N. Guru and Sanphui, Palash and Shan, Ning and Shete, Ganesh and Singh, Amit and Sun, Changquan C. and Swift, Jennifer A. and Thaimattam, Ram and Thakur, Tejender S. and Thaper, Rajesh Kumar and Thomas, Sajesh P. and Tothadi, Srinu and Vangala, Venu R. and Vishweshwar, Peddy and Weyna, David R. and Zaworotko, Michael J.} } @article { ISI:000300036000006, title = {Preparation of cross-linked enzyme aggregates of L-aminoacylase via co-aggregation with polyethyleneimine}, journal = {Journal of Molecular Catalysis B-Enzymatic}, volume = {74}, number = {3-4}, year = {2012}, month = {FEB}, pages = {184-191}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

L-Aminoacylase from Aspergillus melleus was co-aggregated with polyethyleneimine and subsequently cross-linked with glutaraldehyde to obtain aminoacylase-polyethyleneimine cross-linked enzyme aggregates (termed as AP-CLEA). Under the optimum conditions, AP-CLEA expressed 74.9\% activity recovery and 81.2\% aggregation yield. The said method of co-aggregation and cross-linking significantly improved the catalytic stability of L-aminoacylase with respect to temperature and storage. AP-CLEA were employed for enantioselective synthesis of three unnatural amino acids (namely: phenylglycine, homophenylalanine and 2-naphthylalanine) via chiral resolution of their ester-. amide- and N-acetyl derivatives. The enantioselectivity of AP-CLEA was the highest for hydrolysis of amino acid amides; was moderate for hydrolysis of N-acetyl amino acids and was the least for hydrolysis of amino acid esters. Furthermore, AP-CLEA were found to retain more than 92\% of the initial activity after five consecutive batches of (RS)-homophenylalanine hydrolysis suggesting an adequate operational stability of the biocatalyst. (C) 2011 Elsevier B.V. All rights reserved.

}, keywords = {chiral resolution, Cross-linked enzyme aggregates, L-Aminoacylase, Polyethyleneimine, Unnatural amino acids}, issn = {1381-1177}, doi = {10.1016/j.molcatb.2011.10.003}, author = {Vaidya, Bhalchandra K. and Kuwar, Suyog S. and Golegaonkar, Sandeep B. and Nene, Sanjay N.} } @article { ISI:000300474900013, title = {Probing influence of mesophasic transformation on performance of self-emulsifying system: effect of ion}, journal = {Molecular Pharmaceutics}, volume = {9}, number = {2}, year = {2012}, month = {FEB}, pages = {318-324}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Self-emulsifying systems are mixtures of oils and surfactants, ideally isotropic, sometimes including cosolvents, which emulsify under conditions of gentle agitation, similar to those which would be encountered in the gastrointestinal tract. The process of self-emulsification has remained the center of attraction for most researchers. Controlled hydration of self-emulsifying systems shows formation of an intermediate gel phase which upon rupture forms an emulsion. Current work was undertaken to understand and explore the microstructural properties of intermediate gel phase which are believed to influence the performance (droplet size) of the final formulation. The effect of additives on microstructural properties of intermediate gel phase has also been investigated. Microstructural elucidation of hydrated samples of intermediate regimes was done by using techniques such as small angle X-ray scattering, differential scanning calorimetry and rheology. Samples from intermediate regimes showed formation of local lamellar structure which swelled with hydration. In the present work, the effect of addition of salt form of naproxen (sodium and potassium) and naproxen (base) on microstructural properties of intermediate regimes was investigated. Systems containing naproxen salts formed larger droplets whereas naproxen base formed smaller ones. Microstructural properties of intermediate lamellar structures were well correlated with performance of the final formulation. The current studies indicate that by controlling the properties of intermediate regimes optimized formulations with desired performance can be tailor-made.

}, keywords = {emulsion, lamellar structure, liquid crystal, Microstructure, Naproxen, self-emulsifying system}, issn = {1543-8384}, doi = {10.1021/mp200541r}, author = {Patil, Sharvil S. and Venugopal, Edakkal and Bhat, Suresh K. and Mahadik, Kakasaheb R. and Paradkar, Anant R.} } @article { ISI:000306585900004, title = {Production, purification, and characterization of a beta-glucosidase of penicillium funiculosum NCL1}, journal = {Applied Biochemistry and Biotechnology}, volume = {167}, number = {5}, year = {2012}, month = {JUL}, pages = {959-972}, publisher = {HUMANA PRESS INC}, address = {999 RIVERVIEW DRIVE SUITE 208, TOTOWA, NJ 07512 USA}, abstract = {

Penicillium funiculosum NCL1, a filamentous fungus, produced significantly higher levels of beta-glucosidase. The effect of initial pH, incubation temperature, and different carbon sources on extracellular beta-glucosidase production was studied in submerged fermentation. At 30 A degrees C with initial pH 5.0, enzyme production was increased by 48-fold upon induction with paper mill waste, as compared to commercial cellulose powder. In zymogram analysis, four isoforms of beta-glucosidases were observed with wheat bran whereas a minimum of one isoform was observed with other carbon sources. A major beta-glucosidase (Bgl3A) with the apparent molecular weight of similar to 120 kDa, induced by paper mill waste, was purified 19-fold to homogeneity, with a specific activity of 1,796 U/mg. Bgl3A was a monomeric glycoprotein with 29\% of neutral carbohydrate content. It showed optimum activity at pH 4.0 and 5.0, optimum temperature at 60 A degrees C, and exhibited a half-life of 1 h at 60 A degrees C. K (m) of Bgl3A was found to be 0.057 mM with p-nitrophenyl beta-d-glucoside and V (max) was 1,920 U/mg. The purified enzyme exhibited glucose tolerance with a K (i) of 1.5 mM. Bgl3A readily hydrolyzed glucosides with beta-linkage. Bgl3A activity was enhanced (156\%) by Zn2+ and was not affected by other metal cations and reagents. The supplementation of Bgl3A (5 U/mg) with Trichoderma reesei cellulase complex (5 FPU/mg) resulted in about 70\% of enhanced glucose production, which emphasizes the industrial importance of Bgl3A.

}, keywords = {beta-Glucosidase, Paper mill waste, Penicillium funiculosum NCL1, Purification, Thermostability}, issn = {0273-2289}, doi = {10.1007/s12010-012-9645-4}, author = {Ramani, Gurusamy and Meera, Balasubramanian and Vanitha, Chinnathambi and Rao, Mala and Gunasekaran, Paramasamy} } @article { ISI:000301128300003, title = {Radical mediated deoxygenation of inositol benzylidene acetals: conformational analysis, DFT calculations, and mechanism}, journal = {Carbohydrate Research}, volume = {351}, year = {2012}, month = {APR}, pages = {26-34}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Xanthates of 1,3-benzylidene acetal derivatives of myo- and neo-inositols undergo dideoxygenation under Barton-McCombie conditions, as a result of intramolecular abstraction of the benzylidene acetal hydrogen and subsequent cleavage of the acetal ring. Scrutiny of structure of these bicyclic inositol derivatives shows that although the conformation of the two rings can vary depending on the configuration of the inositol ring and the phase in which the molecules are present, both the xanthates lead to the formation of the same dideoxyinositol. DFT calculations on these molecular systems suggest that neo-inositol derivatives undergo conformational change prior to radical formation while myo- inositol derivatives undergo conformational change subsequent to radical formation, during the deoxygenation reaction. A low barrier for intramolecular hydrogen transfer supports the extreme facility of this deoxygenation reaction. (C) 2012 Elsevier Ltd. All rights reserved.

}, keywords = {Deoxygenation, DFT, Inositol, Mechanism, Radical, Xanthate}, issn = {0008-6215}, doi = {10.1016/j.carres.2012.01.001}, author = {Gurale, Bharat P. and Vanka, Kumar and Shashidhar, Mysore S.} } @article { ISI:000301712600016, title = {Rapid self-healing hydrogels}, journal = {Proceedings of the National Academy of Sciences of the United States of America}, volume = {109}, number = {12}, year = {2012}, month = {MAR}, pages = {4383-4388}, publisher = {NATL ACAD SCIENCES}, address = {2101 CONSTITUTION AVE NW, WASHINGTON, DC 20418 USA}, abstract = {

Synthetic materials that are capable of autonomous healing upon damage are being developed at a rapid pace because of their many potential applications. Despite these advancements, achieving self-healing in permanently cross-linked hydrogels has remained elusive because of the presence of water and irreversible cross-links. Here, we demonstrate that permanently cross-linked hydrogels can be engineered to exhibit self-healing in an aqueous environment. We achieve this feature by arming the hydrogel network with flexible-pendant side chains carrying an optimal balance of hydrophilic and hydrophobic moieties that allows the side chains to mediate hydrogen bonds across the hydrogel interfaces with minimal steric hindrance and hydrophobic collapse. The self-healing reported here is rapid, occurring within seconds of the insertion of a crack into the hydrogel or juxtaposition of two separate hydrogel pieces. The healing is reversible and can be switched on and off via changes in pH, allowing external control over the healing process. Moreover, the hydrogels can sustain multiple cycles of healing and separation without compromising their mechanical properties and healing kinetics. Beyond revealing how secondary interactions could be harnessed to introduce new functions to chemically crosslinked polymeric systems, we also demonstrate various potential applications of such easy-to-synthesize, smart, self-healing hydrogels.

}, keywords = {adhesives, biomimetic materials, Hydrophobicity, molecular dynamics, smart materials}, issn = {0027-8424}, doi = {10.1073/pnas.1201122109}, author = {Phadke, Ameya and Zhang, Chao and Arman, Bedri and Hsu, Cheng-Chih and Mashelkar, Raghunath Anant and Lele, Ashish K. and Tauber, Michael J. and Arya, Gaurav and Varghese, Shyni} } @article {42510, title = {Sequential energy and electron transfer in polynuclear complex sensitized TiO2 nanoparticles}, journal = {Journal of Physical Chemistry Letters}, volume = {3}, year = {2012}, month = {MAY}, pages = {1543{\textendash}1548}, abstract = {

Polynuclear{\textendash}polypyridyl complexes exhibit a directional energy-transfer property that can improve their photosensitization activity. In the present work, the energy-transfer process is explored in a trinuclear Ru2∧Os1 complex using transient absorption spectroscopy. This study reveals an efficient excitation energy transfer from the terminal (RuII complex) to the core (OsII complex) region in the ultrafast time domain (400 fs{\textendash}40 ps). The excitation energy funnel is useful in improving the functionalized core activity. This is evidenced in an interfacial electron-transfer study of Ru2∧Os1, Ru2∧Ru1, and Os1 complex sensitized TiO2 nanoparticle (TiO2 NP) systems. The intramolecular energy transfer causes sequential excitation of the core part of the Ru2∧Os1 complex, which leads to multiexponential electron injection into TiO2 NP. Besides this, the electronic coupling between the metal ion centers stabilizes the positive charge within the trinuclear complex, which results in a slow charge recombination reaction. This study shows that polynuclear complexes can be very useful for their panchromatic effects, unidirectional energy- and electron-transfer properties.

}, doi = {10.1021/jz3005305}, author = {Verma, Sandeep and Kar, Prasenjit and Banerjee, Tanmay and Das, Amitava and Ghosh, Hirendra N.} } @article { ISI:000311350000013, title = {Simple one pot synthesis of nano gold-mesoporous silica and its oxidation catalysis}, journal = {Catalysis Today}, volume = {198}, number = {1, SI}, year = {2012}, month = {DEC}, pages = {92-97}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

A simple one pot synthesis strategy using a non ionic triblock copolymer P123 as reducing as well as templating agent has been employed to prepare nano gold particles incorporated in the pores of mesoporous silica catalyst. The catalyst is characterized by XRD, nitrogen adsorption desorption isotherms at 77 K and TEM. The presence of small gold nanopartilces (similar to 2-4 nm) clearly demonstrated that this strategy can be effective in incorporating Au inside mesochannels. The catalyst reduced at 300 degrees C in H-2 was found to be active for oxidation reactions, such as CO oxidation, and benzyl alcohol. (C) 2012 Elsevier B. V. All rights reserved.

}, keywords = {Alcohol oxidation, CO oxidation, Gold catalysis, Mesoporous silica}, issn = {0920-5861}, doi = {10.1016/j.cattod.2012.05.053}, author = {Sekhar, A. C. Sunil and Sivaranjani, Kumarsrinivasan and Gopinath, Chinnakonda S. and Vinod, C. P.} } @article { ISI:000298839400032, title = {Strength from weakness: the role of CH center dot center dot center dot N hydrogen bond in the formation of wave-like topology in crystals of aza-heterocycles}, journal = {Crystengcomm}, volume = {14}, number = {2}, year = {2012}, month = {OCT}, pages = {519-524}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Crystal engineering has succeeded in the design and construction of various architectures such as tapes, ribbons, rosettes, layers etc. Though wavy layer packing is known to occur in crystals, no crystal engineering attempts have been ventured to create wavy layer topology in crystals. Aromatic nitrogen heterocyclics (ANHs) are known to preferentially self assemble in lateral fashion through edge-to-edge CH center dot center dot center dot N hydrogen bonds. Exploiting this preferential lateral assembly of ANHs, we have engineered wavy layer architectures in the crystals of various substituted quinolines.

}, issn = {1466-8033}, doi = {10.1039/c1ce05997a}, author = {Shivakumar, Kota and Vidyasagar, Adiyala and Naidu, Andra and Gonnade, Rajesh G. and Sureshan, Kana M.} } @article { ISI:000312564500027, title = {Studies toward the synthesis of potent anti-inflammatory peptides solomonamides A and B: synthesis of a macrocyclic skeleton and key fragment 4-amino-6-(2 {\textquoteleft}-amino-4 {\textquoteleft}-hydroxyphenyl)-3-hydroxy-2-methyl-6-oxohexanoic acid (AHMOA)}, journal = {Organic Letters}, volume = {14}, number = {24}, year = {2012}, month = {DEC}, pages = {6222-6225}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

A first synthetic effort toward total synthesis of highly potent solomonamides is disclosed. An efficient strategy to synthesize this class of compounds, along with the synthesis of a core macrocycle (shown in red) and the key fragment AHMOA, is described.

}, issn = {1523-7060}, doi = {10.1021/ol303149k}, author = {Kashinath, K. and Vasudevan, N. and Reddy, D. Srinivasa} } @article { ISI:000310947900007, title = {Synthesis of isomeric corniculatolides}, journal = {Tetrahedron Letters}, volume = {53}, number = {47}, year = {2012}, month = {NOV}, pages = {6343-6346}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

Synthesis of three natural macrolides 11-O-methylcorniculatolide A, 11-O-methylisocorniculatolide A and isocorniculatolide A is reported using a simple, straight forward and high-yielding route. The present synthesis confirms the assigned molecular structures and provides an access to sufficient quantities of the natural products for the biological evaluation. In addition, we have determined the anti-TB potential of the three natural compounds using Alamar-Blue assay (H(37)Rv) and found no significant inhibitory activity at 100 mu g/ml. Excellent yields, short sequence and useful SAR information are the highlights of the present work. (C) 2012 Elsevier Ltd. All rights reserved.

}, keywords = {Diaryl ether, Isocorniculatolide, Macrocyclization, Mitsunobu reaction, Total synthesis}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2012.09.010}, author = {Raut, Gajanan N. and Chakraborty, Kasturi and Verma, Priyanka and Gokhale, Rajesh S. and Reddy, D. Srinivasa} } @article {43253, title = {TDR Targets: a chemogenomics resource for neglected diseases}, journal = {Nucleic Acids Research}, volume = {40}, year = {2012}, month = {JAN}, pages = {D1118-D1127}, abstract = {The TDR Targets Database (http://tdrtargets.org) has been designed and developed as an online resource to facilitate the rapid identification and prioritization of molecular targets for drug development, focusing on pathogens responsible for neglected human diseases. The database integrates pathogen specific genomic information with functional data (e.g. expression, phylogeny, essentiality) for genes collected from various sources, including literature curation. This information can be browsed and queried using an extensive web interface with functionalities for combining, saving, exporting and sharing the query results. Target genes can be ranked and prioritized using numerical weights assigned to the criteria used for querying. In this report we describe recent updates to the TDR Targets database, including the addition of new genomes (specifically helminths), and integration of chemical structure, property and bioactivity information for biological ligands, drugs and inhibitors and cheminformatic tools for querying and visualizing these chemical data. These changes greatly facilitate exploration of linkages (both known and predicted) between genes and small molecules, yielding insight into whether particular proteins may be druggable, effectively allowing the navigation of chemical space in a genomics context.}, doi = {10.1093/nar/gkr1053}, author = {Magarinos, Maria P. and Carmona, Santiago J. and Crowther, Gregory J. and Ralph, Stuart A. and Roos, David S. and Shanmugam, Dhanasekaran and Van Voorhis, Wesley C.} } @article { ISI:000298712000050, title = {Theoretical study of metal-metal cooperativity in the homogeneous water gas shift reaction}, journal = {Inorganic Chemistry}, volume = {51}, number = {1}, year = {2012}, month = {JAN}, pages = {377-385}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The possibility of metal-metal cooperativity in improving the yield of the homogeneous water gas shift reaction (WGSR) has been investigated through full quantum mechanical density functional theory calculations. The calculations indicate that bimetallic catalysts would be likely to be more highly active than mononuclear metal-based catalysts for the WGSR. The results have implications for the design of improved WGSR catalysts in the future.

}, issn = {0020-1669}, doi = {10.1021/ic201788t}, author = {Kuriakose, Nishamol and Kadam, Shantanu and Vanka, Kumar} } @article { ISI:000303304900028, title = {TiO2-Au plasmonic nanocomposite for enhanced dye-sensitized solar cell (DSSC) performance}, journal = {Solar Energy}, volume = {86}, number = {5}, year = {2012}, month = {MAY}, pages = {1428-1434}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

Anatase TiO2 nanoparticles dressed with gold nanoparticles were synthesized by hydrothermal process by using mixed precursor and controlled conditions. Diffused Reflectance Spectra (DRS) reveal that in addition to the expected TiO2 interband absorption below 360 nm gold surface plasmon feature occurs near 564 nm. It is shown that the dye sensitized solar cells made using TiO2-Au plasmonic nanocomposite yield superior performance with conversion efficiency (CE) of similar to 6\% (no light harvesting), current density (J(SC)) of similar to 13.2 mA/cm(2), open circuit voltage (V-oc) of similar to 0.74 V and fill factor (FF) 0.61; considerably better than that with only TiO2 nanoparticles (CE similar to 5\%, J(SC) similar to 12.6 mA/cm(2), V-oc similar to 0.70 V, FF similar to 0.56). (C) 2012 Elsevier Ltd. All rights reserved.

}, keywords = {Anatase TiO2, Au, Dye-sensitized solar cells, Hybrid composite, hydrothermal}, issn = {0038-092X}, doi = {10.1016/j.solener.2012.02.002}, author = {Muduli, Subas and Game, Onkar S. and Dhas, Vivek V. and Vijayamohanan, K. and Bogle, Kashinath A. and Valanoor, N. and Ogale, Satishchandra B.} } @article {42809, title = {Total synthesis and structural revision of stagonolide D}, journal = {Journal of Organic Chemistry}, volume = {77}, year = {2012}, month = {FEB}, pages = {2169{\textendash}2175}, abstract = {

The total synthesis of the putative structure of stagonolide D has been completed. The relative and absolute configuration of stagonolide D was established by synthesizing its optical antipode. The adopted strategy involves the construction of the central macrolide employing ring-closing metathesis (RCM), followed by selective protecting group manipulations and a final concomitant -OTBS deprotection and displacement of an -OMs placed next to it, resulting in the formation of the epoxide ring.

}, doi = {10.1021/jo202138g}, author = {Vadhadiya, Paresh M. and Puranik, Vedavati G. and Ramana, Chepuri V.} } @article { ISI:000300041700017, title = {Towards biodegradable elastomers: green synthesis of carbohydrate functionalized styrene-butadiene-styrene copolymer by click chemistry}, journal = {Green Chemistry}, volume = {14}, number = {2}, year = {2012}, month = {DEC}, pages = {348-356}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Random attachment of sugar molecules to synthetic polymers is an important strategy to induce biodegradability in these polymers. The present study successfully employs {\textquoteleft}{\textquoteleft}click{\textquoteright}{\textquoteright} chemistry to introduce low levels of sugar molecules onto styrene-butadiene-styrene (SBS) copolymer, a widely used commodity polymer which is not biodegradable. Spectral, morphological and thermal studies of the modified polymers were carried out to show the dramatic changes in the properties of these modified polymers. Thermal stability of glucose linked SBS had onset of degradation at 428 degrees C, down from 478 degrees C observed for SBS. Morphology studied by WAXRD and SEM showed destructuring of the polymer domains of SBS, which is beneficial for biodegradation of these polymers. Previous studies showed that sugars anchored by hydrolysable ester groups onto polystyrene were biodegradable; current studies show that sugars anchored by unhydrolyzable C-C bonds on the butadiene component of SBS copolymer are also significantly biodegradable.

}, issn = {1463-9262}, doi = {10.1039/c1gc16146f}, author = {Singh, Rakesh and Varma, Anjanikumar} } @article { ISI:000308414500020, title = {Unusual conformational similarity of two peptide folds featuring sulfonamide and carboxamide on the backbone}, journal = {Chemical Communications}, volume = {48}, number = {78}, year = {2012}, month = {AUG}, pages = {9747-9749}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Two folded peptides featuring carboxamide and sulfonamide at the core of the peptide fold have been shown to possess almost similar conformational features, despite the well-known fact that carboxamides and sulfonamides have strikingly different hydrogen-bonding and geometrical preferences.

}, issn = {1359-7345}, doi = {10.1039/c2cc34533a}, author = {Vijayadas, Kuruppanthara N. and Davis, Hilda C. and Kotmale, Amol S. and Gawade, Rupesh L. and Puranik, Vedavati G. and Rajamohanan, Pattuparambil R. and Sanjayan, Gangadhar J.} } @article { ISI:000308089500003, title = {Water and a protic ionic liquid acted as refolding additives for chemically denatured enzymes}, journal = {Organic \& Biomolecular Chemistry}, volume = {10}, number = {37}, year = {2012}, month = {JUN}, pages = {7475-7478}, publisher = {ROYAL SOC CHEMISTRY}, type = {Article}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

In this communication, we present the ability of water and a protic ionic liquid, triethyl ammonium phosphate (TEAP) to act as refolding additives for the urea-induced chemical denaturated state of the two enzymes, alpha-chymotrypsin and succinylated Con A. We show that the enzymatic activity is regained and in certain circumstances enhanced.

}, issn = {1477-0520}, doi = {10.1039/c2ob26001h}, author = {Attri, Pankaj and Venkatesu, P. and Kumar, Anil} } @article { ISI:000320036300013, title = {Ant-pro reverse-turn motif. structural features and conformational characteristics}, journal = {European Journal of Organic Chemistry}, number = {17, SI}, year = {2013}, month = {JUN}, pages = {3529-3542}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

This article details the characteristic conformational features of the Ant-Pro reverse turn ? a folded pseudo -turn motif that displays a closed nine-membered-ring hydrogen-bonded network involving just two amino acid residues, namely anthranilic acid (Ant; a constrained -amino acid), and proline (Pro; a constrained -amino acid). The results from the extensive investigation of ten crystal structures and their NMR conformations in the solution state provide a clear idea about the conformational characteristics of the Ant-Pro reverse turn. The Ant and Pro residues, which form the turn segment, maintain a perfect antiperiplanar orientation throughout, leaving little possibility for the formation of the otherwise possible six-membered hydrogen-bonding that requires a coplanar disposition of the two amino acid residues, as clearly evident from investigation of several crystal structures. The closed hydrogen-bonded network observed in the Ant-Pro reverse turn motif, formed in the forward direction of the sequence (12 amino acid interactions) involving only two amino acid residues, is in stark contrast to the native -turns that involve four residues to form hydrogen-bonded network featuring backward 14 amino acid interactions. The readily available two-residue Ant-Pro motif raises the possibility of a practical utility, particularly in the application of rigidifying flexible peptide backbones by inserting the robust Ant-Pro reverse turn motifs into their backbone.

}, keywords = {Peptides, Peptidomimetics, Protein folding, Protein structures}, issn = {1434-193X}, doi = {10.1002/ejoc.201201739}, author = {Thorat, Vijaykumar H. and Ingole, Tukaram S. and Vijayadas, Kuruppanthara N. and Nair, Roshna V. and Kale, Sangram S. and Ramesh, Veera V. E. and Davis, Hilda C. and Prabhakaran, Panchami and Gonnade, Rajesh G. and Gawade, Rupesh L. and Puranik, Vedavati G. and Rajamohanan, Pattuparambil R. and Sanjayan, Gangadhar J.} } @article { ISI:000322853000052, title = {Aryne insertion reactions leading to bioactive fused quinazolinones: diastereoselective total synthesis of cruciferane}, journal = {Organic Letters}, volume = {15}, number = {15}, year = {2013}, month = {AUG}, pages = {4006-4009}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Insertion reactions of an in situ generated arynes to a variety of suitably substituted 1,3-quinazolin-4-ones have been demonstrated for a new efficient one-step approach to a diverse range of fused quinazolinone architectures. The present protocol has been effectively utilized to accomplish the concise total synthesis of recently isolated bioactive natural products tryptanthrin, phaitanthrins A-C, and cruciferane.

}, issn = {1523-7060}, doi = {10.1021/ol4018062}, author = {Vaidya, Sagar D. and N. P. Argade} } @article { ISI:000320746200022, title = {Biochemical characterization of recombinant cinnamoyl CoA reductase 1 (Ll-CCRH1) from Leucaena leucocephala}, journal = {International Journal of Biological Macromolecules}, volume = {58}, year = {2013}, month = {JUL}, pages = {154-159}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Recombinant cinnamoyl CoA reductase 1 (Ll-CCRH1) protein from Leucaena leucocephala was overexpressed in Escherichia coli BL21 (DE3) strain and purified to apparent homogeneity. Optimum pH for forward and reverse reaction was found to be 6.5 and 7.8 respectively. The enzyme was most stable around pH 6.5 at 25 degrees C for 90 min. The enzyme showed k(cat)/k(m) for feruloyl, caffeoyl, sinapoyl, coumaroyl CoA, coniferaldehyde and sinapaldehyde as 4.6, 2.4, 2.3, 1.7, 1.9 and 1.2 (x10(6) M-1 s(-1)), respectively, indicating affinity of enzyme for feruloyl CoA over other substrates and preference of reduction reaction over oxidation. Activation energy, E-a for various substrates was found to be in the range of 20-50 kJ/mol. Involvement of probable carboxylate ion, histidine, lysine or tyrosine at the active site of enzyme was predicted by pH activity profile. SAXS studies of protein showed radius 3.04 nm and volume 49.25 nm(3) with oblate ellipsoid shape. Finally, metal ion inhibition studies revealed that Ll-CCRH1 is a metal independent enzyme. (C) 2013 Elsevier B.V. All rights reserved.

}, keywords = {Activation energy, Cinnamoyl CoA esters, Cinnamoyl CoA reductase 1, SAXS, stability}, issn = {0141-8130}, doi = {10.1016/j.ijbiomac.2013.03.050}, author = {Sonawane, Prashant and Vishwakarma, Rishi Kishore and Khan, Bashir Mohammad} } @article { ISI:000316636600004, title = {Biodegradation of phenol by the yeast candida tropicalis: an investigation by NMR spectroscopy}, journal = {Applied Biochemistry and Biotechnology}, volume = {169}, number = {7}, year = {2013}, month = {APR}, pages = {2029-2037}, publisher = {HUMANA PRESS INC}, address = {999 RIVERVIEW DRIVE SUITE 208, TOTOWA, NJ 07512 USA}, abstract = {

The process of phenol biodegradation by the yeast Candida tropicalis NCIM 3556 in aqueous medium was studied by H-1, C-13, and DOSY NMR techniques. Samples at regular intervals were centrifuged to separate the cells, and H-1 spectral data were collected at 400 MHz. Though a gradual decrease in the concentration of phenol was observed, after an incubation period of similar to 8 h, formation of any intermediate products could not be detected. Experiments carried out with uniformly C-13-labeled phenol also failed to detect formation of any carboxylic acid intermediates during degradation. The studies indicated that the phenol was completely degraded to carbon dioxide and water in approximately 20 h. Self-diffusion coefficient measurements showed that the lifetime of phenol in the bound form is too small to impart any change in its diffusion behavior and the intermediates formed are converted to carbon dioxide and water at a very fast rate.

}, keywords = {biocatalysis, Carboxylic acid, Diffusion, Enzyme, NMR spectroscopy, phenol}, issn = {0273-2289}, doi = {10.1007/s12010-013-0119-0}, author = {Phalgune, U. D. and Rajamohanan, P. R. and Gaikwad, B. G. and Varma, R. J. and George, S.} } @article { ISI:000317712000021, title = {Can molecular cages be effective at small molecule activation? a computational investigation}, journal = {Inorganic Chemistry}, volume = {52}, number = {8}, year = {2013}, month = {APR}, pages = {4238-4243}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Several approaches have been investigated in recent years in the area of small molecule activation. The current work introduces a new concept in this field: that of molecular cages, containing only main group elements, serving to activate small molecules. Full quantum mechanical calculations employing DFT/SCS-MP2 methods indicate that recently synthesized Ga-N cage compounds would be excellent candidates for mediating in important reactions such as the catalysis of ammonia borane dehydrogenation. The current work therefore opens up exciting new possibilities in small molecule activation research.

}, issn = {0020-1669}, doi = {10.1021/ic3019887}, author = {Kuriakose, Nishamol and Vanka, Kumar} } @article { ISI:000325400600023, title = {CAP/EOM-CCSD method for the study of potential curves of resonant states}, journal = {Physical Chemistry Chemical Physics}, volume = {15}, number = {41}, year = {2013}, month = {SEP}, pages = {17915-17921}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

The equation-of-motion coupled-cluster (EOM-CC) method along with the complex absorbing potential (CAP) is used for the study of resonance in e(-)-N-2 and e(-)-CO. Resonance position and width are studied as a function of bond length. We report the potential curves (PC) of the resonance states.

}, issn = {1463-9076}, doi = {10.1039/c3cp52552j}, author = {Ghosh, Aryya and Karne, Anagha S. and Pal, Sourav and Vaval, Nayana} } @article { ISI:000313230200031, title = {Catalytic and DFT study of selective ethylene oligomerization by nickel(II) oxime-based complexes}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {366}, year = {2013}, month = {JAN}, pages = {238-246}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The reactivity of nickel(II) thiophenealdoxime complex (3) toward oligomerization of ethylene in the presence of an alkylaluminum co-catalyst has been studied. The complex was found to be a selective ethylene dimerization catalyst in the presence of co-catalysts such as methylalumoxane (MAO) and diethylaluminum chloride (DEAC). With DEAC, the productivity was considerably higher than with MAO. Under optimum conditions the productivity reaches 388 kg/mol catalyst/h/bar with DEAC whereas for MAO this value was 119 kg/mol catalyst/h/bar. Complex 3 displays good ethylene conversions of up to a maximum of 90\% with exceptionally high alpha-selectivity for 1-butene (\>99.5\%) amongst C-4 products. Computational studies using density functional theory (DFT) were also carried out to ascertain the decomposition pathway for 3 as well as that for Ni(II) complex of the pyridine ketoxime ligand 2. The results suggest that loss of one of the two bidentate oxime ligands attached to the metal center through reaction with DEAC is likely for both 2 and 3. Further, calculations indicate that the subsequent decomposition step was significantly more probable for 3 than for 2 thus explaining why the pyridine ketoxime ligand bound nickel complex 2 was experimentally found to be more stable than the thiophene aldoxime bound nickel complex 3. Calculations also show that the proton of the -OH group (oxime) plays a major role in the stability of the molecules. This was confirmed experimentally by synthesizing the Ni(II) dichloro complex of Pyridine-2-carbaldehyde O-methyloxime 5 and reacting it with ethylene under similar conditions. 5 was found to be highly active even at low co-catalyst concentrations. (c) 2012 Elsevier B.V. All rights reserved.

}, keywords = {Butene-1, Ethylene dimerization, Ni(II) complex, Thiophene aldoxime}, issn = {1381-1169}, doi = {10.1016/j.molcata.2012.09.029}, author = {Tayade, Kamlesh N. and Mane, Manoj V. and Sen, Suman and Murthy, C. N. and Tembe, Gopal L. and Pillai, S. Muthukumaru and Vanka, Kumar and Mukherjee, Soumen} } @article { ISI:000313077100009, title = {Characterization of the structures and dynamics of phosphoric acid doped benzimidazole mixtures: a molecular dynamics study}, journal = {Journal of Molecular Modeling}, volume = {19}, number = {1}, year = {2013}, month = {JAN}, pages = {109-118}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Benzimidazole-based polymer membranes like poly(2,5-benzimidazole) (ABPBI) doped with phosphoric acid (PA) are electrolytes that exhibit high proton conductivity in fuel cells at elevated temperatures. The benzimidazole (BI) moiety is an important constituent of these membranes, so the present work was performed in order to achieve a molecular understanding of the BI-PA interactions in the presence of varying levels of the PA dopant, using classical molecular dynamics (MD) simulations. The various hydrogen-bonding interactions, as characterized based on structural properties and hydrogen-bond lifetime calculations, show that both BI and PA molecules exhibit dual proton-acceptor/donor functionality. An examination of diffusion coefficients showed that the diffusion of BI decreases with increasing PA uptake, whereas the diffusion of PA slightly increases. The hydrogen-bond lifetime calculations pointed to the existence of competitive hydrogen bonding between various sites in BI and PA.

}, keywords = {Diffusion coefficient, Hydrogen bond, molecular dynamics, Radial distribution functions}, issn = {1610-2940}, doi = {10.1007/s00894-012-1519-8}, author = {More, Minal and Pahari, Swagata and Roy, Sudip and Venkatnathan, Arun} } @article { ISI:000322512300025, title = {Cloning, overexpression, crystallization and preliminary X-ray crystallographic analysis of a slow-processing mutant of penicillin G acylase from Kluyvera citrophila}, journal = {Acta Crystallographica Section F-Structural Biology and Crystallization Communications}, volume = {69}, number = {8}, year = {2013}, month = {AUG}, pages = {925-929}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

{Kluyvera citrophila penicillin G acylase (KcPGA) has recently attracted increased attention relative to the well studied and commonly used Escherichia coli PGA (EcPGA) because KcPGA is more resilient to harsh conditions and is easier to immobilize for the industrial hydrolysis of natural penicillins to generate the 6-aminopenicillin (6-APA) nucleus, which is the starting material for semi-synthetic antibiotic production. Like other penicillin acylases, KcPGA is synthesized as a single-chain inactive pro-PGA, which upon autocatalytic processing becomes an active heterodimer of alpha and beta chains. Here, the cloning of the pac gene encoding KcPGA and the preparation of a slow-processing mutant precursor are reported. The purification, crystallization and preliminary X-ray analysis of crystals of this precursor protein are described. The protein crystallized in two different space groups, P1, with unit-cell parameters a = 54.0

}, issn = {1744-3091}, doi = {10.1107/S174430911301943X}, author = {Varshney, Nishant Kumar and Ramasamy, Sureshkumar and Brannigan, James A. and Wilkinson, Anthony J. and Suresh, C. G.} } @article {42550, title = {Comparison of methods for identifying periodically varying genes}, journal = {International Journal of Bioinformatics Research and Applications}, volume = {9}, year = {2013}, month = {SEP}, pages = {53-70}, doi = {DOI: 10.1504/IJBRA.2013.050653}, author = {Vijayan, V. and Deshpande, P. and Gadgil, Chetan J. and Gadgil, Mugdha} } @article { ISI:000330613400010, title = {Crystallization: key thermodynamic, kinetic and hydrodynamic aspects}, journal = {Sadhana-Academy Proceedings in Engineering Sciences}, volume = {38}, number = {6}, year = {2013}, month = {DEC}, pages = {1287-1337}, publisher = {INDIAN ACAD SCIENCES}, address = {C V RAMAN AVENUE, SADASHIVANAGAR, P B \#8005, BANGALORE 560 080, INDIA}, abstract = {

Crystallization is extensively used in different industrial applications, including the production of a wide range of materials such as fertilizers, detergents, food and pharmaceutical products, as well as in the mineral processing industries and treatment of waste effluents. In spite of the wide-spread use of crystallization, a clear understanding of the thermodynamic, kinetic and hydrodynamic aspects of the design methodologies are not yet well established. More often than not crystallization is still considered an art especially in fine-chemicals, pharmaceuticals and life-sciences sector. It is essential to understand and relate key thermodynamic, kinetic and hydrodynamic aspects to crystallizer performance, not just in terms of yield but also in terms of product quality (characterized by particle size distribution, morphology, polymorphism and the amount of strain as well as the uptake of solvent or impurities in the crystal lattice). This paper attempts to do that by critically reviewing published experimental and modelling studies on establishing and enhancing state-of-the-art thermodynamic, kinetic and hydrodynamic aspects of crystallization. Efforts are made to discuss and raise points for emerging modelling tools needed for a flexible design and operation of crystallizers and crystallization processes that are needed to meet the ever increasing demand on precise product specifications. Focus is on bringing out the trends which can be used as perspectives for future studies in this field.

}, keywords = {CFD, Crystallization, growth, Nucleation, polymorphism, supersaturation}, issn = {0256-2499}, author = {Vedantam, Sreepriya and Ranade, Vivek V.} } @article { ISI:000315707600041, title = {Design and performance aspects of a custom-built ambient pressure photoelectron spectrometer toward bridging the pressure gap: oxidation of Cu, Ag, and Au surfaces at 1 mbar O-2 pressure}, journal = {Journal of Physical Chemistry C}, volume = {117}, number = {9}, year = {2013}, month = {MAR}, pages = {4717-4726}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The critical features of a custom-built laboratory version ambient pressure photoelectron spectrometer (Lab-APPES) are presented. A double front cone differential pumping arrangement and an aperture free design employed in the electrostatic lens regime improve the data collection and data quality. In contrast to the conventional X-ray photoelectron spectrometers (XPS) operating at ultrahigh vacuum (UHV), it is possible to explore the electronic structure of solid surfaces under working conditions or closer to working conditions with Lab-APPES. Especially surface-dependent phenomena can be explored up to 1 mbar pressure and up to 873 K by conventional heating methods and at least up to 1273 K by a laser heating method. Simultaneous XPS and reaction kinetic measurements on solid surfaces make the Lab-APPES an important tool to measure the dynamic electronic structure changes on material surfaces under reaction conditions. The interaction of O-2 with polycrystalline foils of Cu, Ag, and Au from UHV to 1 mbar and up to 773 K has been studied.

}, issn = {1932-7447}, doi = {10.1021/jp312706s}, author = {Roy, Kanak and Vinod, C. P. and Gopinath, Chinnakonda S.} } @article { ISI:000317082100007, title = {Effective fragment potential method in Q-CHEM: a guide for users and developers}, journal = {Journal of Computational Chemistry}, volume = {34}, number = {12}, year = {2013}, month = {MAY}, pages = {1060-1070}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

A detailed description of the implementation of the effective fragment potential (EFP) method in the Q-CHEM electronic structure package is presented. The Q-CHEM implementation interfaces EFP with standard quantum mechanical (QM) methods such as HartreeFock, density functional theory, perturbation theory, and coupled-cluster methods, as well as with methods for electronically excited and open-shell species, for example, configuration interaction, time-dependent density functional theory, and equation-of-motion coupled-cluster models. In addition to the QM/EFP functionality, a fragment-only feature is also available (when the system is described by effective fragments only). To aid further developments of the EFP methodology, a detailed description of the C++ classes and EFP module{\textquoteright}s workflow is presented. The EFP input structure and EFP job options are described. To assist setting up and performing EFP calculations, a collection of Perl service scripts is provided. The precomputed EFP parameters for standard fragments such as common solvents are stored in Q-CHEM{\textquoteright}s auxiliary library; they can be easily invoked, similar to specifying standard basis sets. The instructions for generating user-defined EFP parameters are given. Fragments positions can be specified by their center of mass coordinates and Euler angles. The interface with the IQMOL and WEBMO software is also described. (c) 2013 Wiley Periodicals, Inc.

}, keywords = {effective fragment potential, EFP library, hybrid QM, IQMOL, MM, modular code, nonempirical force field, Q-CHEM, WEBMO}, issn = {0192-8651}, doi = {10.1002/jcc.23223}, author = {Ghosh, Debashree and Kosenkov, Dmytro and Vanovschi, Vitalii and Flick, Joanna and Kaliman, Ilya and Shao, Yihan and Gilbert, Andrew T. B. and Krylov, Anna I. and Slipchenko, Lyudmila V.} } @article { ISI:000326745100016, title = {Efficient, direct synthesis of dimethyl carbonate from CO2 using a solid, calcined zirconium phenylphosphonate phosphite catalyst}, journal = {RSC Advances}, volume = {3}, number = {46}, year = {2013}, month = {OCT}, pages = {23993-23996}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol with 100 mol\% selectivity using a solid, reusable, hydrophobic, calcined zirconium phenylphosphonate phosphite catalyst is reported for the first time. DMC yield as high as 26 mmol g(-1) catalyst correlated with the concentration of acid and base sites is obtained.

}, issn = {2046-2069}, doi = {10.1039/c3ra44368j}, author = {Unnikrishnan, Pulikkeel and Varhadi, Poonam and Srinivas, Darbha} } @article { ISI:000315874200009, title = {Electronic transition dipole moments and dipole oscillator strengths within fock-space multi-reference coupled cluster framework: an efficient and novel approach}, journal = {Journal of Chemical Physics}, volume = {138}, number = {9}, year = {2013}, month = {MAR}, pages = {094108}, publisher = {AMER INST PHYSICS}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

Within the Fock-space multi-reference coupled cluster framework, we have evaluated the electronic transition dipole moments, which determine absorption intensities. These depend on matrix elements between two different wave functions (e. g., ground state to the excited state). We present two different ways, to calculate these transition moments. In the first method, we construct the ground and excited state wave functions with the normal exponential ansatz of Fock-space coupled cluster method and then calculate the relevant off-diagonal matrix elements. In the second approach, we linearize the exponential form of the wave operator which will generate the left vector, by use of Lagrangian formulation. The right vector is obtained from the exponential ansatz. In order to relate the transition moments to oscillator strengths, excitation energies need to be evaluated. The excitation energies are obtained from the Fock-space multi-reference framework. The transition dipole moments of the ground to a few excited states, together with the oscillator strengths of a few molecules, are presented. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4793277]

}, issn = {0021-9606}, doi = {10.1063/1.4793277}, author = {Bhattacharya, Debarati and Vaval, Nayana and Pal, Sourav} } @article { ISI:000328182900006, title = {Ester vs. amide on folding: a case study with a 2-residue synthetic peptide}, journal = {Organic \& Biomolecular Chemistry}, volume = {11}, number = {48}, year = {2013}, month = {DEC}, pages = {8348-8356}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Although known for their inferiority as hydrogen-bonding acceptors when compared to amides, esters are often found at the C-terminus of peptides and synthetic oligomers (foldamers), presumably due to the synthetic readiness with which they are obtained using protected peptide coupling, deploying amino acid esters at the C-terminus. When the H-bonding interactions deviate from regularity at the termini, peptide chains tend to {\textquoteleft}{\textquoteleft}fray apart{\textquoteright}{\textquoteright}. However, the individual contributions of C-terminal esters in causing peptide chain end-fraying goes often unnoticed, particularly due to diverse competing effects emanating from large peptide chains. Herein, we describe a striking case of a comparison of the individual contributions of C-terminal ester vs. amide carbonyl as a H-bonding acceptor in the folding of a peptide. A simple two-residue peptide fold has been used as a testing case to demonstrate that amide carbonyl is far superior to ester carbonyl in promoting peptide folding, alienating end-fraying. This finding would have a bearing on the fundamental understanding of the individual contributions of stabilizing/destabilizing non-covalent interactions in peptide folding.

}, issn = {1477-0520}, doi = {10.1039/c3ob41967c}, author = {Vijayadas, Kuruppanthara N. and Nair, Roshna V. and Gawade, Rupesh L. and Kotmale, Amol S. and Prabhakaran, Panchami and Gonnade, Rajesh G. and Puranik, Vedavati G. and Rajamohanan, Pattuparambil R. and Sanjayan, Gangadhar J.} } @article { ISI:000327467000009, title = {Exploring the effectiveness of different Lewis pair combinations in caged structures for the catalysis of ammonia borane dehydrogenation: a DFT study}, journal = {Physical Chemistry Chemical Physics}, volume = {15}, number = {48}, year = {2013}, month = {OCT}, pages = {20857-20867}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Zero dimensional cage structures containing four phenyl rings separated by imine linkers have recently been synthesized. In the current work, through a computational investigation using density functional theory (DFT), we demonstrate that modifying such cages by replacing the 2, 4, 6 carbon atoms in the phenyl rings to yield new rings, as well as replacing the imine moiety in the linker by other electronegative atoms, can yield interesting new cages that can be reactive in catalysing reactions such as the dehydrogenation of ammonia borane-an important reaction in hydrogen storage research. Specifically, it is predicted that phosphorus-nitrogen pairs (phosphorus in the 2, 4, 6 positions in the ring, nitrogen in the linker position), germanium-nitrogen and germanium-phosphorus pair combinations would lead to effective Lewis pairs that can work in tandem to dehydrogenate ammonia borane efficiently under room temperature conditions.

}, issn = {1463-9076}, doi = {10.1039/c3cp53557f}, author = {Pal, Amrita and Vanka, Kumar} } @article { ISI:000319006300007, title = {Extended coupled cluster through nth perturbation order for molecular response properties: a comparative study}, journal = {Chemical Physics}, volume = {417}, year = {2013}, month = {MAY}, pages = {45-51}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

In this paper, we have presented and analyzed the extended coupled cluster (ECC) energy functional, truncated up to nth perturbation order in which expansion is limit to operators of the single and double excitations. The expression for the first order energy derivatives based on the above truncation schemes has been derived and numerically analyzed. We have done a comparative study for dipole moment in various perturbative ECC (n) methods (2 \<= n \<= 5) for three systems (HF, H2O and BH) at equilibrium geometry. We have particularly studied two variants of ECC (4) and ECC (5*) method for stretched geometry. We have analyzed the contribution of important terms present in ECC functional based on perturbative argument. We have compared our results with standard coupled cluster (CCSD) as well as cubic truncated ECC and also benchmarked with the full CI results wherever available. (c) 2013 Elsevier B.V. All rights reserved.

}, keywords = {Dipole moment, Energy functional, Extended coupled cluster}, issn = {0301-0104}, doi = {10.1016/j.chemphys.2013.03.012}, author = {Gupta, Jitendra and Manohar, Prashant Uday and Ghosh, Aryya and Vaval, Nayana and Pal, Sourav} } @article { ISI:000328864800072, title = {First total synthesis of hunanamycin A}, journal = {Organic Letters}, volume = {15}, number = {17}, year = {2013}, month = {SEP}, pages = {4556-4559}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The first total synthesis of hunanamycin A, an antibiotic natural product with a pyrido[1,2,3-de]quinoxaline-2,3-dione core from a marine-derived Bacillus hunanensis, is disclosed. The present effort provides access to sufficient amounts of scarce hunanamycin A for further biological evaluation and confirmation of the assigned absolute configuration. In addition, four new analogues of the natural product are reported.

}, issn = {1523-7060}, doi = {10.1021/ol402110e}, author = {Shingare, Rahul D. and Velayudham, R. and Gawade, Jalindar R. and Reddy, D. Srinivasa} } @article { ISI:000318538100003, title = {Fock space multireference coupled cluster theory: study of shape resonance}, journal = {International Journal of Quantum Chemistry}, volume = {113}, number = {12}, year = {2013}, month = {JUN}, pages = {1690-1695}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

The complex absorbing potential along with correlated independent particle potential (CIP) Fock space multireference coupled cluster method is used for the study of resonances. We have studied shape resonance of e(-) - F-2, e(-) - N2O and e(-) -CO molecules. In particular, we have studied e(-) - F-2 scattering at different bond lengths to know whether F-2(-) is bound at the equilibrium bond length of F-2. (C) 2013 Wiley Periodicals, Inc.

}, keywords = {correlated independent particle potential, Fock-space multireference coupled cluster theory, shape resonance}, issn = {0020-7608}, doi = {10.1002/qua.24387}, author = {Bhattacharya, Sumantra and Vaval, Nayana and Pal, Sourav} } @article { ISI:000319134800020, title = {Functional characterization of a flavonoid glycosyltransferase gene from withania somnifera (Ashwagandha)}, journal = {Applied Biochemistry and Biotechnology}, volume = {170}, number = {3}, year = {2013}, month = {JUN}, pages = {729-741}, publisher = {HUMANA PRESS INC}, address = {999 RIVERVIEW DRIVE SUITE 208, TOTOWA, NJ 07512 USA}, abstract = {

Glycosylation of flavonoids is mediated by family 1 uridine diphosphate (UDP)-dependent glycosyltransferases (UGTs). Until date, there are few reports on functionally characterized flavonoid glycosyltransferases from Withania somnifera. In this study, we cloned the glycosyltransferase gene from W. somnifera (UGT73A16) showing 85-92 \% homology with UGTs from other plants. UGT73A16 was expressed as a His(6)-tagged fusion protein in Escherichia coli. Several compounds, including flavonoids, were screened as potential substrates for UGT73A16. HPLC analysis and hypsochromic shift indicated that UGT73A16 transfers a glucose molecule to several different flavonoids. Based on kinetic parameters, UGT73A16 shows more catalytic efficiency towards naringenin. Here, we explored UGT73A16 of W. somnifera as whole cell catalyst in E. coli. We used flavonoids (genistein, apigenin, kaempferol, naringenin, biochanin A, and daidzein) as substrates for this study. More than 95 \% of the glucoside products were released into the medium, facilitating their isolation. Glycosylation of substrates occurred on the 7- and 3-hydroxyl group of the aglycone. UGT73A16 also displayed regiospecific glucosyl transfer activity towards 3-hydroxy flavone compound, which is the backbone of all flavonols and also for a chemically synthesized compound, not found naturally. The present study generates essential knowledge and molecular as well as biochemical tools that allow the verification of UGT73A16 in glycosylation.

}, keywords = {Flavonoid, glycosylation, Glycosyltransferase, Hypsochromic shift, Plant secondary product glycosyltransferase (PSPG), Withania somnifera}, issn = {0273-2289}, doi = {10.1007/s12010-013-0230-2}, author = {Singh, Somesh and Vishwakarma, Rishi. K. and Kumar, R. J. Santosh and Sonawane, Prashant D. and Ruby and Khan, Bashir Mohammad} } @article { ISI:000323669900005, title = {Functional characterization of a glucosyltransferase specific to flavonoid 7-O-glucosides from withania somnifera}, journal = {Plant Molecular Biology Reporter}, volume = {31}, number = {5}, year = {2013}, month = {OCT}, pages = {1100-1108}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Flavonoids are a large class of phenylpropanoid-derived secondary metabolites, which are usually glycosylated by UDP-glycosyltransferases with one or more sugar groups. Here, we report the cloning and biochemical characterization of a flavonoid glycosyltransferase gene from Withania somnifera (WsGT), which is an important medicinal plant used in Ayurvedic formulations. Using PCR primers, designed for a highly conserved region of previously reported glycosyltransferases, we were able to isolate the corresponding fragment of the WsGT gene. Rapid amplification of cDNA ends (RACE) was then employed to isolate full-length cDNA, which had an open reading frame of 1,371 bp that encode for 456 amino acids. Phylogenetic analysis indicated that WsGT was similar to that of family 1 GT-B glycosyltransferase. Biochemical analysis revealed that WsGT interacts with UDP-glucose and was capable of regiospecifically glycosylating flavonoid-7-ols, such as apigenin, naringenin, luteolin, diadzein and genistein. Expression profiling studies showed that WsGT was highly expressed in young and mature leaves of W. somnifera. Furthermore, exposure to salicylic acid enhanced the expression of WsGT in the leaves and heat shock treatment resulted in decreased expression of WsGT after an initial increase. This may suggest the role of WsGT in response to abiotic/biotic stresses.

}, keywords = {Diadzein, Flavonoids, Glycosyltransferase, Withania somnifera}, issn = {0735-9640}, doi = {10.1007/s11105-013-0573-4}, author = {Kumar, R. J. Santosh and Ruby and Singh, Somesh and Sonawane, Prashant D. and Vishwakarma, R. K. and Khan, Bashir Mohammad} } @article { ISI:000324265500024, title = {Functional nanoparticles obtained from cellulose: engineering the shape and size of 6-carboxycellulose}, journal = {Chemical Communications}, volume = {49}, number = {78}, year = {2013}, month = {AUG}, pages = {8818-8820}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Agricultural residue derived cellulose and cotton cellulose were used to synthesize quasi-spherical nanoparticles of 6-carboxycellulose having diameter 25-35 nm. This provides a new range of functionalized nanostructured celluloses with increased versatility and applications. The nanoparticles were efficient in stabilizing carbon nanotube dispersions and were effective anti-microbial agents against E. coli.

}, issn = {1359-7345}, doi = {10.1039/c3cc44551h}, author = {Sharma, Priyanka R. and Varma, Anjanikumar} } @article { ISI:000326674800001, title = {GIAO/DFT studies on 1,2,4-triazole-5-thiones and their propargyl derivatives}, journal = {Magnetic Resonance in Chemistry}, volume = {51}, number = {12}, year = {2013}, month = {DEC}, pages = {767-774}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

Density functional theory (DFT)/Becke-Lee-Yang-Parr (B3LYP) and gauge-including atomic orbital (GIAO) calculations were performed on a number of 1,2,4-triazole derivatives, and the optimized structural parameters were employed to ascertain the nature of their predominant tautomers. C-13 and N-15 NMR chemical shifts of 3-substituted 1,2,4-triazole-5-thiones and their propargylated derivatives were calculated via GIAO/DFT approach at the B3LYP level of theory with geometry optimization using a 6-311++G** basis set. A good agreement between theoretical and experimental C-13 and N-15 NMR chemical shifts could be found for the systems investigated. The data generated were useful in predicting N-15 chemical shifts of all the nitrogen atoms of the triazole ring, some of which could not be obtained in solution state N-15 HMBC/HSQC NMR measurements. The energy profile computed for the dipropargylated derivatives was found to follow the product distribution profile of regioisomers formed during propargylation of 1,2,4-triazole thiones. Copyright (c) 2013 John Wiley \& Sons, Ltd.

}, keywords = {1, 2, 4-triazole-5-thiones, C-13, DFT, GIAO, N-15, NMR, Regioisomers, tautomers}, issn = {0749-1581}, doi = {10.1002/mrc.4012}, author = {Phalgune, Usha D. and Vanka, Kumar and Rajamohanan, P. R.} } @article { ISI:000317352000009, title = {Hydrate phase equilibrium of ternary gas mixtures containing carbon dioxide, hydrogen and propane}, journal = {Journal of Chemical Thermodynamics}, volume = {61}, year = {2013}, month = {JUN}, pages = {58-63}, publisher = {ACADEMIC PRESS LTD- ELSEVIER SCIENCE LTD}, address = {24-28 OVAL RD, LONDON NW1 7DX, ENGLAND}, abstract = {

Hydrate phase equilibrium of the ternary guest mixtures containing carbon dioxide, hydrogen and propane at two different compositions were determined. Addition of mole composition of 2.5\% propane to the fuel gas (CO2 (40\%)/H-2 (60\%)) mixture reduces the hydrate formation conditions by 66\% at the temperature of 278.4 K. A Clausius-Clapeyron plot for the experimental results was plotted and from the slope, the enthalpy of hydrate dissociation was calculated. The enthalpy of dissociation of the mixed hydrate formed from a ternary gas mixture containing mole composition 38.1\% CO2, 59.4\% H-2 and 2.5\% C3H8 was found to be 110 kJ.mol(-1) and hence it was concluded that the mixed hydrate formed structure II (sII) hydrates. Whereas for the ternary gas mixture containing mole composition 80.0\% CO2, 18.8\% H-2, and 1.2\% C3H8, the enthalpy of dissociation of the mixed hydrate was found to be 78 kJ.mol(-1) and hence we believe the mixed hydrate formed structure I (sI) hydrate. (C) 2013 Elsevier Ltd. All rights reserved.

}, keywords = {Carbon dioxide capture, Gas hydrates, Global warming, Phase equilibrium, Pre-combustion, Thermodynamics}, issn = {0021-9614}, doi = {10.1016/j.jct.2013.02.003}, author = {Babu, Ponnivalavan and Yang, Ting and Veluswamy, Hari Prakash and Kumar, Rajnish and Linga, Praveen} } @article { ISI:000314177300008, title = {Influence of the sophorolipid molecular geometry on their self-assembled structures}, journal = {Chemistry-an Asian Journal}, volume = {8}, number = {2}, year = {2013}, month = {FEB}, pages = {369-372}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, keywords = {bolaamphiphiles, helical structures, p-p stacking, Self-assembly, sophorolipids}, issn = {1861-4728}, doi = {10.1002/asia.201200935}, author = {Dhasaiyan, Prabhu and Banerjee, Agnimitra and Visaveliya, Nikunjkumar and Bhagavatula L. V. Prasad} } @article {42654, title = {Interatomic coulombic decay in (HF)n,(n=2-3) clusters using CAP/EOM-CCSD method}, journal = {Molecular Physics}, volume = {112}, year = {2013}, month = {NOV}, pages = {669-673}, type = {Article}, abstract = {

The equation-of-motion coupled-cluster method along with the complex absorbing potential has been applied to study the interatomic Coulombic decay mechanism in hydrogen-bonded clusters. We have applied this method to calculate the lifetime of the F 2s inner-valence ionised state of (HF)(n) (n = 2-3) clusters. The lifetime is found to be very short and decreases substantially with increasing the number of HF monomer.

}, keywords = {complex absorbing potential (CAP), equation-of-motion coupled-cluster (EOM-CC), HF clusters, interatomic Coulombic decay (ICD)}, issn = {0026-8976}, doi = {10.1080/00268976.2013.852263}, author = {Ghosh, Aryya and Pal, Sourav and Vaval, Nayana} } @article { ISI:000323509900012, title = {Lagrange multiplier approach for excited state properties through intermediate hamiltonian formulation of fock space multireference coupled-cluster theory}, journal = {Journal of Chemical Physics}, volume = {139}, number = {7}, year = {2013}, month = {AUG}, pages = {074108}, publisher = {AMER INST PHYSICS}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

In this paper, we present a formulation based on Lagrange multiplier approach for efficient evaluation of excited state energy derivatives in Fock space coupled cluster theory within the intermediate Hamiltonian framework. The formulation is applied to derive the explicit generic expressions up to second order energy derivatives for [1, 1] sector of Fock space with singles and doubles approximation. Its advantage, efficiency, and interconnection in comparison to the Lagrange multiplier approach in traditional formulation of Fock space, which is built on the concept of Bloch equation based effective Hamiltonian, has been discussed. Computational strategy for their implementation has also been discussed in some detail. (C) 2013 AIP Publishing LLC.

}, issn = {0021-9606}, doi = {10.1063/1.4817943}, author = {Gupta, Jitendra and Vaval, Nayana and Pal, Sourav} } @article { ISI:000320005100018, title = {Mapping ion-induced mesophasic transformation in lyotropic in situ gelling system and its correlation with pharmaceutical performance}, journal = {Pharmaceutical Research}, volume = {30}, number = {7}, year = {2013}, month = {JUL}, pages = {1906-1914}, publisher = {SPRINGER/PLENUM PUBLISHERS}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

To investigate influence of ion induced mesophasic transformation on pharmaceutical performance of in situ gelling system consisting of glyceryl monooleate. The prepared system showed mesophasic transformation during its conversion from sol to gel upon controlled hydration. The process of mesophasic transformation was studied by SAXS, DSC, rheology and plane polarized light microscopy. Further the influence of additives i.e. naproxen salts (sodium and potassium) and naproxen (base) on the process of mesophasic transformation was also elucidated. It was observed that addition of salt form of naproxen transformed W/O emulsions into cubic mesophase whereas addition of base form of naproxen formed reverse hexagonal (H-II) phase upon controlled hydration. The cubic mesophase formed by naproxen salts retarded the drug release for initial 3 h whereas H-II phase showed sustained drug release characteristics for naproxen base following Higuchi drug release kinetics. The current work suggests that formulations with tailor made pharmaceutical performance can be developed by selecting proper additives in the system so as to obtain the desired mesophase {\textquoteleft}on demand{\textquoteright} thereby controlling drug release characteristics.

}, keywords = {cubic phase, hexagonal phase, liquid crystal, mesophasic transformation, sustained drug release}, issn = {0724-8741}, doi = {10.1007/s11095-013-1033-4}, author = {Patil, Sharvil S. and Venugopal, Edakkal and Bhat, Suresh K. and Mahadik, Kakasaheb R. and Paradkar, Anant R.} } @article { ISI:000318589100018, title = {Metal or nonmetal cooperation with a phenyl group: route to catalysis? a computational investigation}, journal = {ACS Catalysis}, volume = {3}, number = {5}, year = {2013}, month = {MAY}, pages = {920-927}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Full quantum mechanical calculations demonstrate that cooperativity in the form of the activation of the M-C bond (M: transition metal or boron, C: the ipso carbon of the coordinated phenyl group) can lead to effective catalysis pathways. Calculations show that the presence of an aromatic bidentate ligand attached to a transition metal, or even a main group element, such as boron, can lead to effective catalysts for,a, range of important reactions, such as the dehydrogenation of ammonia borane and formic acid and the activation of the N-H, bond in aromatic amities. Moreover, it is shown that the design of tridentate pincer complexes with the aromatic group at a terminal end can lead to effective M-C cooperativity. As such, the current work introduces a new concept in cooperativity and bond activation chemistry.

}, keywords = {catalysis, Density functional theory, metal-ligand cooperativity, small molecule activation}, issn = {2155-5435}, doi = {10.1021/cs400174u}, author = {Ghatak, Kamalika and Mane, Manoj and Vanka, Kumar} } @article { ISI:000324794900010, title = {Molecular characterization and differential expression studies of an oxidosqualene cyclase (OSC) gene of Brahmi (Bacopa monniera)}, journal = {Physiology and Molecular Biology of Plants}, volume = {19}, number = {4}, year = {2013}, month = {OCT}, pages = {547-553}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Triterpenoid saponins are the class of secondary metabolites, synthesized via isoprenoid pathway. Oxidosqualene cyclases (OSCs) catalyzes the cyclization of 2, 3-oxidosqualene to various triterpene skeletons, the first committed step in triterpenoid biosynthesis. A full-length oxidosqualene cyclase cDNA from Bacopa monniera (BmOSC) was isolated and characterized. The open reading frame (ORF) of BmOSC consists of 2,292 bp, encoding 764 amino acid residues with an apparent molecular mass of 87.62 kDa and theoretical pI 6.21. It contained four QxxxxxW motifs, one Asp-Cys-Thr-Ala-Glu (DCTAE) motif which is highly conserved among the triterpene synthases and another MWCYCR motif involved in the formation of triterpenoid skeletons. The deduced amino acid sequence of BmOSC shares 80.5 \% \& 71.8 \% identity and 89.7 \% \& 83.5 \% similarity with Olea europaea mixed amyrin synthase and Panax notoginseng dammarenediol synthase respectively. Phylogenetic analysis revealed that BmOSC is closely related with other plant OSCs. Quantitative real-time PCR (qRT-PCR) data showed that BmOSC is expressed in all tissues examined with higher expression in stem and leaves as compared to roots and floral parts.

}, issn = {0971-5894}, doi = {10.1007/s12298-013-0195-1}, author = {Vishwakarma, Rishi K. and Sonawane, Prashant and Singh, Somesh and Kumari, Uma and Ruby and Khan, Bashir Mohammad} } @article { ISI:000319073500006, title = {Molecular cloning, biochemical characterization, and differential expression of an acetyl-CoA C-acetyltransferase gene (AACT) of brahmi (Bacopa monniera)}, journal = {Plant Molecular Biology Reporter}, volume = {31}, number = {3}, year = {2013}, month = {JUN}, pages = {547-557}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Bacopa monniera (Brahmi) is an important Indian medicinal herb found in wet damp and marshy places. It produces medicinally important compounds known as bacosides along with alkaloids like brahmine and herpestine. Bacosides are triterpenoid saponins and their biosynthesis takes place via the isoprenoid pathway starting with acetyl-CoA. Acetyl-CoA C-acetyltransferase (AACT; EC 2.3.1.9), also known as acetoacetyl-CoA thiolase (Thiolase II), catalyzes the condensation of two acetyl-CoA to form 4-C compound acetoacetyl-CoA. Acetoacetyl-CoA is an important starting molecule for biosynthesis of various metabolites. Here, we report the cDNA cloning and characterization of acetyl-CoA C-acetyltransferase gene from B. monniera. The full-length gene was isolated using a RACE PCR protocol. The cDNA encoding AACT was designated as BmAACT (FJ947159) revealed an ORF of 1,218 bp and 405 amino acids, and shares 80 \% similarity with other plant AACTs. Phylogenetic analysis showed that BmAACT is related closely to other dicot plants AACTs. The BmAACT gene was over-expressed in Escherichia coli as a 6X His-tag fusion protein and purified to homogeneity by Ni-NTA and gel filtration chromatography. Activity of recombinant protein was confirmed by thiolytic cleavage of acetoacetyl-CoA in the presence of 5 mM Mg2+, showing K (m) and V (max) of 20.67 mu M and 96.21 mu mol/min, respectively, with high catalytic efficiency (k (cat) = 2.30 x 10(5) min(-1)). Quantitative real-time PCR analysis showed that the expression of BmAACT is tissue-specific, and accumulation of transcripts is greater in roots and petals, followed by sepals, stem, leaf and pedicel.

}, keywords = {Acetyl-CoA C-acetyltransferase, Bacopa monniera, Isoprenoid pathway, Triterpenoid saponin}, issn = {0735-9640}, doi = {10.1007/s11105-012-0523-6}, author = {Vishwakarma, Rishi K. and Ruby and Singh, Somesh and Sonawane, Prashant D. and Srivastava, Sameer and Kumari, Uma and Kumar, R. J. Santosh and Khan, Bashir Mohammad} } @article { ISI:000318320300033, title = {Multipole moments using extended coupled cluster method}, journal = {Chemical Physics Letters}, volume = {568}, year = {2013}, month = {MAY}, pages = {170-175}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Using analytic extended coupled cluster (ECC) response approach quadrupole moments, dipole-quadrupole polarizabilities and dipole polarizabilities are studied. In the current implementation of the functional we have included all the double linked terms within (CCSD) approximation. These terms will be important for the accurate description of properties at the stretched geometries. We report the properties for carbon monoxide and hydrogen fluoride molecules, as a function of bond distance and compare our results for carbon monoxide with the full Cl results. We have also reported the properties of methane, tetrafluoromethane, acetylene, difluoroacetylene, water and ammonia. (C) 2013 Elsevier B.V. All rights reserved.

}, issn = {0009-2614}, doi = {10.1016/j.cplett.2013.03.013}, author = {Joshi, Sayali P. and Vaval, Nayana} } @article { ISI:000323014200005, title = {Nanoparticle size controls aggregation in lamellar nonionic surfactant mesophase}, journal = {Langmuir}, volume = {29}, number = {31}, year = {2013}, month = {AUG}, pages = {9643-9650}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We show that the size of silica nanoparticles influences the nature of their aggregation in an aqueous solution of a relatively hydrophobic nonionic surfactant, C12E4. We present results for dispersions of silica nanopartides with sizes varying from 8 to 26 nm, in a 75: 25 C12E4/water system, that forms a lamellar phase, L-alpha, at room temperature. Addition of silica particles does not affect the formation of the L-alpha phase. Nanoparticles smaller than about 11 nm aggregate irreversibly in the C12E4/water system. However, nanoparticles larger than about 15 nm aggregate in the L-alpha phase, but are dispersed at temperatures above the L-alpha order-disorder temperature. Thus, in contrast to the smaller particles, aggregation of silica nanopartides larger than about 15 nm is reversible with temperature. We use small-angle neutron scattering (SANS) demonstrate that these results can be explained by the size-dependent wrapping of nanoparticles by surfactant bilayers. Larger particles, above 15 nm in size, are sterically stabilized by the formation of an adsorbed surfactant bilayer. The cost of bilayer bending inhibits adsorption onto the highly curved surfaces of smaller particles, and these {\textquoteleft}{\textquoteleft}bare{\textquoteright}{\textquoteright} particles aggregate irreversibly.

}, issn = {0743-7463}, doi = {10.1021/la4021977}, author = {Venugopal, Edakkal and Aswal, Vinod K. and Kumaraswamy, Guruswamy} } @article { ISI:000327052700035, title = {Oxidative dehydrogenation of ethyl benzene to styrene over hydrotalcite derived cerium containing mixed metal oxides}, journal = {Green Chemistry}, volume = {15}, number = {11}, year = {2013}, month = {SEP}, pages = {3259-3267}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Cerium containing mixed oxides derived from hydrotalcites was prepared and its catalytic activity was studied for oxidative dehydrogenation of ethyl benzene to styrene. Structural, spectroscopic and morphological features of the catalyst have been thoroughly examined with various physico-chemical characterization methods. Raman spectroscopy studies show evidence for oxygen vacancies in lower loadings of cerium which enhanced the oxygen migration. The transmission electron microscopy image showed good dispersion of ceria clusters on the mixed metal oxide. The catalytic activity results suggested that the conversion of ethyl benzene and styrene yield is stable for at least 12 hours without any significant catalyst deactivation. The styrene selectivity and ethyl benzene conversion were higher in a catalyst containing 0.03 mole percentage of cerium. Structural features of the spent catalysts have also been examined to demonstrate the stability of the catalyst during the reaction.

}, issn = {1463-9262}, doi = {10.1039/c3gc41321g}, author = {Venugopal, Ashok Kumar and Venugopalan, Aswathy Thareparambil and Kaliyappan, Periyasamy and Raja, Thirumalaiswamy} } @article { ISI:000326355100005, title = {Performance of the EOMIP-CCSD(2) method for determining the structure and properties of doublet radicals: a benchmark investigation}, journal = {Journal of Chemical Theory and Computation}, volume = {9}, number = {10}, year = {2013}, month = {OCT}, pages = {4313-4331}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We present a benchmark study on the performance of the EOMIP-CCSD(2) method for computation of structure and properties of doublet radicals. The EOMIP-CCSD(2) method is a second-order approximation to the standard EOMIP-CCSD method. By retaining the black box nature of the standard EOMIP-CCSD method and adding favorable N-5 scaling, the EOMIP-CCSD(2) method can become the method of choice for predicting the structure and spectroscopic properties of large doublet radicals. The EOMIP-CCSD(2) method overcomes the typical problems associated with the standard single reference ab initio treatment of doublet radicals. We compare our results for geometries and harmonic vibrational frequencies with those obtained using the standard EOMIP-CCSD method, as well as unrestricted Hartree-Fock (UHF)- and restricted open-shell Hartree-Fock (ROHF)-based single-reference coupled-cluster and second order many-body perturbation theory (MBPT(2)) methods. The effect of the basis set on the quality of the results has been studied using a hierarchy of Dunning{\textquoteright}s correlation-consistent aug-cc-pVXZ (X = D, T, Q) basis sets. Numerical results show that the EOMIP-CCSD(2) method, despite its N-5 scaling, gives better agreement with experimental results, compared to the UHF- and ROHF-based MBPT(2), as well as the single-reference coupled-cluster methods.

}, issn = {1549-9618}, doi = {10.1021/ct400316m}, author = {Dutta, Achintya Kumar and Vaval, Nayana and Pal, Sourav} } @article { ISI:000313012200051, title = {Polarizability of few electron quantum dots: extended coupled-cluster response approach}, journal = {Chemical Physics Letters}, volume = {555}, year = {2013}, month = {JAN}, pages = {263-267}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The dipole polarizability is studied for few electron quantum dots using extended coupled cluster linear response method (ECCLR). The polarizability of pure parabolic quantum dots depends only on the number of electrons and the parabolic confinement strength. We added impurity in a GAUSSIAN form to the external parabolic potential and used ECCLR to calculate polarizability. To examine the effect of external potential, we changed the parabolic confinement to square-well and repeated all calculations. We mainly looked at eigenvalue spectrum and charge density specially when the system shifts towards lower density regions. (C) 2012 Elsevier B. V. All rights reserved.

}, issn = {0009-2614}, doi = {10.1016/j.cplett.2012.10.071}, author = {Heidari, Ideh and Vaval, Nayana and Pal, Sourav and Kanhere, Dilip G.} } @article { ISI:000324098200003, title = {Porous Co3O4 nanorods as superior electrode material for supercapacitors and rechargeable Li-ion batteries}, journal = {Journal of Applied Electrochemistry}, volume = {43}, number = {10}, year = {2013}, month = {OCT}, pages = {995-1003}, publisher = {SPRINGER}, address = {VAN GODEWIJCKSTRAAT 30, 3311 GZ DORDRECHT, NETHERLANDS}, abstract = {

Porous aggregated nanorods of Co3O4 with a surface area of similar to 100 m(2) g(-1) synthesized without using any templates or surfactants give very high specific capacitance of similar to 780 F g(-1) when used as electrode in a faradaic supercapacitor, with a cycle life of more than 1,000 cycles. Further, in Li-ion batteries when used as an anode, the Co3O4 nanorods achieved a capacity of 1155 mA h g(-1) in the first cycle and upon further cycling it is stabilized at 820 mA h g(-1) for more than 25 cycles. Detailed characterization indicated the stability of the material and the improved performance is attributed to the shorter Li-insertion/desertion pathways offered by the highly porous nanostructures. The environmentally benign and easily scalable method of synthesis of the porous Co3O4 nanorods coupled with the superior electrode characteristics in supercapacitors and Li-ion batteries provide efficient energy storage capabilities with promising applications.

}, keywords = {Cobalt oxide, Electrode materials, Li-ion battery, Porous nanostructures, supercapacitor}, issn = {0021-891X}, doi = {10.1007/s10800-013-0593-7}, author = {Vijayanand, S. and Kannan, Ramaiyan and Potdar, H. S. and Pillai, V. K. and Joy, Pattayil Alias} } @article { ISI:000324842900004, title = {Probing the active site of cinnamoyl CoA reductase 1 (Ll-CCRH1) from Leucaena leucocephala}, journal = {International Journal of Biological Macromolecules}, volume = {60}, year = {2013}, month = {SEP}, pages = {33-38}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Lack of three dimensional crystal structure of cinnamoyl CoA reductase (CCR) limits its detailed active site characterization studies. Putative active site residues involved in the substrate/NADPH binding and catalysis for Leucaena leucocephala CCR (Ll-CCRH1; GenBank: DQ986907) were identified by amino acid sequence alignment and homology modeling. Putative active site residues and proximal H215 were subjected for site directed mutagenesis, and mutated enzymes were expressed, purified and assayed to confirm their functional roles. Mutagenesis of S136, Y170 and K174 showed complete loss of activity, indicating their pivotal roles in catalysis. Mutant S212G exhibited the catalytic efficiencies less than 10\% of wild type, showing its indirect involvement in substrate binding or catalysis. R51G, D77G, F30V and I31N double mutants showed significant changes in K-m values, specifying their roles in substrate binding. Finally, chemical modification and substrate protection studies corroborated the presence Ser, Tyr, Lys, Arg and carboxylate group at the active site of Ll-CCRH1. (c) 2013 Elsevier B.V. All rights reserved.

}, keywords = {Chemical modification, Cinnamoyl CoA reductase 1, Docking simulations, homology modeling, Site directed mutagenesis, Substrate protection}, issn = {0141-8130}, doi = {10.1016/j.ijbiomac.2013.05.005}, author = {Sonawane, Prashant and Patel, Krunal and Vishwakarma, Rishi Kishore and Srivastava, Sameer and Singh, Somesh and Gaikwad, Sushama M. and Khan, Bashir Mohammad} } @article { ISI:000324405700012, title = {Proposing late transition metal complexes as frustrated Lewis pairs - a computational investigation}, journal = {Dalton Transactions}, volume = {42}, number = {38}, year = {2013}, month = {JUL}, pages = {13866-13873}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

There has been considerable interest in recent times to develop transition metal complex systems that can demonstrate metal-ligand cooperativity. It has recently been shown (Wass et al., J. Am. Chem. Soc., 2011, 133, 18463) that early transition metals can cooperate with ligands carrying phosphines as pendant groups, working as metal analogues to frustrated Lewis pairs (FLPs) to mediate in a variety of important reactions. What the current work attempts to do is to show how this concept of metal containing FLPs can be expanded to include late transition metal complexes as well: complexes that have been modified from existing systems that serve as efficient catalysts for homogeneous polymerization. A modified palladium complex has been considered in this regard as an example of a potential late transition metal FLP and studied with full quantum mechanical calculations. The calculations indicate that this complex would be effective at catalyzing ammonia borane dehydrogenation. The possibility of competing side reactions such as reductive elimination have also been considered, and it has been found that such processes would also yield stable products which could act as an FLP in catalyzing reactions such as the dehydrogenation of ammonia borane. The current work therefore expands the scope of metal containing FLPs to include late transition metals and demonstrates computationally the potential of such complexes for exhibiting metal-ligand cooperativity.

}, issn = {1477-9226}, doi = {10.1039/c3dt51677f}, author = {Pal, Amrita and Vanka, Kumar} } @article { ISI:000313985200009, title = {Solving the problem of negative populations in approximate accelerated stochastic simulations using the representative reaction approach}, journal = {Journal of Computational Chemistry}, volume = {34}, number = {5}, year = {2013}, month = {FEB}, pages = {394-404}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

Methods based on the stochastic formulation of chemical kinetics have the potential to accurately reproduce the dynamical behavior of various biochemical systems of interest. However, the computational expense makes them impractical for the study of real systems. Attempts to render these methods practical have led to the development of accelerated methods, where the reaction numbers are modeled by Poisson random numbers. However, for certain systems, such methods give rise to physically unrealistic negative numbers for species populations. The methods which make use of binomial variables, in place of Poisson random numbers, have since become popular, and have been partially successful in addressing this problem. In this manuscript, the development of two new computational methods, based on the representative reaction approach (RRA), has been discussed. The new methods endeavor to solve the problem of negative numbers, by making use of tools like the stochastic simulation algorithm and the binomial method, in conjunction with the RRA. It is found that these newly developed methods perform better than other binomial methods used for stochastic simulations, in resolving the problem of negative populations. (C) 2012 Wiley Periodicals, Inc.

}, keywords = {approximate methods, binomial distributions, Gillespie algorithm, Kinetic Monte Carlo, Poisson distributions, representative reaction approach, Stochastic simulations}, issn = {0192-8651}, doi = {10.1002/jcc.23158}, author = {Kadam, Shantanu and Vanka, Kumar} } @article {42703, title = {Stepwise metal-ligand cooperation via a reversible aromatization-deconjugation-sequence in ruthenium complexes with a tetradentate phenanthroline-based ligand}, journal = {Chemistry - A European Journal}, volume = {19}, year = {2013}, month = {MAR}, pages = {3407{\textendash}3414}, abstract = {

The synthesis and reactivity of ruthenium complexes containing the tetradentate phenanthroline-based phosphine ligand 2,9-bis((di-tert-butylphosphino)methyl)-1,10-phenanthroline (PPhenP) is described. The hydrido chloro complex [RuHCl(PPhenP)] (2) undergoes facile dearomatization upon deprotonation of the benzylic position, to give [RuH(PPhenP-H)] (4). Addition of dihydrogen to 4 causes rearomatization of the phenanthroline moiety to trans-[Ru(H)2(PPhenP)] (5), followed by hydrogenation of an aromatic heterocycle in the ligand backbone, to give a new dearomatized and deconjugated complex [RuH(PPhenP*-H)] (6). These aromatization/deconjugation steps of the coordinated ligand were demonstrated to be reversible and operative in the dehydrogenation of primary alcohols without the need for a hydrogen acceptor. This aromatization/deconjugation sequence constitutes an unprecedented mode of a stepwise cooperation between the metal center and the coordinated ligand.

}, doi = {10.1002/chem.201204003}, author = {Langer, Robert and Fuchs, Ido and Vogt, Matthias and Balaraman, Ekambaram and Diskin-Posner, Yael and Shimon, Linda J. W. and Ben-David, Yehoshoa and Milstein, David} } @article { ISI:000316064700007, title = {Structural and catalytic properties of a novel vanadium containing solid core mesoporous silica shell catalysts for gas phase oxidation reaction}, journal = {Journal of Chemical Sciences}, volume = {125}, number = {1}, year = {2013}, month = {JAN}, pages = {63-69}, publisher = {INDIAN ACAD SCIENCES}, address = {C V RAMAN AVENUE, SADASHIVANAGAR, P B \#8005, BANGALORE 560 080, INDIA}, abstract = {

A novel vanadium containing solid core mesoporous silica shell catalyst was synthesized with different Si/V ratios by sol-gel method under neutral conditions. The synthesized materials were characterized by various techniques and gas phase diphenyl methane oxidation reaction. The mesoporosity combined with microporosity are formed by incorporation of octadecyltrichloro silane and triethylamine in the catalyst and it was found out from E-DAX and BET-surface area analysis. The material was found to be nanocrystalline. Vanadium is present as V4 + species in as-synthesized samples and convert to V5 + on calcination. Most of the vanadium is present in tetrahedral or square pyramidal environment. Incorporation of vanadium in silica framework was confirmed by Si-29 MAS NMR analysis. Among the various vanadium containing solid core mesoporous silica shell catalysts, the Si/V = 100 ratio exhibited maximum efficiency towards diphenyl methane to benzophenone gas phase reaction. The optimum condition required for maximum conversion and selectivity was found out from the catalytic studies.

}, keywords = {diphenylmethane, Gas phase oxidation, vanadium containing solid core mesoporous silica shell}, issn = {0974-3626}, doi = {10.1007/s12039-013-0365-2}, author = {Venkatathri, N. and Pillai, Vijayamohanan K. and Rajini, A. and Raju, M. Nooka and Reddy, I. A. K.} } @article { ISI:000323177900012, title = {Study of interatomic coulombic decay of Ne(H2O)(n) (n=1,3) clusters using equation-of-motion coupled-cluster method}, journal = {Journal of Chemical Physics}, volume = {139}, number = {6}, year = {2013}, month = {AUG}, pages = {Article No. 064112}, publisher = {AMER INST PHYSICS}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

Interatomic Coulombic decay (ICD) is an efficient and ultrafast radiationless decay mechanism which can be initiated by removal of an electron from the inner-valence shell of an atom or molecule. Generally, the ICD mechanism is prevailed in weakly bound clusters. A very promising approach, known as CAP/EOM-CC, consists of the combination of complex absorbing potential (CAP) with the equation-of-motion coupled-cluster (EOM-CC) method, is applied for the first time to study the nature of the ICD mechanism. We have applied this technique to determine the lifetime of an auto-ionized, inner-valence excited state of the NeH2O, Ne(H2O)(2), and Ne(H2O)(3) systems. The lifetime is found to be very short and decreases significantly with the number of neighboring water molecules. (C) 2013 AIP Publishing LLC.

}, issn = {0021-9606}, doi = {10.1063/1.4817966}, author = {Ghosh, Aryya and Pal, Sourav and Vaval, Nayana} } @article { ISI:000325738700001, title = {Sugar furanoid trans-vicinal diacid as a gamma-turn inducer: synthesis and conformational study}, journal = {Organic \& Biomolecular Chemistry}, volume = {11}, number = {40}, year = {2013}, month = {OCT}, pages = {6874-6878}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

A simple method for the synthesis of a sugar furanoid trans vicinal diacid and its incorporation into the N-terminal tetrapeptide sequence (H-Phe-Trp-Lys-Thr-OH) to get glycopeptide 8 has been described. 2D NMR and MD simulation studies of 8 clearly show that the sugar diacid adopts a gamma-turn conformation towards the N-terminus.

}, issn = {1477-0520}, doi = {10.1039/c3ob41462k}, author = {Vangala, Madhuri and Dhokale, Snehal A. and Gawade, Rupesh L. and Pattuparambil, Rajamohanan R. and Puranik, Vedavati G. and Dhavale, Dilip D.} } @article { ISI:000326010300003, title = {Switching the H-bonding network of a foldamer by modulating the backbone chirality and constitutional ratio of amino acids}, journal = {Organic \& Biomolecular Chemistry}, volume = {11}, number = {41}, year = {2013}, month = {NOV}, pages = {7072-7075}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

This communication describes the folding propensity of a hetero-foldamer motif featuring proline (Pro) and anthranilic acid (Ant) residues in a 1:2:1 (alpha: beta: alpha) constitutional ratio. Structural investigations unequivocally suggest that the hydrogen-bonding network of this foldamer motif can be switched between 9-membered and 6-membered by modulating the backbone chirality and constitutional ratio of the amino acid residues.

}, issn = {1477-0520}, doi = {10.1039/c3ob41369a}, author = {Ramesh, Veera V. E. and Vijayadas, Kuruppanthara N. and Dhokale, Snehal A. and Gonnade, Rajesh G. and Rajamohanan, Pattuparambil R. and Sanjayan, Gangadhar J.} } @article { ISI:000317596800004, title = {Synthesis and catalytic activity of monodisperse gold-mesoporous silica core-shell nanocatalysts}, journal = {Catalysis Science \& Technology}, volume = {3}, number = {5}, year = {2013}, month = {FEB}, pages = {1190-1193}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Core-shell nanostructures, where gold nanoparticles of sub 10 nm size are successfully encapsulated inside porous silica spheres, have been prepared. The detailed characterization of the catalyst shows a high surface area and good mesoporosity. The sinter resistance of the catalyst under repeated cycles of the CO oxidation reaction is observed.

}, issn = {2044-4753}, doi = {10.1039/c3cy20772b}, author = {Sekhar, A. C. Sunil and Meera, C. J. and Kottavarithottil Ziyad and Gopinath, Chinnakonda S. and Vinod, C. P.} } @article { ISI:000315060600030, title = {Synthesis of all four nucleoside-based beta-amino acids as protected precursors for the synthesis of polyamide-DNA with alternating alpha-amino acid and nucleoside-beta-amino acids}, journal = {Tetrahedron}, volume = {69}, number = {3}, year = {2013}, month = {JAN}, pages = {1210-1216}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

A simple approach is described for the synthesis of all four orthogonally protected nucleoside-beta-amino acids from commercially available starting materials. Synthesis of a model tetrameric DNA sequence in 5{\textquoteright}-3{\textquoteright}direction employing trityl strategy and glycine as alpha-amino acid alternating with nucleoside-beta amino acids is described. (C) 2012 Elsevier Ltd. All rights reserved.

}, keywords = {Antisense therapeutics, Neutral DNA analogues, Nucleoside-beta amino acids}, issn = {0040-4020}, doi = {10.1016/j.tet.2012.11.028}, author = {Seema Bagmare and Varada, Manojkumar and Banerjee, Anjan and Kumar, Vaijayanti A.} } @article { ISI:000316693100020, title = {Synthesis of palmyrolide A and its cis-isomer and mechanistic insight into trans-cis isomerisation of the enamide macrocycle}, journal = {Chemical Communications}, volume = {49}, number = {32}, year = {2013}, month = {MAR}, pages = {3342-3344}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Concise and protecting-group free synthesis of ent-palmyrolide A and (-)-cis-palmyrolide A were achieved starting from commercially available (S)-citronellal. The key fragment of palmyrolide A, {\textquoteleft}{\textquoteleft}(5S,7S)-7-hydroxy-5,8,8-trimethylnonanamide{\textquoteright}{\textquoteright}, which makes up the most challenging part of the target molecule, was prepared in just three steps. A plausible mechanism for the trans-cis isomerization of the double bond in the macrocycle has been investigated.

}, issn = {1359-7345}, doi = {10.1039/c3cc40541a}, author = {Philkhana, Satish Chandra and Seetharamsingh, B. and Dangat, Yuvraj B. and Vanka, Kumar and Reddy, D. Srinivasa} } @article { ISI:000318748300011, title = {Thermodynamic behavior of hydrophobically modified polyacrylamide containing random distribution of hydrophobes: experimental and theoretical investigations}, journal = {Polymer}, volume = {54}, number = {11}, year = {2013}, month = {MAY}, pages = {2676-2689}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Two series of Hydrophobically Modified Polyacrylamides (HMPAMs) were prepared by free radical copolymerization of trimethylsilylacrylamide with 3-pentadecylcyclohexylacrylamide (PDCAM) or dodecylacrylamide (DDAM) followed by removal of trimethylsilyl protecting groups. The solution properties of HMPAMs were studied in dilute aqueous solution by fluorescence spectroscopy, NMR and viscometry. The properties in aqueous solution of HMPAMs clearly displayed the formation of hydrophobic interactions between alkyl stickers. While dodecyl containing HMPAMs mainly showed a progressive collapse of the copolymer coil with the increasing fraction of hydrophobic moieties (weak intra-chain associations), pentadecylcyclohexyl groups containing HMPAMs exhibited a much lower solubility in water due to strong intra- and inter-chain associations. Experimental data were analyzed using the mean field theory developed by Semenov and Rubinstein (SR) for associating polymers. Using a set of realistic parameters, taking into account the solubility of the backbone, the fraction of stickers and the strength of hydrophobic attractions, we show that the SR model offers a quantitative description of the thermodynamic properties of HMPAMs in terms of individual and collective behavior of polymers chains; i.e. swelling and phase separation, respectively. (C) 2013 Elsevier Ltd. All rights reserved.

}, keywords = {Associating polymer, Polyacrylamide, Self-assembling}, issn = {0032-3861}, doi = {10.1016/j.polymer.2013.03.039}, author = {Hourdet, Dominique and Ducouret, Guylaine and Varghese, Sony and Badiger, Manohar V. and Wadgaonkar, Prakash P.} } @article {PACHFULE, title = {Two-stage fermentation process for enhanced mannitol production using Candida magnoliae mutant R9}, journal = {Bioprocess and Biosystems Engineering}, volume = {36}, number = {2}, year = {2013}, month = {FEB}, pages = {193-203}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Mutants of Candida magnoliae NCIM 3470 were generated by treatment of ultra-violet radiations, ethyl methyl sulphonate and N-methyl-N{\textquoteright}-nitro-N-nitrosoguanidine. Mutants with higher reductase activity were screened by means of 2,3,5-triphenyl tetrazolium chloride agar plate assay. Among the screened mutants, the mutant R9 produced maximum mannitol (i.e. 46 g l(-1)) in liquid fermentation medium containing 250 g l(-1) glucose and hence was selected for further experiments. Preliminary optimization studies were carried out on shake-flask level which increased the mannitol production to 60 g l(-1) in liquid fermentation medium containing 300 g l(-1) glucose. A two-stage fermentation process comprising of growth phase and production phase was employed. During the growth phase, glucose was supplemented and aerobic conditions were maintained. Thereafter, the production phase was initiated by supplementing fructose and switching to anaerobic conditions by discontinuing aeration and decreasing the speed of agitation. The strategy of two-stage fermentation significantly enhanced the production of mannitol up to 240 g l(-1), which is the highest among all fermentative production processes and corresponds to 81 \% yield and 4 g l(-1) h(-1) productivity without formation of any by-product.

}, keywords = {Candida magnoliae, D-Mannitol, Mutagenesis, Strain improvement, Two-stage fermentation}, issn = {1615-7591}, doi = {10.1007/s00449-012-0775-4}, author = {Savergave, Laxman S. and Gadre, Ramchandra V. and Vaidya, Bhalchandra K. and Jogdand, Vitthal V.} } @article { ISI:000323018700017, title = {Zirconium phenyl phosphonate phosphite as a highly active, reusable, solid acid catalyst for producing fatty acid polyol esters}, journal = {Applied Catalysis A-General}, volume = {462}, year = {2013}, month = {JUL}, pages = {129-136}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The application of zirconium phenyl phosphonate phosphite (ZrPP) as a solid acid catalyst for producing polyol esters by esterification of glycerol or trimethylolpropane with a fatty acid (C-8-C-18.1) is reported for the first time. ZrPP exhibits high catalytic activity and in particular, (di + tri) esters selectivity (92.3 mol\%). These esters of polyols are known for their application as biolubricants. The catalyst prepared using phosphorous acid to phenyl phosphonic acid molar ratio of 3:1 was found superior. The influence of process parameters on activity and selectivity of the catalyst was investigated. ZrPP was reusable in at least three recycling experiments. Hydrophobicity due to exposed phenyl groups on the surface is the possible cause for superior esterification activity of this novel, solid catalyst. (C) 2013 Elsevier B.V. All rights reserved.

}, keywords = {Biolubricants, Esterification of fatty acid, Fatty acid glycerides, Hydrophobic solid acid catalyst, Polyol esters, Zirconium phenyl phosphonate phosphite}, issn = {0926-860X}, doi = {10.1016/j.apcata.2013.04.043}, author = {Varhadi, Poonam and Kotwal, Mehejabeen and Srinivas, D.} } @article { ISI:000338486300020, title = {1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU): a highly efficient catalyst in glycerol carbonate synthesis}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {391}, year = {2014}, month = {SEP}, pages = {144-149}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Transesterification of dimethyl carbonate (DMC) with glycerol (GLY) was investigated using various amines as catalysts. Amidines like 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) were found to be the best catalysts for this reaction. Best results: 98\% conversion of GLY with 96\% selectivity to GC (TON: 9408), were obtained with DBU as a catalyst. Effect of various reaction conditions on activity and selectivity were investigated using DBU as catalyst. The mechanism of the reaction was investigated with the help of H-1, C-13 and N-15 NMR analysis and OFT calculations. (C) 2014 Elsevier B.V. All rights reserved.

}, keywords = {DBU, Glycerol, Glycerol carbonate, transesterification}, issn = {1381-1169}, doi = {10.1016/j.molcata.2014.04.016}, author = {Munshi, Mudassir K. and Gade, Swapna M. and Mane, Manoj V. and Mishra, Deepti and Pal, Sourav and Vanka, Kumar and Rane, Vilas H. and Kelkar, Ashutosh A.} } @article { ISI:000345460800001, title = {Accounting of noise to solve the problem of negative populations in approximate accelerated stochastic simulations}, journal = {RSC Advances}, volume = {4}, number = {102}, year = {2014}, month = {OCT}, pages = {58127-58136}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

The advent of different approximate accelerated stochastic simulation methods has helped considerably in reducing the computational load of the exact simulation algorithms. However, along with the reduction in the computational load comes the risk of driving the molecular numbers to the regime of negative numbers during the simulations. Over the years, various methods have been developed in order to solve the problem by using different strategies. Some methods have employed binomial numbers to model the reactions, while others have tried the partitioning of the reaction network. In this manuscript, we have proposed a new approach where the noise inherent in the choice of the number of firings of a given reaction during a time step is taken into account. This idea of noise accounting is used in conjunction with the accelerated stochastic method: the Representative Reaction Approach (RRA). It is found that the new method is successful at solving the problem of negative numbers, and compares very favorably with other state-of-the-art stochastic simulation methods.

}, issn = {2046-2069}, doi = {10.1039/c4ra05865h}, author = {Kadam, Shantanu and Vanka, Kumar} } @article {43349, title = {Antimicrobial and dna damaging activity of ochratoxin a extracted from Penicillium species}, journal = {International Journal of Pharma and Bio Sciences}, volume = {5}, year = {2014}, month = {OCT}, pages = {335-341}, abstract = {The present investigation was carried out by ten bacterial species, Bacillus subtilis, Escherishia coli, Enterobacter aerogenes, Klebsiella pneumoniae, Micrococcus luteus, Pseudomonas aeruginosa, Pseudomonas putida, Proteus mirabilis, Proteus vulgaris, Staphylococcus aureus and five fungal species, Aspergillus terreus, Penicillium aurantiogriseum, P.expansum, Paceliomycs varioti, Fusarium graminarium were screened for their sensitivity against ochratoxin A (OTA) produced by Penicillium verrucosum. Proteus mirabilis was highly sensitive followed by E.aureogens, B.subtilis and K. pneumoniae. Rest of the bacteria was intermediate in their sensitivity when compared with the streptomycin as standard. Similarly P.aurantiogriseum and Paeciolomyces varioti were comparatively more sensitive than the other fungi under study. Aspergillus terreus and P.expansum was sensitive to an intermediate extent. Simultaneously the DNA damaging activity of OTA was also evaluated by PRSET-B plasmid DNA treated with H2O2 plus different concentrations of OTA. The highest DNA stand breaks was observed on even at 25μg/ml of OTA and complete degradation of DNA stand breaks was observed on 30μg/ml of OTA.}, author = {Vankudoth, Koteswara Rao and Sivadevuni, Girisham} } @article { ISI:000342761600095, title = {Asymmetric transfer hydrogenation of imines in water/methanol co-solvent system and mechanistic investigation by DFT study}, journal = {RSC Advances}, volume = {4}, number = {86}, year = {2014}, month = {SEP}, pages = {46351-46356}, publisher = {ROYAL SOC CHEMISTRY}, type = {Article}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Asymmetric transfer hydrogenation of various cyclic imines proceeded efficiently with water/methanol co-solvent media in 20 min with excellent yields and enantioselectivities by employing Rh-TsDPEN catalyst and sodium formate as a hydrogen donor. The role of the co-solvent in enhanced productivity of the reaction was investigated by DFT. The mechanism for ATH of the imines has been discussed on the basis of the DFT study.

}, issn = {2046-2069}, doi = {10.1039/c4ra07964g}, author = {Shende, Vaishali S. and Shingote, Savita K. and Deshpande, Sudhindra H. and Kuriakose, Nishamol and Vanka, Kumar and Kelkar, Ashutosh A.} } @article { ISI:000338818800044, title = {Biological synthesis of cationic gold nanoparticles and binding of plasmid DNA}, journal = {Materials Letters}, volume = {129}, year = {2014}, month = {AUG}, pages = {159-161}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Nanobiotechnology is the development of eco-friendly experimental processes for the synthesis of nanomaterials. The present work focuses on synthesis of cationic gold nanoparticles (C-GNPs) for biological applications, especially in gene and drug delivery studies. A biosynthesis methodology has been developed for the functionalization of gold nanoparticles to cationic nature. The synthesis of C-GNPs was done by using peanut leaf extract in the presence of cysteamine. The formed C-GNPs were characterized by using UV-visible spectroscopy (UV-vis), the particles sizes and shapes were confirmed by a Transmission electron microscope (TEM) and crystallinity of C-GNPs was characterized by diffraction. The binding of plasmid DNA on the C-GNPs was confirmed by agarose gel electrophoresis. (C) 2014 Elsevier B.V. All rights reserved.

}, keywords = {Biomaterials, Cationic, Nanoparticles, Plasmid DNA, synthesis, TEM}, issn = {0167-577X}, doi = {10.1016/j.matlet.2014.05.021}, author = {Raju, D. and Vishwakarma, Rishi K. and Khan, Bashir Mohammad and Mehta, Urmil J. and Ahmad, Absar} } @article { ISI:000339228500017, title = {Can silylenes rival transition metal systems in bond-strengthening pi-back donation? a computational investigation}, journal = {Chemical Communications}, volume = {50}, number = {62}, year = {2014}, month = {AUG}, pages = {8522-8525}, publisher = {ROYAL SOC CHEMISTRY}, type = {Article}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Full quantum chemical calculations with density functional theory (DFT) show that bond-strengthening back-donation to a pi-diborene, recently discovered for transition metal systems (Braunschweig and co-workers, Nat. Chem., 2013, 5, 115-121), would be just as favored for Main Group silylene complexes. This result not only shows the range and applicability of the bond-strengthening back-bonding interaction, but also showcases the capacity of silylene complexes to do new chemistry, such as the cooperative activation of carbon monoxide and carbon dioxide.

}, issn = {1359-7345}, doi = {10.1039/c4cc02470b}, author = {Pal, Amrita and Vanka, Kumar} } @article { ISI:000341359200002, title = {Capturing a novel metastable polymorph of the anticancer drug gefitinib}, journal = {CrystEngComm}, volume = {16}, number = {37}, year = {2014}, month = {AUG }, pages = {8638-8641}, publisher = {ROYAL SOC CHEMISTRY}, type = {Article}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Gefitinib, a life-extending anticancer drug, exhibits solvent-mediated conformational polymorphism to yield stable (form I) and novel metastable (form II) polymorphs. Crystal structure analysis revealed 3D isostructurality in the molecular organization of the polymorphs, and the metastable polymorph undergoes a crystal-to-crystal thermal phase transition to the stable polymorph.

}, issn = {1466-8033}, doi = { 10.1039/c4ce01446d}, author = {Thorat, Shridhar H. and Patwadkar, Manjusha V. and Gonnade, Rajesh G. and Vaidhyanathan, R.} } @inbook {43325, title = {Chemoinformatics approach for the design and screening of focused virtual libraries}, booktitle = {Practical Chemoinformatics}, year = {2014}, pages = {93-131}, publisher = {Springer}, organization = {Springer}, chapter = {Chemoinformatics Approach for the Design and Screening of focused virtual libraries}, address = {India}, abstract = {

It is challenging to handle a large volume of molecular data without appropriate tools. Here, we describe the need and the approaches for the development of focussed virtual libraries to design efficient molecules and optimize them for lead generation. The experimental chemists and biologists are more interested in properties of chemicals and their response to biological system in both beneficial and adverse effects context rather than just their structures. In this chapter, the focus is to relate newly designed chemical structures to their predicted activity, property or toxicity. Property prediction tools save time, money and lives of experimental animals. They come in handy while taking informed decisions especially in certain cases involving pharmacodynamic studies of drug molecules in humans where there are inevitable ethical and safety concerns. Property prediction is an important component in virtual screening which is at the heart of drug design and the most important step where chemoinformatics plays a major role. The other fields where structure{\textendash}activity relation-based principles hold good for virtual screening are agrochemicals and environmental science, specifically the toxicity and biodegradability prediction of pollutant molecules. In this chapter, we will show how to design software tools to handle generation of focussed virtual libraries from a given set of molecules with common features, fragments or bioactivity spectrum.

}, doi = {10.1007/978-81-322-1780-0_2 }, author = {Karthikeyan, Muthukumarasamy and Vyas, Renu} } @article { ISI:000342018100001, title = {Cholesterol depletion by methyl-beta-cyclodextrin augments tamoxifen induced cell death by enhancing its uptake in melanoma}, journal = {Molecular Cancer}, volume = {13}, year = {2014}, month = {SEP}, pages = {Article No. 204}, publisher = {BIOMED CENTRAL LTD}, type = {Article}, address = {236 GRAYS INN RD, FLOOR 6, LONDON WC1X 8HL, ENGLAND}, abstract = {

Background: Despite modern advances in treatment, skin cancer is still one of the most common causes of death in the western countries. Chemotherapy plays an important role in melanoma management. Tamoxifen has been used either alone or in-combination with other chemotherapeutic agents to treat melanoma. However, response rate of tamoxifen as a single agent has been comparatively low. In the present study, we investigated whether treatment with methyl-beta-cyclodextrin (MCD), a cholesterol depleting agent, increases the efficacy of tamoxifen in melanoma cells. Methods: This was a two-part study that incorporated in vitro effects of tamoxifen and MCD combination by analyzing cell survival, apoptosis and cell cycle analysis and in vivo antitumor efficacy on tumor isografts in C57BL/6J mice. Results: MCD potentiated tamoxifen induced anticancer effects by causing cell cycle arrest and induction of apoptosis. Sensitization to tamoxifen was associated with down regulation of antiapoptotic protein Bcl-2, up-regulation of proapoptotic protein Bax, reduced caveolin-1 (Cav-1) and decreased pAkt/pERK levels. Co-administration of tamoxifen and MCD caused significant reduction in tumor volume and tumor weight in mice due to enhancement of drug uptake in the tumor. Supplementation with cholesterol abrogated combined effect of tamoxifen and MCD. Conclusion: Our results emphasize a potential synergistic effect of tamoxifen with MCD, and therefore, may provide a unique therapeutic window for improvement in melanoma treatment.

}, keywords = {Caveolin-1, Cholesterol, Methyl beta-cyclodextrin, Tamoxifen}, issn = {1476-4598}, doi = {10.1186/1476-4598-13-204}, author = {Mohammad, Naoshad and Malvi, Parmanand and Meena, Avtar Singh and Singh, Shivendra Vikram and Chaube, Balkrishna and Vannuruswamy, Garikapati and Kulkarni, Mahesh J. and Bhat, Manoj Kumar} } @article { ISI:000330822900026, title = {Clay encapsulated Cu(OH)(x) promoted homocoupling of arylboronic acids: an efficient and eco-friendly protocol}, journal = {Applied Catalysis A-General}, volume = {470}, year = {2014}, month = {JAN}, pages = {232-238}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Cu(OH)(x) has been encapsulated over montmorillonite-KSF by simple ologomeric deposition strategy. The resulting catalyst has been employed for selective homocoupling of arylboronic acids under ambient conditions without requirement of any ligand or base. This catalyst is easy to recover and shows excellent reusability without losing its activity. Techniques like XRD, SEM, TPR, IR, BET surface area measurement and XPS were used to characterize the catalyst. The present method promises for the simple and clean homocoupling of arylboronic acids. (C) 2013 Elsevier B.V. All rights reserved.

}, keywords = {Biaryls, clay, Copper, Heterogenous catalyst, Homocoupling}, issn = {0926-860X}, doi = {10.1016/j.apcata.2013.10.048}, author = {Dar, Bashir Ahmad and Singh, Snehil and Pandey, Nalini and Singh, A. P. and Sharma, Priti and Lazar, Anish and Sharma, Meena and Vishwakarma, Ram A. and Singh, Baldev} } @article { ISI:000344589700016, title = {Complex absorbing potential based equation-of-motion coupled cluster method for the potential energy curve of CO2- anion}, journal = {Journal of Chemical Physics}, volume = {141}, number = {16}, year = {2014}, month = {OCT}, pages = {Article No. 164113}, publisher = {AMER INST PHYSICS}, type = {Article}, address = {1305 WALT WHITMAN RD, STE 300, MELVILLE, NY 11747-4501 USA}, abstract = {

The equation-of-motion coupled cluster method employing the complex absorbing potential has been used to investigate the low energy electron scattering by CO2. We have studied the potential energy curve for the (2)Pi(u) resonance states of CO2- upon bending as well as symmetric and asymmetric stretching of the molecule. Specifically, we have stretched the C-O bond length from 1.1 angstrom to 1.5 angstrom and the bending angles are changed between 180 degrees and 132 degrees. Upon bending, the low energy (2)Pi(u) resonance state is split into two components, i.e., (2)A(1), B-2(1) due to the Renner-Teller effect, which behave differently as the molecule is bent. (c) 2014 AIP Publishing LLC.

}, issn = {0021-9606}, doi = {10.1063/1.4899280}, author = {Ghosh, Aryya and Vaval, Nayana and Pal, Sourav and Bartlett, Rodney J.} } @article { ISI:000341579600004, title = {Coupled cluster methods for autoionisation resonances}, journal = {International Reviews in Physical Chemistry}, volume = {33}, number = {3}, year = {2014}, month = {SEP}, pages = {397-425}, publisher = {TAYLOR \& FRANCIS LTD}, address = {4 PARK SQUARE, MILTON PARK, ABINGDON OX14 4RN, OXON, ENGLAND}, abstract = {

The quantum chemical calculation of autoionisation resonances in many-electron systems is a highly challenging task due to the ionisation continuum involved. Recently, advances were reported where conventionally used ab initio codes can be employed to compute autoionisation resonances. This is made possible by the use of analytical continuation tools such as complex scaling and complex absorbing potential (CAP) in the electronic structure codes. We review the formulation and the use of complex scaling and CAP in coupled cluster methods for the electron correlated calculation of energy position and autoionisation decay rate of resonance states. The application of analytically continued coupled cluster method for the correlated calculation of interatomic or intermolecular Coulombic decay process is also discussed.

}, keywords = {autoionisation resonances, complex absorbing potential, complex scaling, equation-of-motion coupled cluster, Fock space multi-reference-coupled cluster, intermolecular Coulombic decay}, issn = {0144-235X}, doi = {10.1080/0144235X.2014.935585}, author = {Sajeev, Y. and Ghosh, A. and Vaval, N. and Pal, S.} } @article { ISI:000341409900005, title = {Donor decomposition by lewis acids in Ziegler-Natta catalyst systems: a computational investigation}, journal = {Organometallics}, volume = {33}, number = {17}, year = {2014}, month = {SEP}, pages = {4357-4367}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The development of new donors (Lewis bases, usually containing oxygen atoms) is one of the chief areas of research in Ziegler-Natta (ZN) olefin polymerization systems. The addition of such donors has led to improvement in the activity and selectivity of ZN systems. However, in order for the donor to be effective, it has to be chemically stable and resistant to decomposition by Lewis acidic species such as AlEt3. Discussed in the current work is the chemical stability of different ester donors, including aromatic benzoate donors and the silyl ester-a promising new donor class in ZN systems. Full quantum chemical calculations with density functional theory (DFT) indicate that esters can undergo decomposition through different pathways upon interaction with species such as the AlEt3 dimer: Al2Et6. Moreover, the studies show that the active, supported titanium catalyst species can cause donor decomposition and, in fact, is likely to be the greater threat to donor decomposition than Al2Et6. This explains why the addition of excess donors can lead to the poisoning of the active site in ZN systems. We have also computationally investigated means of improving the silyl ester donors in order to make them more robust and resilient to donor decomposition by Al2Et6 and the supported active titanium species.

}, issn = {0276-7333}, doi = {10.1021/om5001259}, author = {Kumawat, Jugal and Gupta, Virendra Kumar and Vanka, Kumar} } @article { ISI:000335620500016, title = {Effect of self-assembly on triiodide diffusion in water based polymer gel electrolytes: an application in dye solar cell}, journal = {Journal of Colloid and Interface Science}, volume = {425}, year = {2014}, month = {JUL}, pages = {110-117}, publisher = {ACADEMIC PRESS INC ELSEVIER SCIENCE}, type = {Article}, address = {525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USA}, abstract = {

The preparation of ordered polymer gels from the amphiphilic block copolymers, Pluronic (R) F77, P123 and polyethylene glycol in the presence of ionic liquid, iodine and organic additives is presented. At 35\%(w/w) concentration these copolymers (F77 and P123) self-assembled into cubic liquid crystalline phase in aqueous solution and characterized by using SAXS and AFM measurements. The effects of micellar aggregation formed by polymers on the ionic transport and triiodide diffusion have been studied by electro-chemistry and SANS experiments. The ionic migration or triiodide diffusion through these polymer gels is found to be affected by the PEO/PPO content in the polymer backbone. These gels were successfully employed as an electrolyte in a dye sensitized solar cell. A remarkable solar to electricity conversion efficiency and good stability was obtained using Pluronic (R) F77 based gel, which is attributed to its thermoreversible sol to gel transition. (C) 2014 Elsevier Inc. All rights reserved.

}, keywords = {Amphiphilic block copolymer, Dye solar cell, Micellar nanochannels, SANS, SAXS, Self-assembly, Water based gel electrolytes}, issn = {0021-9797}, doi = {10.1016/j.jcis.2014.03.047}, author = {Soni, S. S. and Fadadu, K. B. and Vekariya, R. L. and Debgupta, Joyashish and Patel, K. D. and Gibaud, A. and Aswal, Vinod K.} } @article { ISI:000340530500007, title = {Electronic transition dipole moment: a semi-biorthogonal approach within valence universal coupled cluster framework}, journal = {International Journal of Quantum Chemistry}, volume = {114}, number = {18, SI}, year = {2014}, month = {SEP}, pages = {1212-1219}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

Electronic dipole strengths (square of transition moments) and oscillator strengths are evaluated for various transitions, arising from the ground state to a few valence excited states. Parallel to two other methods of calculating the dipole strength within the Fock-space multireference coupled cluster framework, a new semi-biorthogonal approach is formulated and implemented in this article. This semi-biorthogonal approach can evaluate dipole strengths at a lower computational effort than the biorthogonal approach without compromising on the accuracy. This new method is compared and tested against the previously developed expectation value and biorthogonal approach for various molecular transitions. (C) 2014 Wiley Periodicals, Inc.

}, keywords = {electronic transition dipole, Fock-space, oscillator strength, semi-biorthogonal expectation value}, issn = {0020-7608}, doi = {10.1002/qua.24691}, author = {Bhattacharya, Debarati and Vaval, Nayana and Pal, Sourav} } @article { ISI:000343018200079, title = {Enhancing cubosome functionality by coating with a single layer of poly-epsilon-lysine}, journal = {ACS Applied Materials \& Interfaces}, volume = {6}, number = {19}, year = {2014}, month = {OCT}, pages = {17126-17133}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We report the preparation and characterization of monoolein cubosomes that can be easily surface modified through adsorption of a single layer of cationic poly-epsilon-lysine. Poly-epsilon-lysine coated cubosomes show remarkable stability in serum solution, are nontoxic and, are readily internalized by HeLa cells. The poly-epsilon-lysine coating provides chemical handles for further bioconjugation of the cubosome surface. We also demonstrate that the initial release rate of a hydrophilic drug, Naproxen sodium, from the cubosomes is retarded with just a single layer of polymer. Interestingly, cubosomes loaded with Naproxen sodium, recently shown to have anticancer properties, cause more apoptosis in HeLa cells when compared to free unencapsulated drug.

}, keywords = {bioconjugation, cubosomes, drug delivery vehicle, dual loading, theranostics}, issn = {1944-8244}, doi = {10.1021/am5047872}, author = {Deshpande, Sonal and Venugopal, Edakkal and Ramagiri, Shobha and Bellare, Jayesh R. and Kumaraswamy, Guruswamy and Singh, Neetu} } @article { ISI:000341831600037, title = {Evolution of an adenine-copper cluster to a highly porous cuboidal framework: solution-phase ripening and gas-adsorption properties}, journal = {Chemistry-A European Journal}, volume = {20}, number = {38}, year = {2014}, month = {SEP}, pages = {12262-12268}, publisher = {WILEY-V C H VERLAG GMBH}, type = {Article}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

The synthesis and directed evolution of a tetranu-clear copper cluster, supported by 8-mercapto-N9-propyladenine ligand, to a highly porous three-dimensional cubic framework in the solid state is reported. The structure of this porous framework was unambiguously characterized by Xray crystallography. The framework contains about 62\% solvent-accessible void; the presence of a free exocyclic amino group in the porous framework facilitates reversible adsorption of gas and solvent molecules. Oriented growth of framework in solution was also tracked by force and scanning electron microscopy studies, leading to identification of an intriguing ripening process, over a period of 30 days, which also revealed formation of cuboidal aggregates in solution. The elemental composition of these cuboidal aggregates was ascertained by EDAX analysis.

}, keywords = {cuboidal frameworks, gas adsorption, metal-organic frameworks, Ostwald ripening, solution-phase ripening}, issn = {0947-6539}, doi = {10.1002/chem.201403115}, author = {Venkatesh, V. and Pachfule, Pradip and Banerjee, Rahul and Verma, Sandeep} } @article { ISI:000342545900037, title = {Extended coupled cluster method for potential energy surface: a decoupled approach}, journal = {Chemical Physics Letters}, volume = {612}, year = {2014}, month = {SEP}, pages = {209-213}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Extended coupled cluster (ECC) method has been implemented extensively for the calculation of molecular properties. In this Letter we report the potential energy surface (PES) study using coupled and a decoupled approximation of ECC. HF, N-2 and C-2 are studied as test systems. N-2 and C-2 being doubly and triply bonded, are considered to be interesting systems for PES study. We compare our results with full CI (FCI) results wherever available. Decoupled approach within ECC framework shows good convergence for all the molecules. (C) 2014 Elsevier B.V. All rights reserved.

}, issn = {0009-2614}, doi = {10.1016/j.cplett.2014.08.016}, author = {Joshi, Sayali P. and Vaval, Nayana} } @article {43348, title = {Factors influence on growth, don and niv production by two species of fusarium isolated from finger millets [eleusine coracana l.]}, journal = {International Journal of Pharmacy and Pharmaceutical Sciences}, volume = {6}, year = {2014}, month = {DEC}, pages = {312-317}, abstract = {ABSTRACT Objective: The present investigations (In vitro) on an influence of different synthetic and food based [flour] media, pH, temperature and microbial nutrients on growth, Deoxynivalenol [DON] and Nivalenol [NIV] production by Fusarium aethiopicum and F. culmorum was carried out. Methods: Fusarium species associated with the finger millets were isolated and identified phenotypically and further confirmed by molecular methods by Polymerase Chain Reaction [PCR]. Monosporic seven day old F. aethiopicum and F. culmorum were grown in CYA broth and incubated at 27{\textpm}2{\textdegree}C on rotary shaker for 21 days at 120 rpm. At the end of 21 day incubation period, cultures were harvested for determination of fungal biomass. The resultant culture filtrates were extracted twice with ethyl acetate and concentrated to get and final concentration of 1 ml in methanol and employed for RP-HPLC analysis for detection of DON and NIV production. Results: Finger millets flour medium induced the highest amount of mycelial growth, DON and NIV production by F. aethiopicum. However, F. culmorum achieved highest amount of hyphal growth, DON and NIV production under the influence of yeast extract sucrose [YES] medium. Maize flour medium, rice flour medium and sorghum flour medium was next preffered substrates. Optimum pH of 5.5-6.5 and temperature of 20-35{\textdegree}C for growth, DON and NIV production was observed. Both the species of Fusarium failed to grow and produce toxins at pH 2.5-3.5 and temperature of 40{\textdegree}C. Yeast extract was most favorable for maximum DON and NIV production, which increased with an increase in its concentration. On the other hand, malt extract and beef extract induced good growth and mycotoxin production at comparatively higher concentration in both the species of Fusarium under study. Conclusion: Comparatively food based media were the better substrates than synthetic media for both growth and DOIN and NIV production by two species of Fusarium under investigation. A positive correlation coefficient [r] on growth [0.458], DON [0.744] and NIV [0.882] was recorded among the media and both the species of Fusarium. Keywords: Finger millets, F. aethiopicum, F. culmorum, Synthetic media, pH, Temperature, Microbial nutrients, DON, NIV, HPLC}, author = {Vankudoth, Koteswara Rao and Penugonda, Shilpa and Sivadevuni, Girisham and Reddy, S. M.} } @article { ISI:000340267600082, title = {Flexible microwave absorbers based on barium hexaferrite, carbon black, and nitrile rubber for 2-12 GHz applications}, journal = {Journal of Applied Physics}, volume = {116}, number = {2}, year = {2014}, month = {JUL}, pages = {024902}, publisher = {AMER INST PHYSICS}, address = {CIRCULATION \& FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA}, abstract = {

Flexile single layer electromagnetic wave absorbers were designed by incorporating appropriate amounts of carbon black in a nitrile butadiene rubber matrix along with an optimized amount of magnetic counterpart, namely, barium hexaferrite for applications in S, C, and X-bands. Effective dielectric permittivity and magnetic permeability were measured using cavity perturbation method in the frequency range of 2-12 GHz. The microwave absorbing characteristics of the composites were studied in the S, C, and X-bands employing a model in which an electromagnetic wave is incident normally on a metal terminated single layer. Reflection loss exceeding -20 dB is obtained for all the samples in a wide frequency range of 2-12 GHz when an appropriate absorber thickness between 5 and 9 mm is chosen. The impact of carbon black is clearly observed in the optimized composites on the mechanical strength, thickness, band width of absorption, dielectric properties, and absorptivity. (C) 2014 AIP Publishing LLC.

}, issn = {0021-8979}, doi = {10.1063/1.4886382}, author = {Vinayasree, S. and Soloman, M. A. and Sunny, Vijutha and Mohanan, P. and Kurian, Philip and Joy, Pattayil Alias and Anantharaman, Maliemadom R.} } @article { ISI:000333581400004, title = {Functionalization of cardanol: towards biobased polymers and additives}, journal = {Polymer Chemistry}, volume = {5}, number = {9}, year = {2014}, month = {OCT}, pages = {3142-3162}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Among the renewable resource materials, cashew nut shell liquid (CNSL) is considered as an important starting material due to its unique structural features, abundant availability and low cost. A large number of chemicals and products have been developed starting from CNSL by taking advantage of the three reactive sites, namely, phenolic hydroxyl, aromatic ring and unsaturation(s) in the alkenyl side chain. This comprehensive review deals with general information on CNSL, its purification and separation methods, reactivity and applications in polymer chemistry.

}, issn = {1759-9954}, doi = {10.1039/c3py01194a}, author = {Voirin, Coline and Caillol, Sylvain and Sadavarte, Nilakshi V. and Tawade, Bhausaheb V. and Boutevin, Bernard and Wadgaonkar, Prakash P.} } @article { ISI:000333787700019, title = {Functionalized celluloses and their nanoparticles: morphology, thermal properties, and solubility studies}, journal = {Carbohydrate Polymers}, volume = {104}, year = {2014}, month = {APR}, pages = {135-142}, publisher = {ELSEVIER SCI LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Agricultural residues derived cellulose was used to synthesize a new series of carboxy functionalized cellulosic nanoparticles (quasi-spherical shaped, 13.2-21.5\% carboxyl content) and macro-sized 6-carboxycelluloses (long-fibril shaped, 1.7-22\% carboxyl content). The DP (50-70) and yield (upto 46\%) of nanoparticles were manipulated by controlling the reaction temperature and time. TGA/DTG thermographs of the carboxycelluloses gave thermostability data and co-related well with the residual crystalline, amorphous, and anhydroglucuronic acid content. The particle shape and size had no effect on the thermal stability. Some derivatives were fully or partially soluble in aqueous alkali and non-aqueous solvents, which can lead to increased versatility of these polymers. (C) 2014 Elsevier Ltd. All rights reserved.

}, keywords = {6-Carboxycellulose, cellulose, DTG, Morphology, Nanoparticles, TGA}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2014.01.015}, author = {Sharma, Priyanka R. and Varma, Anjanikumar} } @article { ISI:000346662700009, title = {Geometry-dependent lifetime of Interatomic coulombic decay using equation-of-motion coupled cluster method}, journal = {Journal of Chemical Physics}, volume = {141}, number = {23}, year = {2014}, month = {DEC}, pages = {Article No. 234108}, publisher = {AMER INST PHYSICS}, address = {1305 WALT WHITMAN RD, STE 300, MELVILLE, NY 11747-4501 USA}, abstract = {

Electronically excited atom or molecule in an environment can relax via transferring its excess energy to the neighboring atoms or molecules. The process is called Interatomic or Intermolecular coulombic decay (ICD). The ICD is a fast decay process in environment. Generally, the ICD mechanism predominates in weakly bound clusters. In this paper, we have applied the complex absorbing potential approach/equation-of-motion coupled cluster (CAP/EOMCCSD) method which is a combination of CAP and EOMCC approach to study the lifetime of ICD at various geometries of the molecules. We have applied this method to calculate the lifetime of ICD in Ne-X; X = Ne, Mg, Ar, systems. We compare our results with other theoretical and experimental results available in literature. (C) 2014 AIP Publishing LLC.

}, issn = {0021-9606}, doi = {10.1063/1.4903827}, author = {Ghosh, Aryya and Vaval, Nayana} } @article { ISI:000344998100063, title = {Green chemistry approach to styrene from ethylbenzene and air on MnxTi1-xO2 catalyst}, journal = {RSC Advances}, volume = {4}, number = {100}, year = {2014}, month = {OCT}, pages = {57087-57097}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Styrene (ST) is an industrially important commodity chemical, and design of a suitable catalyst, which provides high ethyl benzene (EB) conversion and styrene selectivity at Lower temperature with sustainable activity, is one of the major challenges in the field of heterogeneous catalysis. Manganese incorporated in titania (MnxT1-xO2) anatase Lattice, prepared via the solution combustion method, was evaluated for oxidative dehydrogenation (ODH) of EB with O-2 or air. MnxTi1-xO2 catalysts were characterized by different physiochemical methods. Up to 15\% Mn could be introduced into the TiO2 Lattice. TEM and XRD indicate disordered mesoporosity, further confirmed by adsorption isotherm analysis. MnxTi1-xO2 catalysts were evaluated for ST synthesis from EB using air or oxygen as oxidant between 440 and 570 degrees C. Reaction conditions have been varied systematically, such as catalyst composition, and EB/air/O-2 flow. MnxTi1-xO2 shows sustainable 55\% styrene yield for 45 h without deactivation under optimum conditions. A thorough analysis of spent catalysts demonstrates the conversion of initial anatase phase MnxTi1-xO2 to Mn3O4 supported on the rutile (R) phase of TiO2. The above change occurs in the first few hours of reaction and the Mn3O4 on R-TiO2 phase is the active phase of the catalyst and responsible for sustainable activity for Longer duration.

}, issn = {2046-2069}, doi = {10.1039/c4ra11814f}, author = {Negi, Sanjay Singh and Venugopalan, Aswathy Thareparambil and Raja, Thirumalaiswamy and Singh, Anand Pal and Gopinath, Chinnakonda S.} } @article { ISI:000334168400024, title = {Ground state of naphthyl cation: singlet or triplet?}, journal = {Journal of Chemical Physics}, volume = {140}, number = {11}, year = {2014}, month = {MAR}, pages = {114312}, publisher = {AMER INST PHYSICS}, address = {1305 WALT WHITMAN RD, STE 300, MELVILLE, NY 11747-4501 USA}, abstract = {

We present a benchmark theoretical investigation on the electronic structure and singlet- triplet(ST) gap of 1- and 2-naphthyl cations using the CCSD(T) method. Our calculations reveal that the ground states of both the naphthyl cations are singlet, contrary to the results obtained by DFT/B3LYP calculations reported in previous theoretical studies. However, the triplet states obtained in the two structural isomers of naphthyl cation are completely different. The triplet state in 1-naphthyl cation is (pi,sigma) type, whereas in 2-naphthyl cation it is (pi,sigma) type, The S-T gaps in naphthyl cations and the relative stability ordering of the singlet and the triplet states are highly sensitive to the basis set quality as well as level of correlation, and demand for inclusion of perturbative triples in the coupled-cluster ansatz. (c) 2014 AIP Publishing LLC.

}, issn = {0021-9606}, doi = {10.1063/1.4868485}, author = {Dutta, Achintya Kumar and Manohar, Prashant Uday and Vaval, Nayana and Pal, Sourav} } @article { ISI:000345826600002, title = {Heterogeneous foldamers from aliphatic-aromatic amino acid building blocks: current trends and future prospects}, journal = {European Journal of Organic Chemistry}, volume = {46}, number = {35}, year = {2014}, month = {DEC}, pages = {7763-7780}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

Chemists{\textquoteright} constant pursuit of understanding of the underlying principles of nature{\textquoteright}s most intricate phenomenon such as protein folding has led to the development of the field of foldamers. The emergence of diverse classes of unnatural amino acid building blocks has unleashed countless opportunities to design, develop and explore the structural and functional aspects of synthetic peptides. One current trend in foldamer chemistry is the heterofoldamer approach, which involves systematic stoichiometric variation of various natural/unnatural amino acid residues, leading to conformational ordering with intriguing structural architectures. In this regard, the incorporation of aromatic amino acids provides efficient structural rigidification and tunability to the molecular scaffolds, which can exhibit a range of secondary structural features. Recent times have witnessed an upsurge of foldamers featuring aliphatic-aromatic residues with diverse structural propensities. This review is an effort to cover this rapidly developing field of foldamer science and also to envisage its future perspectives.

}, keywords = {Amino acids, Conformation analysis, Foldamers, hydrogen bonding, Peptides, Stacking interactions}, issn = {1434-193X}, doi = {10.1002/ejoc.201402877}, author = {Nair, Roshna V. and Vijayadas, Kuruppanthara N. and Roy, Arup and Sanjayan, Gangadhar J.} } @article { ISI:000340469800024, title = {Highly efficient chiral resolution of DL-arginine by cocrystal formation followed by recrystallization under preferential-enrichment conditions}, journal = {Chemistry-A European Journal}, volume = {20}, number = {33}, year = {2014}, month = {AUG}, pages = {10343-10350}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

An excellent chiral symmetry-breaking spontaneous enantiomeric resolution phenomenon, denoted preferential enrichment, was observed on recrystallization of the 1:1 cocrystal of dl-arginine and fumaric acid, which is classified as a racemic compound crystal with a high eutectic ee value (\>95\%), under non-equilibrium crystallization conditions. On the basis of temperature-controlled video microscopy and in situ time-resolved solid-state (CNMR)-C-13 spectroscopic studies on the crystallization process, a new mechanism of phase transition that can induce preferential enrichment is proposed.

}, keywords = {Amino acids, chiral resolution, cocrystals, Crystal growth, phase transitions}, issn = {0947-6539}, doi = {10.1002/chem.201402446}, author = {Iwama, Sekai and Kuyama, Kazunori and Mori, Yuko and Manoj, Kochunnoonny and Gonnade, Rajesh G. and Suzuki, Katsuaki and Hughes, Colan E. and Williams, P. Andrew and Harris, Kenneth D. M. and Veesler, Stephane and Takahashi, Hiroki and Tsue, Hirohito and Tamura, Rui} } @article { ISI:000331675300001, title = {Hybrid diphosphorus ligands in rhodium catalysed asymmetric hydroformylation}, journal = {Coordination Chemistry Reviews}, volume = {262}, year = {2014}, month = {MAR}, pages = {1-15}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

This review aims to illustrate recent advances in the application of hybrid diphosphorus ligands for the Rh catalysed hydroformylation of alkenes, discussing the most prevalent classes of hybrid systems, i.e. phosphine-phosphinite, phosphine-phosphonite, phosphine-phosphite, phosphite-phosphoramidite and phosphite-phosphoramidite and comparing their performance with relevant C-2 symmetric counterparts. In order to introduce the field and put the results in context, a short overview on Rh hydroformylation is provided. Available spectroscopic (in situ) data on the coordination modes of hybrid phosphorus ligands and the catalytic performance of these systems in asymmetric hydroformylation of vinyl arenes are reported. Potential avenues for future research are shortly discussed. (C) 2013 Elsevier B.V. All rights reserved.

}, keywords = {Asymmetric hydroformylation, Catalyst resting state, Hybrid ligand design, In situ spectroscopy, Rhodium}, issn = {0010-8545}, doi = {10.1016/j.ccr.2013.10.024}, author = {Chikkali, Samir H. and van der Vlugt, Jarl Ivar and Reek, Joost N. H.} } @article { ISI:000335273100012, title = {Hydrogen storage in clathrate hydrates: Current state of the art and future directions}, journal = {Applied Energy}, volume = {122}, year = {2014}, month = {JUN}, pages = {112-132}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Hydrogen is looked upon as the next generation clean energy carrier, search for an efficient material and method for storing hydrogen has been pursued relentlessly. Improving hydrogen storage capacity to meet DOE targets has been challenging and research efforts are continuously put forth to achieve the set targets and to make hydrogen storage a commercially realizable process. This review comprehensively summarizes the state of the art experimental work conducted on the storage of hydrogen as hydrogen clathrates both at the molecular level and macroscopic level. It identifies future directions and challenges for this exciting area of research. Hydrogen storage capacities of different clathrate structures - sI, sII, sH, sVI and semi clathrates have been compiled and presented. In addition, promising new approaches for increasing hydrogen storage capacity have been described. Future directions for achieving increased hydrogen storage and process scale up have been outlined. Despite few limitations in storing hydrogen in the form of clathrates, this domain receives prominent attention due to more environmental-friendly method of synthesis, easy recovery of molecular hydrogen with minimum energy requirement, and improved safety of the process. (C) 2014 Elsevier Ltd. All rights reserved.

}, keywords = {Clathrates, Gas hydrates, Hydrogen hydrates, Hydrogen storage, Promoters, Storage capacity}, issn = {0306-2619}, doi = {10.1016/j.apenergy.2014.01.063}, author = {Veluswamy, Hari Prakash and Kumar, Rajnish and Linga, Praveen} } @article { ISI:000330999600057, title = {IFN-gamma signaling maintains skin pigmentation homeostasis through regulation of melanosome maturation}, journal = {Proceedings of the National Academy of Sciences of the United States of America}, volume = {111}, number = {6}, year = {2014}, month = {FEB}, pages = {2301-2306}, publisher = {NATL ACAD SCIENCES}, address = {2101 CONSTITUTION AVE NW, WASHINGTON, DC 20418 USA}, abstract = {

Cellular homeostasis is an outcome of complex interacting processes with nonlinear feedbacks that can span distinct spatial and temporal dimensions. Skin tanning is one such dynamic response that maintains genome integrity of epidermal cells. Although pathways underlying hyperpigmentation cascade are recognized, negative feedback regulatory loops that can dampen the activated melanogenesis process are not completely understood. In this study, we delineate a regulatory role of IFN-gamma in skin pigmentation biology. We show that IFN-gamma signaling impedes maturation of the key organelle melanosome by concerted regulation of several pigmentation genes. Withdrawal of IFN-gamma signal spontaneously restores normal cellular programming. This effect in melanocytes is mediated by IFN regulatory factor-1 and is not dependent on the central regulator microphthalmia-associated transcription factor. Chronic IFN-gamma signaling shows a clear hypopigmentation phenotype in both mouse and human skin. Interestingly, IFN-gamma KO mice display a delayed recovery response to restore basal state of epidermal pigmentation after UV-induced tanning. Together, our studies delineate a new spatiotemporal role of the IFN-gamma signaling network in skin pigmentation homeostasis, which could have implications in various cutaneous depigmentary and malignant disorders.

}, keywords = {detanning, gene regulation, interferon, melanin}, issn = {0027-8424}, doi = {10.1073/pnas.1304988111}, author = {Natarajan, Vivek T. and Ganju, Parul and Singh, Archana and Vijayan, Vinaya and Kirty, Kritika and Yadav, Shalini and Puntambekar, Shraddha and Bajaj, Sonali and Dani, Prachi P. and Kar, Hemanta K. and Gadgil, Chetan J. and Natarajan, Krishnamurthy and Rani, Rajni and Gokhale, Rajesh S.} } @article {43346, title = {Influence of different species of Penicillium and their culture filtrates on seed germination and seedling growth of sorghum}, journal = {Journal of Biochemical Technology}, volume = {5}, year = {2014}, month = {DEC}, pages = {832 - 837}, abstract = {The present investigations influence of Penicillium species and their culture filtrates on the seed germination and seedling growth of sorghum was studied. Culture filtrate of P. nordicum, P. verrucosum, P. chrysogenum, P. commune, P. citrinum, P.camemberti and P. digitatum were comparatively more toxic and significantly inhibited the seed germination and seedling growth varied with the species. However, pathogenicity of different inoculum of Penicillium species also exhibited varying seedling growth inhibition with P. citrinum, P. chrysogenum, P. commune, P. italicum, P. verrucosum and P. expansum assayed by water agar method. A significant phytotoxicity of these species inhibited coleoptile 32-70\%, radicle 10-87\% and leaf growth 20-86\% with correlation coefficient 0.65, 0.67 and 0.79\%, and were observed respectively. In-vitro mycotoxin production was assayed by culture filtrates of major mycotoxigenic strains revealed production of ochratoxin A (OTA), cyclopiazonic acid (CPA), rubratoxin B (RTB), griseofulvin (GRI), citrinin (CIT), patulin (PAT), penitrem A (PENA) and mycophenolic acid (MPA) screened by TLC/HPLC. Toxicity of species of Penicillium on seed germination, coleoptile, radicle, and leaf elongation inhibition may be attributed to the toxin-chemotypes produced by the species of Penicillium. However, even non-toxigenic strains of Penicillium also caused mild inhibition which may be attributed to the presence of other toxin-chemotypes.}, author = {Vankudoth, Koteswara Rao} } @article { ISI:000341543000009, title = {Intermediate hamiltonian fock space multireference coupled cluster approach to core excitation spectra}, journal = {Journal of Chemical Theory and Computation}, volume = {10}, number = {9}, year = {2014}, month = {SEP}, pages = {3656-3668}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The Fock space multireference coupled cluster (FSMRCC) method provides an efficient approach for the direct calculation of excitation energies. In intermediate Hamiltonian (IH-FSMRCC) formulation, the method is free from intruder state problems and associated convergence difficulties, even with a large model space. In this paper, we demonstrate that the IH-FSMRCC method with suitably chosen model space can be used for the accurate description of core excitation spectra of molecules, and our results are in excellent agreement with the experimental values. We have investigated the effect of choice of model space on the computed results. Unlike the equation-of-motion (EOM)-based method, the IH-FSMRCC does not require any special technique for convergence and in singles and doubles approximation gives a performance comparable to that of the standard EOMEE-CCSD method, even better in some of the cases.

}, issn = {1549-9618}, doi = {10.1021/ct500285e}, author = {Dutta, Achintya Kumar and Gupta, Jitendra and Vaval, Nayana and Pal, Sourav} } @article { ISI:000338118400007, title = {Iodine-catalyzed aromatization of tetrahydrocarbazoles and its utility in the synthesis of glycozoline and murrayafoline A: a combined experimental and computational investigation}, journal = {Organic \& Biomolecular Chemistry}, volume = {12}, number = {27}, year = {2014}, month = {JUN}, pages = {4832-4836}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

A new protocol for the aromatization of tetrahydrocarbazoles has been achieved using a catalytic amount of iodine, giving high yields. The role of iodine in the aromatization has been explained by DFT, and its wide scope is extended to the total synthesis of glycozoline and murrayafoline A. This method has proven to be tolerant of a broad range of functional groups.

}, issn = {1477-0520}, doi = {10.1039/c4ob00635f}, author = {Humne, Vivek T. and Dangat, Yuvraj B. and Vanka, Kumar and Lokhande, Pradeep} } @inbook {43324, title = {Machine learning methods in chemoinformatics for drug discovery}, booktitle = {Practical Chemoinformatics}, year = {2014}, pages = {133-194}, publisher = {Springer}, organization = {Springer}, chapter = {Machine Learning Methods in Chemoinformatics for Drug Discovery}, abstract = {It is well known that the structure of a molecule is responsible for its biological activity or physicochemical property. Here, we describe the role of machine learning (ML)/statistical methods for building reliable, predictive models in chemoinformatics. The ML methods are broadly divided into clustering, classification and regression techniques. However, the statistical/mathematical techniques which are part of the ML tools, such as artificial neural networks, hidden Markov models, support vector machine, decision tree learning, Random Forest and Naive Bayes and belief networks, are best suited for drug discovery and play an important role in lead identification and lead optimization steps. This chapter provides stepwise procedures for building ML-based classification and regression models using state-of-art open-source and proprietary tools. A few case studies using benchmark data sets have been carried out to demonstrate the efficacy of the ML-based classification for drug designing}, doi = {10.1007/978-81-322-1780-0_3}, author = {Karthikeyan, Muthukumarasamy and Vyas, Renu} } @article { ISI:000338283000052, title = {Molecular cloning and characterization of genistein 4{\textquoteright}-O-glucoside specific glycosyltransferase from Bacopa monniera}, journal = {Molecular Biology Reports}, volume = {41}, number = {7}, year = {2014}, month = {JUL}, pages = {4675-4688}, publisher = {SPRINGER}, address = {VAN GODEWIJCKSTRAAT 30, 3311 GZ DORDRECHT, NETHERLANDS}, abstract = {

Health related benefits of isoflavones such as genistein are well known. Glycosylation of genistein yields different glycosides like genistein 7-O-glycoside (genistin) and genistein 4{\textquoteright}-O-glycoside (sophoricoside). This is the first report on isolation, cloning and functional characterization of a glycosyltransferase specific for genistein 4{\textquoteright}-O-glucoside from Bacopa monniera, an important Indian medicinal herb. The glycosyltransferase from B. monniera (UGT74W1) showed 49 \% identity at amino acid level with the glycosyltransferases from Lycium barbarum. The UGT74W1 sequence contained all the conserved motifs present in plant glycosyltransferases. UGT74W1 was cloned in pET-30b (+) expression vector and transformed into E. coli. The molecular mass of over expressed protein was found to be around 52 kDa. Functional characterization of the enzyme was performed using different substrates. Product analysis was done using LC-MS and HPLC, which confirmed its specificity for genistein 4{\textquoteright}-O-glucoside. Immuno-localization studies of the UGT74W1 showed its localization in the vascular bundle. Spatio-temporal expression studies under normal and stressed conditions were also performed. The control B. monniera plant showed maximum expression of UGT74W1 in leaves followed by roots and stem. Salicylic acid treatment causes almost tenfold increase in UGT74W1 expression in roots, while leaves and stem showed decrease in expression. Since salicylic acid is generated at the time of injury or wound caused by pathogens, this increase in UGT74W1 expression under salicylic acid stress might point towards its role in defense mechanism.

}, keywords = {Bacopa monniera, Expression analysis, Glycosyltransferase, Immuno-localization, Plant secondary product glycosyltransferase motif}, issn = {0301-4851}, doi = {10.1007/s11033-014-3338-8}, author = {Ruby and Kumar, R. J. Santosh and Vishwakarma, Rishi K. and Singh, Somesh and Khan, Bashir Mohammad} } @article { ISI:000333203900024, title = {Nanoporous graphene by quantum dots removal from graphene and its conversion to a potential oxygen reduction electrocatalyst via nitrogen doping}, journal = {Energy \& Environmental Science}, volume = {7}, number = {3}, year = {2014}, month = {MAR}, pages = {1059-1067}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

A simple way to produce an efficient metal-free oxygen reduction electrocatalyst from graphene by generating nanopores in the matrix and subsequently establishing nitrogen-doped active sites along the pore openings is demonstrated. Well-structured nanoporous graphene (pGr) and photoluminescent graphene quantum dots (GQDs) could be simultaneously generated by a chemically assisted oxidative treatment of graphene. The process helped to knock out small pieces of Gr through epoxide formation, which subsequently resulted in the generation of GQD and pGr simultaneously. A longer oxidation time increased the quantity of GQDs and also resulted in a higher photoluminescent (PL) quantum yield. The PL quantum yield of GQD formed after 72 h of the oxidative treatment (GQD-72) was 15.8\%, which is greater than the previous reported values. The TEM images showed matching sizes for GQDs and the pores present in pGr, implying that the pores are generated by the removal of GQDs from graphene during the oxidative treatment. Since pore openings are expected to give higher levels of unsaturation and defect sites in the system and are thus being treated as fertile regions for heteroatom doping, pGr-72 was further subjected to nitrogen (NpGr-72). NpGr-72 displayed excellent activity towards the electrochemical oxygen reduction reaction (ORR) compared to nitrogen-doped non-porous graphene (NGr) and many other reported nitrogen-doped carbon materials. A distinct 50 mV gain in the overpotential and 2.5 times increment in the kinetic current density (j(k)) have been achieved in the case of NpGr-72 compared to NGr. Interestingly, unlike NGr, NpGr-72 effectively reduced the oxygen molecule with a greater involvement of the preferred four-electron pathway. Additionally, the overpotential difference of NpGr-72 with respect to 20 wt\% Pt/C is only 60 mV. Additionally, in a single cell evaluation under anion exchange membrane fuel cell (AEMFC) conditions, NpGr-72 exhibited a maximum power density of 27 mW cm(-2), which is significantly higher than the corresponding value of 10 mW cm(-2) obtained for NGr. Thus, the overall enhancement in the performance characteristics of NpGr-72 is attributed to the higher content of nitrogen (7.8 wt\%) and its large proportion of desired chemical environment, which could be established by utilizing the high level of carbon unsaturation around the pore openings.

}, issn = {1754-5692}, doi = {10.1039/c3ee43648a}, author = {Palaniselvam, Thangavelu and Valappil, Manila Ozhukil and Illathvalappil, Rajith and Kurungot, Sreekumar} } @article { ISI:000343819200016, title = {Nature of the active site in ziegler-natta olefin polymerization catalysis systems - a computational investigation}, journal = {European Journal of Inorganic Chemistry}, number = {29}, year = {2014}, month = {OCT}, pages = {5063-5076}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

Pull quantum chemical calculations with density functional theory (DET) show that a principal role of donors in Ziegler-Nana (ZN) oh-din polymerization catalysts is to coordinate to the metal center at the active sites on the MgCl2 surface. Thereby, the behavior of the catalyst is modulated to favor insertion over termination and, thus, polymerization occurs. This is shown to be true for a range of different donors. The calculations indicate that active sites that feature anionic chloride ligands at the titanium center (the conventional model for the active site) would lead to lower-molecular-weight riolymers. If an -OC2H5 group were present instead of a chloride ligand, the active site would much more effectively produce long chain polymers. Therefore, the current work provides important new insights into the nature of the ZN polymerization process.

}, keywords = {Alkene polymerization, Density functional calculations, heterogeneous catalysis, Insertion, Polymers}, issn = {1434-1948}, doi = {10.1002/ejic.201402180}, author = {Kumawat, Jugal and Gupta, Virendra Kumar and Vanka, Kumar} } @article { ISI:000328952500034, title = {New insights into small molecule activation by acyclic silylenes: a computational investigation}, journal = {Dalton Transactions}, volume = {43}, number = {5}, year = {2014}, month = {NOV}, pages = {2194-2201}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Recently synthesized acyclic silylenes have the potential to rival transition metal complexes in performing single site small molecule activation, which is significant because of the need to find cheap and green alternatives to transition metal complexes for this important class of reactions. However, the current computational study, a full quantum chemical investigation with density functional theory, demonstrates that undesired side reactions would be competitive in these systems during small molecule activation. The current investigation, in addition to shedding light on this problem, also provides solutions on how the undesired side reactions during small molecule activation can be avoided.

}, issn = {1477-9226}, doi = {10.1039/c3dt52817k}, author = {Kuriakose, Nishamol and Vanka, Kumar} } @article { ISI:000334485400001, title = {New role for penicillin acylases: degradation of acyl homoserine lactone quorum sensing signals by Kluyvera citrophila penicillin G acylase}, journal = {Enzyme and Microbial Technology }, volume = {56}, year = {2014}, month = {MAR}, pages = {1-7}, publisher = {ELSEVIER SCIENCE INC}, type = {Article}, address = {360 PARK AVE SOUTH, NEW YORK, NY 10010-1710 USA}, abstract = {

Use of penicillin acylases for the production of semi-synthetic penicillins is well-known. Escherichia coli penicillin G acylase (EcPGA) has been extensively used for this purpose; however, Kluyvera citrophila penicillin G acylase (KcPGA) is assumed to be a better substitute, owing to its increased resilience to extreme pH conditions and ease of immobilization. In the present article we report a new dimension for the amidase activity of KcPGA by demonstrating its ability to cleave bacterial quorum sensing signal molecules, acyl homoserine lactones (AHL) with acyl chain length of 6-8 with or without oxo-substitution at third carbon position. Initial evidence of AHL degrading capability of KcPGA was obtained using CV026 based bioassay method. Kinetic studies performed at pH 8.0 and 50 degrees C revealed 3-oxo-C6 HSL to be the best substrate for the enzyme with V-max and K-m values of 21.37+0.85 mM/h/mg of protein and 0.1+0.01 mM, respectively. C6 HSL was found to be the second best substrate with V-max. and K-m value of 10.06+0.27 mM/h/mg of protein and 0.28+0.02 mM, respectively. Molecular modeling and docking studies performed on the active site of the enzyme support these findings by showing the fitting of AHLs perfectly within the hydrophobic pocket of the enzyme active site. (c) 2013 Elsevier Inc. All rights reserved.

}, keywords = {Acyl homoserine lactones, CV026, KcPGA, Quorum quenching}, issn = {0141-0229}, doi = {10.1016/j.enzmictec.2013.12.010}, author = {Mukherji, Ruchira and Varshney, Nishant Kumar and Panigrahi, Priyabrata and Suresh, C. G. and Prabhune, Asmita} } @article { ISI:000331819800001, title = {Non-coding RNA interact to regulate neuronal development and function}, journal = {Frontiers in Cellular Neuroscience}, volume = {8}, year = {2014}, month = {FEB}, pages = {47}, publisher = {FRONTIERS RESEARCH FOUNDATION}, address = {PO BOX 110, LAUSANNE, 1015, SWITZERLAND}, abstract = {

The human brain is one of the most complex biological systems, and the cognitive abilities have greatly expanded compared to invertebrates without much expansion in the number of protein coding genes. This suggests that gene regulation plays a very important role in the development and function of nervous system, by acting at multiple levels such as transcription and translation. In this article we discuss the regulatory roles of three classes of non-protein coding RNAs (ncRNAs)-microRNAs (miRNAs), piwi-interacting RNA (piRNAs) and long-non-coding RNA (lncRNA), in the process of neurogenesis and nervous function including control of synaptic plasticity and potential roles in neurodegenerative diseases. miRNAs are involved in diverse processes including neurogenesis where they channelize the cellular physiology toward neuronal differentiation. miRNAs can also indirectly influence neurogenesis by regulating the proliferation and self renewal of neural stem cells and are dysregulated in several neurodegenerative diseases. miRNAs are also known to regulate synaptic plasticity and are usually found to be co-expressed with their targets. The dynamics of gene regulation is thus dependent on the local architecture of the gene regulatory network (GRN) around the miRNA and its targets. piRNAs had been classically known to regulate transposons in the germ cells. However, piRNAs have been, recently, found to be expressed in the brain and possibly function by imparting epigenetic changes by DNA methylation. piRNAs are known to be maternally inherited and we assume that they may play a role in early development. We also explore the possible function of piRNAs in regulating the expansion of transposons in the brain. Brain is known to express several lncRNA but functional roles in brain development are attributed to a few lncRNA while functions of most of the them remain unknown. We review the roles of some known lncRNA and explore the other possible functions of lncRNAs including their interaction with miRNAs.

}, keywords = {gene expression regulation, lncRNA, miRNA, network-motifs, piRNA}, issn = {1662-5102}, doi = {10.3389/fncel.2014.00047}, author = {Iyengar, Bharat R. and Choudhary, Ashwani and Sarangdhar, Mayuresh A. and Venkatesh, K. V. and Gadgil, Chetan J. and Pillai, Beena} } @article { ISI:000339540700077, title = {Off-stoichiometric nickel cobaltite nanoparticles: thermal stability, magnetization, and neutron diffraction studies}, journal = {Journal of Physical Chemistry C}, volume = {118}, number = {29}, year = {2014}, month = {JUL}, pages = {16246-16254}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

In the present investigation, we report a detailed examination of the effect of off-stoichiometry introduced in NiCo2O4 by adding excess cobalt. Thus, we compare and analyze the structural and magnetic properties of the Ni075Co2.25O4 and NiCo2O4 cubic systems. A low temperature combustion method was utilized to synthesize stoichiometric (NiCo2O4) and off-stoichiometric (Ni0.75Co2.25O4) nanoparticles on a large scale. The X-ray diffraction pattern for the sample annealed at high temperature (773 K) shows the presence of a much less intense NiO phase (similar to 2-5\%) in Ni0.75Co2.25O4 as compared to that in the case of NiCo2O4 sample (similar to 15-20\%). The Ni 2p and Co 2p XPS spectra reveal the coexistence of Ni2+, Ni3+, Co2+, and Co3+ species on the surface of both the NiCo2O4 and Ni0.75Co2.23O4 samples in differing proportions. In addition to the basic magnetic characterizations using PPMS, these were also analyzed by neutron diffraction. The off-stoichiometric Ni0.75Co2.25O4 sample shows an interesting magnetic phase conversion from frustrated dipolar system to an enhanced magnetic ordering upon annealing. Local moments on the lattice sites of NiCo2O4 and Ni0.75Co2.25O4 samples are further compared by neutron diffraction confirming stronger ordered moments and enhanced structural and thermal stability for the Ni0.75Co2.25O4 sample.

}, issn = {1932-7447}, doi = {10.1021/jp504538y}, author = {Verma, Seema and Kumar, Amit and Pravarthana, D. and Deshpande, Aparna and Ogale, Satishchandra B. and Yusuf, S. M.} } @article { ISI:000337785400041, title = {Organic soluble and uniform film forming oligoethylene glycol substituted BODIPY small molecules with improved hole mobility}, journal = {Physical Chemistry Chemical Physics}, volume = {16}, number = {26}, year = {2014}, month = {MAY}, pages = {13376-13382}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Judiciously chosen side chains of conjugated molecules have a positive impact on charge transport properties when used as the active material in organic electronic devices. Amongst the side chains, oligoethylene glycols (OEGs) have been relatively unexplored due to their hydrophilic nature. OEGs also affect the smooth film formation of conjugated molecules, which preclude device fabrication. However, X-ray diffraction studies have shown that OEGs facilitate intermolecular contact, which is a desirable property for the fabrication of organic electronic devices. Thus the challenge is to design and synthesize organic solvent soluble and uniform film forming conjugated molecules with OEG side chains. We have designed and synthesized conjugated small molecules (CSMs) comprising BODIPY as acceptor and triphenylamine as donor with an OEG side chain. This molecule forms smooth films when processed from organic solvents. In order to understand the impact of the OEG side chain, we have also synthesized alkyl chain analogs. All the molecules exhibit exactly the same HOMO and LUMO energy levels, but the packing in the solid state is different. CSM with methyl side chains exhibit an inter planar distance of 4.15 A. Contrary to this, the OEG side chain containing CSM showed an inter planar spacing of 4.30 A, which is 0.2 A less than the alkyl side chain comprising CSMs. Please note that the length of the hydrophobic and hydrophilic side chains is the same. Interestingly, the OEG side chain comprising CSM showed two orders of higher hole carrier mobilities compared to all the other derivatives. The same molecule also showed an extremely low threshold voltage of -0.27 V indicating the OEG side chains{\textquoteright} favourable interaction between substrate as well as between molecules.

}, issn = {1463-9076}, doi = {10.1039/c4cp01098a}, author = {Singh, Saumya and Venugopalan, Vijay and Krishnamoorthy, Kothandam} } @article { ISI:000336020400012, title = {Partitioned EOMEA-MBPT(2): an efficient N-5 scaling method for calculation of electron affinities}, journal = {Journal of Chemical Theory and Computation}, volume = {10}, number = {5}, year = {2014}, month = {APR}, pages = {1923-1933}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We present an N-5 scaling modification to the standard EOMEA-CCSD method, based on the matrix partitioning technique and perturbative approximations. The method has lower computational scaling and smaller storage requirements than the standard EOMEA-CCSD method and, therefore, can be used to calculate electron affinities of large molecules and clusters. The performance and capabilities of the new method have been benchmarked with the standard EOMEA-CCSD method, for a test set of 20 small molecules, and the average absolute deviation is only 0.03 eV. The method is further used to investigate electron affinities of DNA and RNA nucleobases, and the results are in excellent agreement with the experimental values.

}, issn = {1549-9618}, doi = {10.1021/ct4009409}, author = {Dutta, Achintya Kumar and Gupta, Jitendra and Pathak, Himadri and Vaval, Nayana and Pal, Sourav} } @article { ISI:000341643300008, title = {Pharmacokinetic modeling of caco-2 cell permeability using genetic programming (GP) method}, journal = {Letters in Drug Design \& Discovery}, volume = {11}, number = {9}, year = {2014}, month = {NOV}, pages = {1112-1118}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, abstract = {

An accurate prediction of the pharmacokinetic properties of orally administered drugs is of paramount importance in pharmaceutical industry. Caco-2 cell permeability is a well established parameter for assessing the drug absorption profiles of lead molecules. Due to the restrictions on animal testing, prohibitive in situ models and ethical issues, the development of predictive models is essential. Genetic programming (GP) is an artificial intelligence (AI)-based exclusively data driven modeling paradigm. Given an example input-output data, it searches and optimizes, both the structure and parameters of a well fitting linear/non-linear input-output model. Despite this novelty, GP has not been widely exploited in drug design. Accordingly, in this study we propose a GP based approach for the in silico prediction of Caco-2 cell permeability using a diverse set of molecules. The predictions yielded a high magnitude for the training and test set correlation coefficient with low RMSE, indicating accurate Caco-2 permeability prediction and generalization performance by the GP model. The predictions were better or comparable to artificial neural networks (ANN) and support vector regression (SVR) methods. The GP based modeling approach illustrated will find diverse applications in (QSAR, QSPR and QSTR) modeling for the virtual screening of large libraries.

}, keywords = {ADME modeling, Caco-2 cell permeability, genetic programming, MLP, SVR}, issn = {1570-1808}, author = {Vyas, Renu and Goel, Purva and Karthikeyan, Muthukumarasamy and Tambe, S. S. and Kulkarni, B. D.} } @article { ISI:000330417100005, title = {Proposing efficient new pendant group polymer electrolyte membranes for fuel cells: a computational study}, journal = {Journal of Physical Chemistry C}, volume = {118}, number = {2}, year = {2014}, month = {JAN}, pages = {784-795}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

There is a need to develop new membranes for fuel cells that can conduct protons with high efficiency and at high temperatures. This paper reports a theoretical study of proton transfer barriers in newly proposed polymer electrolyte membranes (PEMs), having pendant nitrogen containing crown ether groups on an alkyl backbone. The proton transfer in the proposed pendant group PEMs would occur without the need of an external agent such as water or phosphoric acid, and without the need for the pendant groups to rotate and reorient themselves after each proton transfer. The current study shows that this would make the proposed PEMs very efficient, with low proton transfer barriers. This has been seen to be true for a range of different PEM cases considered, differing in the number of linker atoms in the alkyl backbone and in the number of nitrogens contained in each pendant group, thus, indicating the potential of the proposed structures as PEMs for fuel cells.

}, issn = {1932-7447}, doi = {10.1021/jp4081349}, author = {Mane, Manoj V. and Vanka, Kumar} } @article { ISI:000339880300021, title = {Proteomics of arsenic stress in the gram-positive organism Exiguobacterium sp PS NCIM 5463}, journal = {Applied Microbiology and Biotechnology}, volume = {98}, number = {15}, year = {2014}, month = {AUG}, pages = {6761-6773}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

The general responses of microorganisms to environmental onslaughts are modulated by altering the gene expression pattern to reduce damage in the cell and produce compensating stress responses. The present study attempts to unravel the response of the Gram-positive Exiguobacterium sp. PS NCIM 5463 in the presence of [As(III)] and arsenate [As(V)] using comparative proteomics via two-dimension gel electrophoresis (2-DE) coupled with identification of proteins using matrix-assisted laser desorption/ionisation (MALDI-TOF/MALDI-TOF/TOF). Out of 926 Coomassie-stained proteins, 45 were differentially expressed (p \< 0.05). Considering the resolution and abundance level, 24 spots (peptides) were subjected to MALDI analysis, identified and categorised into several functional categories, viz., nitrogen metabolism, energy and stress regulators, carbohydrate metabolism, protein synthesis components and others. A functional role of each protein is discussed in Exiguobacterium sp. PS 5463 under arsenic stress and validated at their transcript level using a quantitative real-time polymerase chain reaction. Unlike previous reports that unravel the responses toward arsenic stress in Gram-negative organisms, the present study identified new proteins under arsenic stress in a Gram-positive organism, Exiguobacterium sp. PS NCIM 5463, which could elucidate the physiology of organisms under arsenic stress.

}, keywords = {Arsenic, Exiguobacterium, proteomics, Stress, Transcriptomics}, issn = {0175-7598}, doi = {10.1007/s00253-014-5873-6}, author = {Sacheti, Poonam and Patil, Rajendra and Dube, Ankita and Bhonsle, Hemangi S. and Thombre, Dipalee and Marathe, Sayali and Vidhate, Ravindra and Wagh, Priyanka and Kulkarni, Mahesh J. and Rapole, Srikanth and Gade, Wasudeo N.} } @article { ISI:000339628400010, title = {Quantitative evaluation of the ability of ionic liquids to offset the cold-induced unfolding of proteins}, journal = {Physical Chemistry Chemical Physics}, volume = {16}, number = {30}, year = {2014}, month = {JUN}, pages = {15806-15810}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Significant non-reversible two-state denaturation was observed for proteins such as myoglobin (Mb) and alpha-chymotrypsin (CT) with decreasing temperature in the presence of 1-butyl-3-methylimidazolium-based ([C(4)mim]X-+(-)) ionic liquids (ILs) with various anions (X-). Interestingly, for the first time, ILs having acetate and bromide anions were proven to counteract the cold-induced unfolding of proteins.

}, issn = {1463-9076}, doi = {10.1039/c4cp01001a}, author = {Kumar, Awanish and Rani, Anjeeta and Venkatesu, Pannuru and Kumar, Anil} } @article { ISI:000336442600003, title = {Rapid efficient synthesis and characterization of silver, gold, and bimetallic nanoparticles from the medicinal plant plumbago zeylanica and their application in biofilm control}, journal = {International Journal of Nanomedicine}, volume = {9}, year = {2014}, month = {MAY}, pages = {2635-2653}, publisher = {DOVE MEDICAL PRESS LTD}, address = {PO BOX 300-008, ALBANY, AUCKLAND 0752, NEW ZEALAND}, abstract = {

Background: Nanoparticles (NPs) have gained significance in medical fields due to their high surface-area-to-volume ratio. In this study, we synthesized NPs from a medicinally important plant - Plumbago zeylanica. Materials and methods: Aqueous root extract of P. zeylanica (PZRE) was analyzed for the presence of flavonoids, sugars, and organic acids using high-performance thin-layer chromatography (HPTLC), gas chromatography-time of flight-mass spectrometry (GC-TOF-MS), and biochemical methods. The silver NPs (AgNPs), gold NPs (AuNPs), and bimetallic NPs (AgAuNPs) were synthesized from root extract and characterized using ultraviolet-visible spectra, X-ray diffraction (XRD), energy-dispersive spectrometry (EDS), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The effects of these NPs on Acinetobacter baumannii, Staphylococcus aureus, and Escherichia coli biofilms were studied using quantitative biofilm inhibition and disruption assays, as well as using fluorescence, scanning electron microscopy, and atomic force microscopy. Results: PZRE showed the presence of phenolics, such as plumbagin, and flavonoids, in addition to citric acid, sucrose, glucose, fructose, and starch, using HPTLC, GC-TOF-MS, and quantitative analysis. Bioreduction of silver nitrate (AgNO3) and chloroauric acid (HAuCl4) were confirmed at absorbances of 440 nm (AgNPs), 570 nm (AuNPs), and 540 nm (AgAuNPs), respectively. The maximum rate of synthesis at 50 degrees C was achieved with 5 mM AgNO3 within 4.5 hours for AgNPs; and with 0.7 mM HAuCl4 within 5 hours for AuNPs. The synthesis of AgAuNPs, which completed within 90 minutes with 0.7 mM AgNO3 and HAuCl4, was found to be the fastest. Fourier-transform infrared spectroscopy confirmed bioreduction, while EDS and XRD patterns confirmed purity and the crystalline nature of the NPs, respectively. TEM micrographs and DLS showed about 60 nm monodispersed Ag nanospheres, 20-30 nm Au nanospheres adhering to form Au nanotriangles, and about 90 nm hexagonal blunt-ended AgAuNPs. These NPs also showed antimicrobial and antibiofilm activity against E. coli, A. baumannii, S. aureus, and a mixed culture of A. baumannii and S. aureus. AgNPs inhibited biofilm in the range of 96\%-99\% and AgAuNPs from 93\% to 98\% in single-culture biofilms. AuNPs also showed biofilm inhibition, with the highest of 98\% in S. aureus. AgNPs also showed good biofilm disruption, with the highest of 88\% in A. baumannii. Conclusion: This is the first report on rapid and efficient synthesis of AgNPs, AuNPs and AgAuNPs from P. zeylanica and their effect on quantitative inhibition and disruption of bacterial biofilms.

}, keywords = {AgAuNPs, AgNPs, AuNPs, biofilm inhibition and disruption, GC-TOF-MS, P. zeylanica}, issn = {1178-2013}, doi = {10.2147/IJN.S59834}, author = {Salunke, Gayatri R. and Ghosh, Sougata and Kumar, R. J. Santosh and Khade, Samiksha and Vashisth, Priya and Kale, Trupti S. and Chopade, Snehal and Pruthi, Vikas and Kundu, Gopal and Bellare, Jayesh R. and Chopade, Balu Ananda} } @article {46363, title = {Relativistic equation-of-motion coupled-cluster method: application to closed-shell atomic systems}, journal = {Physical Review Applied}, volume = {89}, year = {2014}, month = {APR }, pages = {042510}, type = {Article}, abstract = {

We report our successful implementation of the relativistic equation-of-motion coupled-cluster (EOMCC) method. This method is employed to compute the principal ionization potentials (IPs) of closed-shell rare-gas atoms, He-like ions, Be-like ions, along with Na+, Al+, K+, Be, andMg. Four-component Dirac spinors are used in the calculations, and the one-and two-electron integrals are evaluated using the Dirac-Coulomb Hamiltonian. Our results are in excellent agreement with available measurements, which are taken from the National Institute of Science and Technology database. The accuracies of the calculations are estimated to be within one half of a percent for He-like and Be-like ions and 1\% for the heavier systems. We also present results using the second-order many-body perturbation theory and random-phase approximation in the EOMCC framework. These results are compared with those of EOMCC at the level of single and double excitations in order to assess the role of the electron correlation effects in the intermediate schemes considered in our calculations.

}, issn = {2469-9926}, doi = {10.1103/PhysRevA.89.042510}, author = {Pathak, Himadri and Sahoo, B. K. and Das, B. P. and Vaval, Nayana and Pal, Sourav} } @article {42640, title = {Relativistic equation-of-motion coupled-cluster method for the double-ionization potentials of closed-shell atoms}, journal = {Physical Review A}, volume = {90}, year = {2014}, month = {JUL}, pages = {Article No. 010501}, doi = {10.1103/PhysRevA.90.010501}, author = {Pathak, Himadri and Ghosh, Aryya and Sahoo, B. K. and Das, B. P. and Vaval, Nayana and Pal, Sourav} } @article { ISI:000346385900016, title = {Relativistic equation-of-motion coupled-cluster method for the ionization problem: application to molecules}, journal = {Physical Review A}, volume = {90}, number = {6}, year = {2014}, month = {DEC}, pages = {Article No. 062501}, publisher = {AMER PHYSICAL SOC}, address = {ONE PHYSICS ELLIPSE, COLLEGE PK, MD 20740-3844 USA}, abstract = {

We report the implementation of the four-component spinor relativistic equation-of-motion (EOM) coupled-cluster method within the single- and double-excitation approximation to calculate the ionization potential of molecules. We have applied this method to calculate vertical ionization potentials of the molecules XH (X = F, Cl, Br, I) along with Cl-2 and Br-2 in their closed-shell configuration. We have also presented intermediate results using the second-order many-body perturbation-theory level in the EOM framework to understand the role of electron correlation. All the calculated values are compared with the available experimental results. Our results are found to be in good agreement with sophisticated experiments, and relative deviation of less than 1\% is achieved for all the considered systems.

}, issn = {1050-2947}, doi = {10.1103/PhysRevA.90.062501}, author = {Pathak, Himadri and Sasmal, Sudip and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article { ISI:000338011200013, title = {Scaling behavior of resistive switching in epitaxial bismuth ferrite heterostructures}, journal = {Advanced Functional Materials}, volume = {24}, number = {25}, year = {2014}, month = {JUL}, pages = {3962-3969}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

Resistive switching (RS) of (001) epitaxial multiferroic BiFeO3/La0.67Sr0.33MnO3/SrTiO3 heterostructures is investigated for varying lengths scales in both the thickness and lateral directions. Macroscale current-voltage analyses in conjunction with local conduction atomic force microscopy (CAFM) reveal that whilst both the local and global resistive states are strongly driven by polarization direction, the type of conduction mechanism is different for each distinct thickness regime. Electrode-area dependent studies confirm the RS is dominated by an interface mechanism and not by filamentary formation. Furthermore, CAFM maps allow deconvolution of the roles played by domains and domain walls during the RS process. It is shown that the net polarization direction, and not domain walls, controls the conduction process. An interface mechanism based on barrier height and width alteration due to polarization reversal is proposed, and the role of electronic reconstruction at the interface is further investigated.

}, issn = {1616-301X}, doi = {10.1002/adfm.201400110}, author = {Rana, Abhimanyu and Lu, Haidong and Bogle, Kashinath A. and Zhang, Qi and Vasudevan, Rama and Thakare, Vishal and Gruverman, Alexei and Ogale, Satishchandra and Valanoor, Nagarajan} } @article { ISI:000341339300024, title = {Second generation, arginine-rich (R-X {\textquoteleft}-R)(4)-type cell-penetrating alpha-omega-alpha-peptides with constrained, chiral omega-amino acids (X {\textquoteleft}) for enhanced cargo delivery into cells}, journal = {Bioorganic \& Medicinal Chemistry Letters}, volume = {24}, number = {17}, year = {2014}, month = {SEP}, pages = {4198-4202}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

The syntheses of novel N-aminoalkyl proline-derived spacers (X{\textquoteright}) in polycationic (R-X{\textquoteright}-R)-motif cell-penetrating alpha-omega-alpha-peptides are described as improved molecular transporters and their structural features studied by CD. FACS analysis shows enhanced cellular uptake and confocal microscopy indicates predominantly cytoplasmic localization. The oligomers are efficient at transporting pDNA into cells. The chirality together with the hydrophobicity and flexibility derived from the spacer chain are found to have marked influence on the cell-penetrating and cargo delivery properties of the cell-penetrating peptides (CPPs). The peptides containing N-(3-aminopropyl)-D-proline spacers are found to be the best at cell penetration and cargo delivery in the present study. (C) 2014 Elsevier Ltd. All rights reserved.

}, keywords = {(R-X-R)-motif, alpha-omega-alpha-Peptide, Cell-penetrating peptide, Constrained chiral amino acid, Peptidomimetics}, issn = {0960-894X}, doi = {10.1016/j.bmcl.2014.07.040}, author = {Patil, Kiran M. and Naik, Rangeetha J. and Vij, Manika and Yadav, Amit K. and Kumar, Vaijayanti A. and Ganguli, Munia and Fernandes, Moneesha} } @article { ISI:000330542900022, title = {Sequential electrochemical unzipping of single-walled carbon nanotubes to graphene ribbons revealed by in situ Raman spectroscopy and imaging}, journal = {ACS Nano}, volume = {8}, number = {1}, year = {2014}, month = {JAN}, pages = {234-242}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We report an in situ Raman spectroscopic and microscopic investigation of the electrochemical unzipping of single-walled carbon nanotubes (SWNTs). Observations of the radial breathing modes (RBMs) using Raman spectral mapping reveal that metallic SWNTs are opened up rapidly followed by gradual unzipping of semiconducting SWNTs. Consideration of the resonant Raman scattering theory suggests that two metallic SWNTs with chiralities (10,4) and (12, 0) get unzipped first at a lower electrode potential (036 V) followed by the gradual unzipping of another two metallic tubes, (9, 3) and (10, 1), at a relatively higher potential (1.16 V). The semiconducting SWNTs with chiralities (11, 7) and (12, 5), however, get open up gradually at +/- 1.66 V. A rapid decrease followed by a subsequent gradual decrease in the metallicity of the SWNT ensemble as revealed from a remarkable variation of the peak width of the G band complies well with the variations of RBM. Cyclic voltammetry also gives direct evidence for unzipping in terms of improved capacitance after oxidation followed by more important removal of oxygen functionalities during the reduction step, as reflected in subtle changes of the morphology confirming the formation of graphene nanoribbons. The density functional-based tight binding calculations show additional dependence of chirality and diameter of nanotubes on the epoxide binding energies, which is in agreement with the Raman spectroscopic results and suggests a possible mechanism of unzipping determined by combined effects of the structural characteristics of SWNTs and applied field.

}, keywords = {density functional-based tight binding calculations, Electrochemistry, graphene, Raman spectral mapping, single-walled carbon nanotubes}, issn = {1936-0851}, doi = {10.1021/nn403289g}, author = {John, Robin and Shinde, Dhanraj B. and Liu, Lili and Ding, Feng and Xu, Zhiping and Vijayan, Cherianath and Pillai, Vijayamohanan K. and Pradeep, Thalappil} } @article { ISI:000346321700065, title = {Size quantization effects on interfacial electron transfer dynamics in Ru(II)-polypyridyl complex sensitized ZnO QDs}, journal = {Journal of Physical Chemistry C}, volume = {118}, number = {49}, year = {2014}, month = {DEC}, pages = {28898-28905}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Quantum-size confinement in semiconductor material offers size based tunability of interband gap energy as well as intraband sublevels. In this work, size quantization of wide bandgap ZnO quantum dots has been explored in the study of interfacial charge separation reaction using a catechol functionalized Ru(II)polypyridyl complex as a photosensitizer molecule. Femtosecond time-resolved transient absorption studies have revealed multiple electron injection events based on discrete conduction band states of ZnO QDs. The electron injection rates have been rationalized for quantum confinement effects owing to different sizes of ZnO QDs. Furthermore, the size dependency of the intrinsic lifetime of electrons injected into discrete energy levels of ZnO QDs has been revealed in charge recombination reaction with the Ru(III)polypyridyl complex cation. The charge recombination dynamics reveals a competing trend of carrier confinement and carrier leak upon reducing particle size. This study shows the optimization of finite size effects in achieving better interfacial charge separation at the dye/semiconductor interface.

}, issn = {1932-7447}, doi = {10.1021/jp5101158}, author = {Verma, Sandeep and Das, Amitava and Ghosh, Hirendra N.} } @article { ISI:000336733100003, title = {Steady state fluorescence studies of wild type recombinant cinnamoyl CoA reductase (Ll-CCRH1) and its active site mutants}, journal = {Journal of Fluorescence}, volume = {24}, number = {3}, year = {2014}, month = {MAY}, pages = {665-673}, publisher = {SPRINGER/PLENUM PUBLISHERS}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Fluorescence quenching and time resolved fluorescence studies of wild type recombinant cinnamoyl CoA reductase (Ll-CCRH1), a multitryptophan protein from Leucaena leucocephala and 10 different active site mutants were carried out to investigate tryptophan environment. The enzyme showed highest affinity for feruloyl CoA (K (a) = 3.72 x 10(5) M-1) over other CoA esters and cinnamaldehydes, as determined by fluorescence spectroscopy. Quenching of the fluorescence by acrylamide for wild type and active site mutants was collisional with almost 100 \% of the tryptophan fluorescence accessible under native condition and remained same after denaturation of protein with 6 M GdnHCl. In wild type Ll-CCRH1, the extent of quenching achieved with iodide (f (a) = 1.0) was significantly higher than cesium ions (f (a) = 0.33) suggesting more density of positive charge around surface of trp conformers under native conditions. Denaturation of wild type protein with 6 M GdnHCl led to significant increase in the quenching with cesium (f (a) = 0.54), whereas quenching with iodide ion was decreased (f (a) = 0.78), indicating reorientation of charge density around trp from positive to negative and heterogeneity in trp environment. The Stern-Volmer plots for wild type and mutants Ll-CCRH1 under native and denatured conditions, with cesium ion yielded biphasic quenching profiles. The extent of quenching for cesium and iodide ions under native and denatured conditions observed in active site mutants was significantly different from wild type Ll-CCRH1 under the same conditions. Thus, single substitution type mutations of active site residues showed heterogeneity in tryptophan microenvironment and differential degree of conformation of protein under native or denatured conditions.

}, keywords = {Active site mutants, Cinnamoyl CoA reductase, fluorescence, Ligand binding, Solute quenching}, issn = {1053-0509}, doi = {10.1007/s10895-013-1343-2}, author = {Sonawane, Prashant and Vishwakarma, Rishi Kishore and Singh, Somesh and Gaikwad, Sushama M. and Khan, Bashir Mohammad} } @article { ISI:000331861500013, title = {Structure and dynamics of benzyl-NX3 (X = Me, Et) trifluoromethanesulfonate ionic liquids}, journal = {Journal of Physical Chemistry B}, volume = {118}, number = {7}, year = {2014}, month = {FEB}, pages = {1831-1838}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Ammonium-based benzyl-NX3 (X = methyl, ethyl) trifluoromethanesulfonate (TFA) ionic liquids (ILs) are low cost, nontoxic, thermally stable ion-conducting electrolytes in fuel cells and batteries. In the present study, we have characterized the structure and dynamics of these ILs using molecular dynamics (MD) simulations and ionic conductivity using electro-chemical impedance spectroscopy (EIS) at varying temperature and relative humidity (RH). Results from MD simulations predict that cation-cation and cation-anion interactions are stronger in benzyltrimethylammonium (BzTMA) compared to benzyltriethylammonium (BzTEA) that diminish with increase in RH. Further, the BzTMA cations show both C-H/Ph (center of mass of phenyl ring) and cation-Ph interactions whereas BzTEA cations show only strong cation-Ph interactions. The C-H/Ph interactions (psi \>= 90 degrees, d(H-Ph) \<= 4 angstrom, theta \< 50 degrees and d(C.Ph) \<= 4.3 angstrom) in BzTMA cations increase with RH and are highest at RH = 90\%. The cumulative impact of electrostatic, cation/Ph, and C-H/Ph interactions results in lower conductivity of BzTMA-TFA IL compared to BzTEA-TFA IL. The EIS measurements show that the trends in ionic conductivity of ILs at RH = 30 and 90\% are qualitatively similar to the Nernst-Einstein conductivity from MD simulations. The ionic conductivity of BzTEA-TFA IL is similar to 3 times higher than BzTMA-TFA IL at 353 K and RH = 90\%.

}, issn = {1520-6106}, doi = {10.1021/jp410487a}, author = {Sunda, Anurag Prakash and Dhavale, Vishal M. and Kurungot, Sreekumar and Venkatnathan, Arun} } @article { ISI:000337786700050, title = {Structure sensitive chemical reactivity by palladium concave nanocubes and nanoflowers synthesised by a seed mediated procedure in aqueous medium}, journal = {Nanoscale}, volume = {6}, number = {13}, year = {2014}, month = {JUN}, pages = {7496-7502}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Palladium nanocubes and their transformation to concave nanocubes and nanoflowers are realised by a seed mediated procedure in aqueous medium and at room temperature using cationic surfactants. The concave nanocubes and nanoflowers were found to be enclosed by high index facets. The under coordinated atoms present on the high index facets make these nanostructures chemically more active towards Suzuki coupling and Heck coupling reactions compared to the conventional nanocubes and spherical nanoparticles of similar size.

}, issn = {2040-3364}, doi = {10.1039/c4nr01283f}, author = {Sreedhal, S. and Sudheeshkumar, V. and Vinod, C. P.} } @article { ISI:000332188200009, title = {Structure, stability, and properties of the trans peroxo nitrate radical: the importance of nondynamic correlation}, journal = {Journal of Physical Chemistry A}, volume = {118}, number = {8}, year = {2014}, month = {FEB}, pages = {1350-1362}, publisher = {AMER CHEMICAL SOC}, type = {Article}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We report a comparative single-reference and multireference coupled-cluster investigation on the structure, potential energy surface, and IR spectroscopic properties of the trans peroxo nitrate radical, one of the key intermediates in stratospheric NOx chemistry. The previous single-reference ab initio studies predicted an unbound structure for the trans peroxo nitrate radical. However, our Fock space multireference coupled-cluster calculation confirms a bound structure for the trans peroxo nitrate radical, in accordance with the experimental results reported earlier. Further, the analysis of the potential energy surface in FSMRCC method indicates a well-behaved minima, contrary to the shallow minima predicted by the single-reference coupled-cluster method. The harmonic force field analysis, of various possible isomers of peroxo nitrate also reveals that only the trans structure leads to the experimentally observed IR peak at 1840 cm(-1). The present study highlights the critical importance of nondynamic correlation in predicting the structure and properties of high-energy stratospheric NOx radicals.

}, issn = {1089-5639}, doi = {10.1021/jp409218c}, author = {Dutta, Achintya Kumar and Dar, Manzoor and Vaval, Nayana and Pal, Sourav} } @article { ISI:000343613000075, title = {Supramolecular transitions in native cellulose-I during progressive oxidation reaction leading to quasi-spherical nanoparticles of 6-carboxycellulose}, journal = {Carbohydrate Polymers}, volume = {113}, year = {2014}, month = {NOV}, pages = {615-623}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Cellulose-I swells considerably in phosphoric acid, and converts to amorphous cellulose via a cellulose-II transition state. Controlled oxidation of cellulose-I to 6-carboxycellulose (6CC) using HNO3-H3PO4-NaNO2 oxidation system led to the selective production of 6CC{\textquoteright}s of varying carboxyl contents (1.7-22\%) as well as various shapes and sizes (macro-sized fibrils of several micron length and/or spherical nanoparticles of 25-35 nm), depending on the reaction conditions. 6CC{\textquoteright}s having less than 14\% carboxyl content were largely in cellulose-II form (WAXRD values in-between cellulose I and cellulose II), whereas at 14-22\% the 6CC{\textquoteright}s were largely amorphous; only trace crystallinity was observed at 19\% and 22\% carboxyl 6CC. Spherical nanoparticles retained a high degree of crystallinity having cellulose-I structure, whereas the macro-sized fibrils were largely converted to cellulose-II structure. Analysis by WAXRD as well as by CP-MAS C-13 NMR studies gave similar conclusions. Reduced molecular weight with progressive oxidation, including presence of oligomers, was also evident from an increase in the reducing-end carbon peak at similar to 92 ppm. For high oxidation levels (\>14\%) the NMR 92-96 ppm peaks disappeared on extracting with dilute alkali, due to soluble oligomers being removed. (C) 2014 Elsevier Ltd. All rights reserved.

}, keywords = {Carboxycellulose, cellulose, Nanoparticles, NMR, WAXRD}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2014.07.056}, author = {Sharma, Priyanka R. and Rajamohanan, Pattuparambil R. and Varma, Anjanikumar} } @article { ISI:000330048400019, title = {Synthesis and electrochemistry of pseudocapacitive multilayer fullerenes and MnO2 nanocomposites}, journal = {Journal of Materials Chemistry A}, volume = {2}, number = {7}, year = {2014}, month = {NOV}, pages = {2152-2159}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Electrode materials with efficient capabilities for ionic and electronic transport are key to high performance supercapacitors. Here, we demonstrate a simple and comparatively low temperature synthesis of functionalized multilayer fullerenes so called carbon nano-onions (CNOs) as the electrode for high performance electrochemical supercapacitors. The exohedral type supercapacitor formed due to nonporous CNOs showed higher specific capacitance than conventional graphitic/mesoporous/activated carbons. Surface redox functionalities of these CNOs add up to significant pseudocapacitance. Further in situ incorporation of MnO2 nanoparticles to these CNOs increased the specific capacitance up to 1207 F g(-1), which is close to the theoretical value of pseudocapacitive MnO2.

}, issn = {2050-7488}, doi = {10.1039/c3ta14076h}, author = {Azhagan, Muniraj Vedi Kuyil and Vaishampayan, Mukta V. and Shelke, Manjusha V.} } @article { ISI:000343072300047, title = {Synthesis and electrochemistry of pseudocapacitive multilayer fullerenes and MnO2 nanocomposites (vol 2, pg 2152, 2014)}, journal = {Journal of Materials Chemistry A}, volume = {2}, number = {40}, year = {2014}, month = {OCT}, pages = {17186}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, issn = {2050-7488}, doi = {10.1039/c4ta90149e}, author = {Azhagan, Muniraj Vedi Kuyil and Vaishampayan, Mukta V. and Shelke, Manjusha V.} } @article { ISI:000331904500008, title = {Synthesis and reactivity of magnetically diverse Au@ Ni core-shell nanostructures}, journal = {Particle \& Particle Systems Characterization}, volume = {31}, number = {2}, year = {2014}, month = {FEB}, pages = {236-244}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

Core-shell bimetallic Au@Ni nanoparticles, with gold cores and thin nickel shells with overall size less than 10 nm, are synthesized and stabilized in pure cubic (fcc) and hexagonal (hcp) phase. Due to their unique crystal, electronic, and geometric structure, they show interesting magnetic and chemical properties. The Au@Ni-fcc is magnetic, whereas Au@Ni-hcp is non-magnetic. Both the bimetallic nanostructures are stable to surface oxidation until 150 degrees C and show excellent catalytic activity for p-nitrophenol reduction reaction.

}, keywords = {Au-Ni nanoparticles, bimetallic nanostructures, magnetic core-shell nanoparticles, oxidation resistance}, issn = {0934-0866}, doi = {10.1002/ppsc.201300195}, author = {Bharathan, Vysakh A. and Raj, Govind K. and Joy, Pattayil Alias and Vinod, Chathakudath P.} } @article { ISI:000340525300012, title = {Synthesis of alpha,beta-unsaturated delta-lactones by vinyl acetate mediated asymmetric cross-aldol reaction of acetaldehyde: mechanistic insights}, journal = {European Journal of Organic Chemistry}, number = {24}, year = {2014}, month = {AUG}, pages = {5247-5255}, publisher = {WILEY-V C H VERLAG GMBH}, type = {Article}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

A tandem asymmetric cross-aldol reaction involving the in situ generation of acetaldehyde from vinyl acetate has been developed that may resolve the challenges associated with the handling of acetaldehyde. The simple protocol, mild reaction conditions and unique harmony of an organocatalyst with a biocatalyst make this method a valuable tool for the synthesis of asymmetric beta-hydroxy aldehydes. By using this methodology we have accessed alpha,beta-unstaurated delta-lactones as well as isochromenones with high enantioselectivities from both asymmetric beta-hydroxy aldehydes and ketones. Systemic density functional theory (DFT) studies were also performed to gain mechanistic insights into the role of hydrogen bonding in the asymmetric cross-aldol reaction of acetaldehyde and in the key cis/trans isomerisation step in the synthesis of d-lactones.

}, keywords = {Aldol reactions, asymmetric catalysis, lactones, reaction mechanisms}, issn = {1434-193X}, doi = {10.1002/ejoc.201402551}, author = {Kumar, Manjeet and Kumar, Arvind and Rizvi, Masood and Mane, Manoj and Vanka, Kumar and Taneja, Subhash C. and Shah, Bhahwal Ali} } @article { ISI:000343613800043, title = {Thermal stability of cellulose and their nanoparticles: Effect of incremental increases in carboxyl and aldehyde groups}, journal = {Carbohydrate Polymers}, volume = {114}, year = {2014}, month = {DEC}, pages = {339-343}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Oxidized cellulose containing carboxyl and aldehyde functional groups represent an important class of cellulose derivatives. In this study effect of incrementally increasing COOH and CHO groups at C2, C3, and C6 positions of cellulose and nanocellulose has been investigated, with a view to understanding their effect on thermal treatment of cellulose. The results show that 2,3-dialdehyde cellulose (DAC) is the most thermally stable oxidized product of cellulose while the most unstable derivatives contain carboxyl group at the C6 position (6CC). Carboxymethylcellulose (CMC), with carboxymethyl group on C6 position, is more stable than 6CC. Multi-functionalized celluloses 2,3,6-tricarboxycellulose and 6-carboxy-2,3-dialdehyde, have the same level of thermal stability as 6CC, showing that the presence of carboxyl at the C6 is a key destabilizing factor in the thermal stability of oxidized cellulose products. More the number of reducing end groups on the polymer chain, lower the thermal stability of the cellulose, as proved by comparing the TGA/DTG of monomeric analogs dextrose, cellobiose and glucuronic acid with the oxidized celluloses. The thermal stability trend observed for oxidized celluloses was DAC \> DCC \> nanoparticles \> dextrose \>glucuronic acid, caused by extent of reducing ends and COOH groups. (C) 2014 Elsevier Ltd. All rights reserved.

}, keywords = {2, 3, 3-Dialdehyde cellulose, 6-Carboxycellulose, 6-Tricarboxycellulose, cellulose, TGA/DTG}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2014.08.032}, author = {Sharma, Priyanka R. and Varma, Anjanikumar} } @article { ISI:000345975300012, title = {Titania nanoparticles stabilized HPA in SBA-15 for the intermolecular hydroamination of activated olefins}, journal = {ChemCatChem}, volume = {6}, number = {12}, year = {2014}, month = {DEC}, pages = {3347-3354}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

A liquid phase hydroamination (HA) of alpha,beta-ethylenic compounds with amines was investigated with TiO2 nanoparticles stabilized 12-tungstophosphoric acid (TPA) in SBA-15. The catalysts were prepared by wet impregnation of TPA/TiO2 nanoparticles into the SBA-15 and calcined at different temperatures. The characterization results reveal that the textural properties and the acidity of the prepared catalysts can be finely controlled with the simple adjustment of the calcination temperature and the structure of the support, decorated with the TiO2 and TPA nanoparticles, was intact even after the modification. The prepared catalysts were investigated for HA of ethyl acrylate with different aromatic and aliphatic amines over a wide range of reaction conditions to optimize the yield and the selectivity of product. It was found that this process is 100\% atom efficient and the catalytic performance depended significantly on the loading of TPA over the catalyst and the calcination temperature. Under optimized reaction conditions, the best catalyst, 15 wt\% TPA/22.4 wt\% TiO2/SBA-15 calcined at 1123 K, offered the highest conversion of p-ethylaniline (70\%) with 100\% chemo-selectivity to the anti-Markovnikov product, i.e., the mono-addition product. The reaction was heterogeneously catalyzed and no contribution from leached TPA into the reaction was observed.

}, keywords = {heteropoly acids, hydroamination, mesoporous materials, nanocatalysts}, issn = {1867-3880}, doi = {10.1002/cctc.201402449}, author = {Sawant-Dhuri, Dhanashri and Balasubramanian, Veerappan V. and Ariga, Katsuhiko and Park, Dae-Hwan and Choy, Jin-Ho and Cha, Wang Soo and Al-deyab, Salem S. and Halligudi, Shivappa B. and Vinu, Ajayan} } @article { ISI:000346037500028, title = {Total synthesis of deoxy-solomonamide B by mimicking biogenesis}, journal = {Organic Letters}, volume = {16}, number = {23}, year = {2014}, month = {DEC}, pages = {6148-6151}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

A total synthesis of Deoxy-solomonamide B was accomplished starting from tryptophan in an efficient manner by mimicking the proposed biogenetic route. The present synthesis utilizes a crotylation, oxidative cleavage of the indole moiety, and macrolactamization as key steps. The use of the indole nucleus as a masked anthranilic acid unit paves the way for the easy synthesis of related macrocycles and natural products where the ortho-acyl aniline moiety is embedded into them, which otherwise is difficult to synthesize.

}, issn = {1523-7060}, doi = {10.1021/ol503011g}, author = {Vasudevan, N. and Kashinath, K. and Reddy, D. Srinivasa} } @article { ISI:000344204600027, title = {Total synthesis of mangiferaelactone}, journal = {Tetrahedron Letters}, volume = {55}, number = {45}, year = {2014}, month = {NOV}, pages = {6263-6265}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

Herein we document the first total synthesis of mangiferaelactone and thus establish its absolute configuration. The central nonenolide ring was constructed using ring closing metathesis and Yamaguchi esterification. The key alcohol fragment was synthesized by the Bernet-Vasella fragmentation of C-ribofuranoside. (C) 2014 Elsevier Ltd. All rights reserved.

}, keywords = {Bernet-Vasella fragmentation, Nonenolide, Ring closing metathesis, Total synthesis, Yamaguchi protocol}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2014.09.084}, author = {Vadhadiya, Paresh M. and Ramana, C. V.} } @article { ISI:000335773800005, title = {Vesicle structures from bolaamphiphilic biosurfactants: experimental and molecular dynamics simulation studies on the effect of unsaturation on sophorolipid self-assemblies}, journal = {Chemistry-A European Journal}, volume = {20}, number = {21}, year = {2014}, month = {MAY}, pages = {6246-6250}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

The formation of giant-vesicle-like structures by self-assembling linolenic acid sophorolipid (LNSL) molecules is revealed. Sophorolipids belong to the class of bolaamphiphilic glycolipid biosurfactants. Interestingly, the number of double bonds present in the hydrophobic core of sophorolipids is seen to have a great influence on the type of self-assembled structures formed. Dye encapsulation results establish the presence of an aqueous compartment inside the LNSL vesicles. Molecular dynamics simulation (MD) studies suggest the existence of two possible conformations of LNSLs inside the self-assembled structures and that LNSL molecules arrange in layered structures.

}, keywords = {bolaamphiphiles, MD simulations, Self-assembly, sophorolipids, vesicles}, issn = {0947-6539}, doi = {10.1002/chem.201304719}, author = {Dhasaiyan, Prabhu and Pandey, Prithvi Raj and Visaveliya, Nikunjkumar and Roy, Sudip and Bhagavatula L. V. Prasad} } @article { ISI:000357587500004, title = {Abiotic stress induces change in cinnamoyl CoA reductase (CCR) protein abundance and lignin deposition in developing seedlings of Leucaena leucocephala}, journal = {Physiology and Molecular Biology of Plants}, volume = {21}, number = {2}, year = {2015}, month = {APR}, pages = {197-205}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Aboitic stress such as drought and salinity are class of major threats, which plants undergo through their lifetime. Lignin deposition is one of the responses to such abiotic stresses. The gene encoding Cinnamoyl CoA Reductase (CCR) is a key gene for lignin biosynthesis, which has been shown to be over-expressed under stress conditions. In the present study, developing seedlings of Leucaena leucocephala (Vernacular name: Subabul, White popinac) were treated with 1 \% mannitol and 200 mM NaCl to mimic drought and salinity stress conditions, respectively. Enzyme linked immunosorbant assay (ELISA) based expression pattern of CCR protein was monitored coupled with Phlorogucinol/HCl activity staining of lignin in transverse sections of developing L. leucocephala seedlings under stress. Our result suggests a differential lignification pattern in developing root and stem under stress conditions. Increase in lignification was observed in mannitol treated stems and corresponding CCR protein accumulation was also higher than control and salt stress treated samples. On the contrary CCR protein was lower in NaCl treated stems and corresponding lignin deposition was also low. Developing root tissue showed a high level of CCR content and lignin deposition than stem samples under all conditions tested. Overall result suggested that lignin accumulation was not affected much in case of developing root however developing stems were significantly affected under drought and salinity stress condition.

}, issn = {0971-5894}, doi = {10.1007/s12298-015-0289-z}, author = {Srivastava, Sameer and Vishwakarma, Rishi K. and Arafat, Yasir Ali and Gupta, Sushim K. and Khan, Bashir Mohammad} } @article { ISI:000352488300022, title = {Activity enhancement upon the incorporation of titanium: au@ti-sio2 core-shell nanocatalysts for the CO oxidation reaction}, journal = {ChemCatChem}, volume = {7}, number = {7}, year = {2015}, month = {APR}, pages = {1222-1230}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

The encapsulation of gold nanoparticles 8-12nm in size within a porous Ti-SiO2 shell to form a core-shell nanoarchitecture was investigated, and the catalytic activity of the resulting structure was probed. Detailed characterization of the synthesized materials shows that the core-shell morphology is lost beyond a certain amount of incorporated titanium, and results in normal gold-supported Ti-SiO2. The material has a high surface area (913m(2)g(-1)) and high porosity, both of which make it an excellent choice for catalytic applications. With the optimum amount of incorporated Ti, the core-shell catalyst shows excellent room-temperature CO oxidation activity over several cycles with retention of its morphology at higher temperatures.

}, keywords = {core-shell structures, gold nanoparticles, Oxidation, Ti-SiO2}, issn = {1867-3880}, doi = {10.1002/cctc.201402954}, author = {Sekhar, Anandakumari C. Sunil and Kottavarithottil Ziyad and Soni, Yogita and Vinod, Chathakudath P.} } @article { ISI:000361075900005, title = {Bacillus encimensis sp nov isolated from marine sediment}, journal = {International Journal of Systematic and Evolutionary Microbiology}, volume = {65}, number = {5}, year = {2015}, month = {MAY}, pages = {1421-1425}, publisher = {SOC GENERAL MICROBIOLOGY}, address = {MARLBOROUGH HOUSE, BASINGSTOKE RD, SPENCERS WOODS, READING RG7 1AG, BERKS, ENGLAND}, abstract = {

A Gram-stain-positive, rod-shaped, endospore-forming, aerobic bacterium designated SGD-V-25(T) was isolated from Veraval sediment sample, India. Strain SGD-V-25(T) was capable of growing at 25-50 degrees C (optimum 37 degrees C), pH 6-12 (optimum pH 7.0) and with 0-5 \% (w/v) NaCl. The taxonomic position of this strain was deduced using a polyphasic approach and the 16S rRNA gene sequence analysis showed that the isolate belongs to the phylum Firmicutes, forming the cluster with Bacillus badius MTCC 1548(T), with which it shares highest similarity of 99.1 \% with 13 nt differences. Other type strains of the genus Bacillus showed less than 96\% similarity. The cell wall contained meso-diaminopimelic acid as the diagnostic diamino acid. The polar lipid profile of strain SGD-V-25(T) showed the presence of diphosphatidylglycerol, phosphatidylglycerol, phsophoglycolipid and two aminophospholipids. The predominant isoprenoid quinone was MK-7. The major cellular fatty acids were iso-C-15:0, anteiso-C-15:0, anteiso-C-17:0 iso-C-16:0, C-16:1 omega 11c and C-16:0. The genomic DNA G + C content of strain SGD-V-25(T) was 37.6 molok. On the basis of phenotypic characteristics, phylogenetic analysis and DNA-DNA hybridization, strain SGD-V-25(T) could be clearly distinguished from closely related members of the genus Bacillus, and the name Bacillus encimensis sp. nov., is proposed to accommodate this strain. The type strain is SGD-V-25(T) (= NCIM 5513(T)=DSM 28241(T)).

}, issn = {1466-5026}, doi = {10.1099/ijs.0.000114}, author = {Dastager, Syed Gulam and Mawlankar, Rahul R. and Mual, Poonam and Verma, Ashish and Krishnamurthi, Srinivasan and Joseph, Neeta and Shouche, Yogesh S.} } @article { ISI:000359166300084, title = {Bacopa monniera recombinant mevalonate diphosphate decarboxylase: biochemical characterization}, journal = {International Journal of Biological Macromolecules}, volume = {79}, year = {2015}, month = {AUG}, pages = {661-668}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Mevalonate diphosphate decarboxylase (MDD; EC 4.1.1.33) is an important enzyme in the mevalonic acid pathway catalyzing the Mg2+-ATP dependant decarboxylation of mevalonate 5-diphosphate (MVAPP) to isopentenyl diphosphate (IPP). Bacopa monniera recombinant MDD (BmMDD) protein was overexpressed in Escherichia coli BL21 (DE3) strain and purified to apparent homogeneity. K-m and V-max for MVAPP were 144 mu M and 52 U mg(-1) respectively. The values of turnover (k(cat)) and k(cat)/K-m, for mevalonate 5-diphosphate were determined to be 40 s(-1) and 2.77 x 10(5) M-1 s(-1) and k(cat) and k(cat)/K-m values for ATP were found to be 30 s(-1) and 2.20 x 10(4) M-1 s(-1), respectively. pH activity profile indicated the involvement of carboxylate ion, lysine and arginine for the activity of enzyme. The apparent activation energy for the BmMDD catalyzed reaction was 12.7 kJ mol(-1). Optimum pH and temperature for the forward reaction was found to be 8.0 and 45 degrees C. The enzyme was most stable at pH 7 at 20 degrees C with the deactivation rate constant (K-d(*)) of 1.69 x 10(-4) and half life (t(1/2)) of 68 h. The cation studies suggested that BmMDD is a cation dependant enzyme and optimum activity was achieved in the presence of Mg2+. (C) 2015 Elsevier B.V. All rights reserved.

}, keywords = {Mevalonate diphosphate decarboxylase, pH activity profile, Phylogenetic analysis, stability}, issn = {0141-8130}, doi = {10.1016/j.ijbiomac.2015.05.041}, author = {Shakeel Abbassi and Vishwakarma, Rishi K. and Patel, Parth and Kumari, Uma and Khan, Bashir Mohammad} } @article { ISI:000347577900102, title = {Biochemical characterization of recombinant mevalonate kinase from Bacopa monniera}, journal = {International Journal of Biological Macromolecules}, volume = {72}, year = {2015}, month = {JAN}, pages = {776-783}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Mevalonate kinase (MK; ATP: mevalonate 5-phosphotransferase; EC 2.7.1.36) plays a key role in isoprenoid biosynthetic pathway in plants. MK catalyzes the phosphorylation of mevalonate to form mevalonate-5-phosphate. The recombinant BmMK was cloned and over-expressed in E. coli BL21 (DE3), and purified to homogeneity by affinity chromatography followed by gel filtration. Optimum pH and temperature for forward reaction was found to be 7.0 and 30 degrees C, respectively. The enzyme was most stable at pH 8 at 25 degrees C with deactivation rate constant (Kd*) 1.398 x 10(-4) and half life (t(1/2)) 49 h. pH activity profile of BmMK indicates the involvement of carboxylate ion, histidine, lysine, arginine or aspartic acid at the active site of enzyme. Activity of recombinant BmMK was confirmed by phosphorylation of RS-mevalonate in the presence of Mg2+, having K-m and V-max 331.9 mu M and 719.1 pKat mu g(-1), respectively. The values of k(cat) and k(cat)/K-m for RS-mevalonate were determined to be 143.82 s(-1) and 0.43332 M-1 s(-1) and k(cat) and k(cat)/K-m values for ATP were found 150.9 s(-1) and 1.023 M-1 s(-1). The metal ion studies suggested that BmMK is a metal dependent enzyme and highly active in the presence of MgCl2. (C) 2014 Elsevier B.V. All rights reserved.

}, keywords = {Bacopa monniera, Enzyme kinetics, Mevalonate kinase, stability}, issn = {0141-8130}, doi = {10.1016/j.ijbiomac.2014.09.030}, author = {Kumari, Uma and Vishwakarma, Rishi K. and Sonawane, Prashant and Shakeel Abbassi and Khan, Bashir Mohammad} } @article { ISI:000362920700039, title = {Bioinspired catecholic flame retardant nanocoating for flexible polyurethane foams}, journal = {Chemistry of Materials}, volume = {27}, number = {19}, year = {2015}, month = {OCT}, pages = {6784-6790}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

An efficient, environmentally friendly, and water-applied flame retardant surface nanocoating based on polydopamine (PDA) was developed for foamed materials such as polyurethane (PU). The PDA nanocoating, deposited by simple dip-coating in an aqueous dopamine solution, consists of a planar sublayer and a secondary granular layer structure that evolve together, eventually turning into a dense, uniform, and conformal layer on all foam surfaces. In contrast to flexible PU foams that are known to be highly flammable without flame retardant additives, micro combustion calorimetry (MCC) and thermogravimetric analysis (TGA) confirm that the neat PDA is relatively inflammable with a strong tendency to form carbonaceous, porous char that is highly advantageous for flame retardancy. By depositing nano coatings of PDA onto flexible PU foams, the flammability of the PU foam was significantly reduced with increasing coating thickness. For the thickest coating (3 days of PDA deposition), the foam quickly self-extinguished and its original shape was completely preserved after exposure to a flame in a torch burn test. In addition to the char forming ability of PDA, it is hypothesized that its catechol units likely scavenge nearby radicals that typically evolve additional fuel for the fire as they attack surrounding materials. This multiple flame retardancy action of PDA (i.e., char formation + radical scavenging) enables flame retardant foams with a peak heat release rate (P-HRR) that is significantly reduced (up to 67\%) relative to control foams, representing much better performance than many conventional additives reported in the literature at comparable or higher loadings.

}, issn = {0897-4756}, doi = {10.1021/acs.chemmater.5b03013}, author = {Cho, Joon Hee and Vasagar, Vivek and Shanmuganathan, Kadhiravan and Jones, Amanda R. and Nazarenko, Sergei and Ellison, Christopher J.} } @article { ISI:000366878300071, title = {Biomimetic synthesis of phaitanthrin e involving a fragmentation of sp(3) carbon-carbon bond: synthesis and rearrangement of phaitanthrin D to phaitanthrin E}, journal = {Organic Letters}, volume = {17}, number = {24}, year = {2015}, month = {DEC}, pages = {6218-6221}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

A biogenetic type total synthesis of alkaloids phaitanthrin D and phaitanthrin E has been described. The Csp(3)-Csp(3) bond cleavage with the release of several heteroatoms bearing unexpected leaving groups in intramolecular substitution reactions on an iminium double bond in the quinazolinones has been demonstrated using HMDS/ZnCl2 or NaHMDS. The mechanistic aspects have been supported by isolation and characterization of appropriate intermediates.

}, issn = {1523-7060}, doi = {10.1021/acs.orglett.5b03203}, author = {Vaidya, Sagar D. and N. P. Argade} } @article { ISI:000350841100024, title = {Biophysical characterization and molecular docking studies of imidazolium based polyelectrolytes-DNA complexes: role of hydrophobicity}, journal = {Biomacromolecules}, volume = {16}, number = {3}, year = {2015}, month = {MAR}, pages = {894-903}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Nonviral gene delivery vectors are acquiring greater attention in the field of gene therapy by replacing the biological viral vectors. DNA-cationic polymer complexes are one of the most promising systems to find application in gene therapy. Hence, a complete insight of their biophysical characterization and binding energy profile is important in understanding the mechanism involved in nonviral gene therapy. In this investigation, the interaction between calf thymus DNA (ctDNA) and imidazolium-based poly(ionic liquids) (PILs) also known as polyelectrolytes with three different alkyl side chains (ethyl, butyl, and hexyl) in physiological conditions using various spectroscopic experiments with constant DNA concentration and varying polyelectrolyte concentrations is reported. UV-visible absorption, fluorescence quenching studies, gel electrophoresis, circular dichroism (CD), and Fourier transform infrared spectroscopy (FTIR) have confirmed the binding of polyelectrolytes with DNA. UV-vis absorption measurements and fluorescence quenching revealed that the binding between DNA and the polyelectrolyte is dominated by electrostatic interactions. Additionally, CD and FTIR results indicated that the DNA retained its B-form with minor perturbation in the phosphate backbone without significant change in the conformation of its base pairs. Preference for alkyl side chains (KPIL-Ethyl Br \< KPIL-Butyl Br \< KPIL-Hexyl Br) toward efficient binding between the polyelectrolyte and DNA was inferred from the binding and quenching constants calculated from the absorption and emission spectra, respectively. Further, in silico molecular docking studies not only validated the observed binding trend but also provided insight into the binding mode of the polyelectrolyte-DNA complex.

}, issn = {1525-7797}, doi = {10.1021/bm5018029}, author = {Manojkumar, Kasina and Charan, K. T. Prabhu and Sivaramakrishna, Akella and Jha, Prakash C. and Khedkar, Vijay M. and Siva, Ramamoorthy and Jayaraman, Gurunathan and Vijayakrishna, Kari} } @article { ISI:000360829900002, title = {Blends of shellac as nanofiber formulations for wound healing}, journal = {Journal of Bioactive and Compatible Polymers}, volume = {30}, number = {5}, year = {2015}, month = {SEP}, pages = {472-489}, publisher = {SAGE PUBLICATIONS LTD}, address = {1 OLIVERS YARD, 55 CITY ROAD, LONDON EC1Y 1SP, ENGLAND}, abstract = {

Shellac is being used in food, pharmaceutical, and agricultural industries. It is seldom used for biomedical applications due to its poor mechanical property and instability. We designed thermoresponsive shellac-based bioactive nanofiber mats that mimic extracellular matrix to extend their utility in wound healing. Various blend compositions of shellac, gelatin, and poly(N-isopropylacrylamide) enriched with a bioactive agent, nadifloxacin, were prepared and nanofiber mats were fabricated. The morphology of the nanofiber formation was influenced by the concentration of polymer, drug, and polymer blend composition. Polymer-drug interactions and thermal and crystalline properties of nanofiber mats were analyzed. The shellac/gelatin/poly(N-isopropylacrylamide) blend of composition 3\%/7\%/3\% (w/v) was chosen to evaluate in vitro drug release. Release studies recorded slow, constant, and sustained release for 140h. The release kinetics and mechanism confirmed zero-order release with resultant r(2) values greater than 0.99, and the Korsmeyer-Peppas release exponent (n) was slightly higher than 0.8, which indicated that drug diffusion was anomalous or non-Fickian type and drug release followed diffusion involving chain stretching. Indirect cytotoxicity studies recorded insignificant toxicity against normal human fibroblast cells. In vivo studies demonstrated that drug-loaded nanofiber mats were more suitable for faster tissue regeneration as compared to nanofiber mats without drug and commercial nadifloxacin cream.

}, keywords = {drug release and mechanism, nanofibers, Shellac, thermoresponsive, tissue regeneration}, issn = {0883-9115}, doi = {10.1177/0883911515585180}, author = {Vannuruswamy, Garikapati and Rathna, Gundloori Venkata Naga and Gadgil, Bhagyashri Shashikant Thorat and Gadad, Anand Panchakshari} } @article { ISI:000366429100003, title = {Breaking and making of rings: a method for the preparation of 4-quinolone-3-carboxylic acid amides and the expensive drug ivacaftor}, journal = {European Journal of Organic Chemistry}, number = {34}, year = {2015}, month = {DEC}, pages = {7433-7437}, publisher = {WILEY-V C H VERLAG GMBH}, address = {POSTFACH 101161, 69451 WEINHEIM, GERMANY}, abstract = {

A simple and convenient method to access 4-quinolone-3-carboxylic acid amides from indole-3-acetic acid amides through one-pot oxidative cleavage of the indole ring followed by condensation (Witkop-Winterfeldt type oxidation) was explored. The scope of the method was confirmed with more than 20 examples and was successfully applied to the synthesis of the drug Ivacaftor, the most expensive drug on the market.

}, keywords = {Amides, Drug design, Fused-ring systems, Oxidation, Ozonolysis}, issn = {1434-193X}, doi = {10.1002/ejoc.201501048}, author = {Vasudevan, N. and Jachak, Gorakhnath R. and Reddy, D. Srinivasa} } @article { ISI:000367464000006, title = {c Squalene synthase gene from medicinal herb bacopa monniera: molecular characterization, differential expression, comparative modeling, and docking studies}, journal = {Plant Molecular Biology Reporter}, volume = {33}, number = {6}, year = {2015}, month = {DEC}, pages = {1675-1685}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

The widespread pharmaceutically important triterpenoid saponins are synthesized via isoprenoid pathway. The formation of squalene is the key regulatory point in triterpene biosynthesis, catalyzed by squalene synthase (SQS). The present study deals with the detailed characterization of SQS by molecular, biochemical, and computational means from Bacopa monniera, an immensely important medicinal plant rich in triterpenoid saponin, bacosides. A full-length SQS gene was isolated from B. monniera, characterized as B. monniera squalene synthase (BmSQS) (1242 bp) encoding 414 amino acids. Deduced amino acid sequence of BmSQS showed highly conserved consensus aspartate-rich motifs (DXXXD) and catalytic site residues. Phylogenetic analysis showed that BmSQS belongs to dicot group having closest relationship with Salvia miltiorrhiza. Semiquantitative and real-time PCR studies showed that the BmSQS messenger RNA (mRNA) expression level was higher in vegetative parts (roots) as compared to floral parts. Methyl jasmonate induces the BmSQS mRNA expression in all tissues tested, while salicylic acid, cold, and salt induce much higher expression in roots. Homology modeling and docking simulations of BmSQS showed the pivotal roles of Asp77, Asp81, Asp213, Asp217, and Tyr168 in catalysis.

}, keywords = {Abiotic stress, Bacopa monniera, Comparative modeling and docking, Differential expression, Isoprenoid pathway, Squalene synthase}, issn = {0735-9640}, doi = {10.1007/s11105-015-0864-z}, author = {Vishwakarma, Rishi K. and Patel, Krunal and Sonawane, Prashant and Kumari, Uma and Singh, Somesh and Ruby and Shakeel Abbassi and Agrawal, Dinesh C. and Tsay, Hsin-Sheng and Khan, Bashir Mohammad} } @article { ISI:000360653900022, title = {Calculation of P,T-odd interaction constant of PbF using Z-vector method in the relativistic coupled-cluster framework}, journal = {Journal of Chemical Physics}, volume = {143}, number = {8}, year = {2015}, month = {AUG}, pages = {084119}, publisher = {AMER INST PHYSICS}, address = {1305 WALT WHITMAN RD, STE 300, MELVILLE, NY 11747-4501 USA}, abstract = {

The effective electric field experienced by the unpaired electron in the ground state of PbF, which is a potential candidate in the search of electron electric dipole moment due to some special characteristics, is calculated using Z-vector method in the coupled cluster single-and double-excitation approximation with four component Dirac spinor. This is an important quantity to set the upper bound limit of the electron electric dipole moment. Further, we have calculated molecular dipole moment and parallel magnetic hyperfine structure constant (A(parallel to)) of Pb-207 in PbF to test the accuracy of the wavefunction obtained in the Z-vector method. The outcome of our calculations clearly suggests that the core electrons have significant contribution to the {\textquoteleft}{\textquoteleft}atom in compound{\textquoteright}{\textquoteright} properties. (C) 2015 AIP Publishing LLC.

}, issn = {0021-9606}, doi = {10.1063/1.4929591}, author = {Sasmal, Sudip and Pathak, Himadri and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article { ISI:000351849100002, title = {Can substituted allenes be highly efficient leaving groups in catalytic processes? a computational investigation}, journal = {Journal of Computational Chemistry}, volume = {36}, number = {11}, year = {2015}, month = {APR}, pages = {795-804}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

There is considerable interest presently in the chemistry of allenes. The current computational investigation looks into the possibility of using allenes and their derivatives as leaving groups. As it is well known, leaving groups are significant in catalytic processes for generating the active site. A full quantum mechanical study using density functional theory shows that allenes and their derivatives can function as excellent leaving groups. Indeed, the calculations show that they can be several orders of magnitude more effective than existing ligands for this purpose. The modification of second generation Grubbs{\textquoteright} catalysts with these ligands suggests that the allene ligand cases that would be most effective are those having electron withdrawing groups, especially those that have the potential for supramolecular interactions between the substituent groups in the free state. (c) 2015 Wiley Periodicals, Inc.

}, keywords = {allenes, carbones, Density functional theory, olefin metathesis, supramolecular interactions}, issn = {0192-8651}, doi = {10.1002/jcc.23855}, author = {Kuriakose, Nishamol and Vanka, Kumar} } @article { ISI:000357034800003, title = {Cell line development for biomanufacturing processes: recent advances and an outlook}, journal = {Biotechnology Letters}, volume = {37}, number = {8}, year = {2015}, month = {AUG}, pages = {1553-1564}, publisher = {SPRINGER}, address = {VAN GODEWIJCKSTRAAT 30, 3311 GZ DORDRECHT, NETHERLANDS}, abstract = {

At the core of a biomanufacturing process for recombinant proteins is the production cell line. It influences the productivity and product quality. Its characteristics also dictate process development, as the process is optimized to complement the producing cell to achieve the target productivity and quality. Advances in the past decade, from vector design to cell line screening, have greatly expanded our capability to attain producing cell lines with certain desired traits. Increasing availability of genomic and transcriptomic resources for industrially important cell lines coupled with advances in genome editing technology have opened new avenues for cell line development. These developments are poised to help biosimilar manufacturing, which requires targeting pre-defined product quality attributes, e.g., glycoform, to match the innovator{\textquoteright}s range. This review summarizes recent advances and discusses future possibilities in this area.

}, keywords = {Biomanufacturing, Biosimilars, Cell line development, CHO cells genomics, Genome editing, Transcriptomics}, issn = {0141-5492}, doi = {10.1007/s10529-015-1843-z}, author = {Le, Huong and Vishwanathan, Nandita and Jacob, Nitya M. and Gadgil, Mugdha and Hu, Wei-Shou} } @article { ISI:000356176200034, title = {Chemical sensing in two dimensional porous covalent organic nanosheets}, journal = {Chemical Science}, volume = {6}, number = {7}, year = {2015}, month = {APR}, pages = {3931-3939}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Two new imide-based crystalline, porous, and chemically stable covalent organic frameworks (COFs) (TpBDH and TfpBDH) have been successfully synthesized employing solvothermal crystallization route. Furthermore, thin layered covalent organic nanosheets (CONs) were derived from these bulk COFs by the simple liquid phase exfoliation method. These 2D CONs showcase increased luminescence intensity compared to their bulk counterparts (COFs). Notably, TfpBDH-CONs showcase good selectivity and prominent, direct visual detection towards different nitroaromatic analytes over TpBDH-CONs. Quite interestingly, TfpBDH-CONs exhibit a superior {\textquoteleft}{\textquoteleft}turn-on{\textquoteright}{\textquoteright} detection capability for 2,4,6-trinitrophenol (TNP) in the solid state, but conversely, they also show a {\textquoteleft}{\textquoteleft}turn-off{\textquoteright}{\textquoteright} detection in the dispersion state. These findings describe a new approach towards developing an efficient, promising fluorescence chemosensor material for both visual and spectroscopic detection of nitroaromatic compounds with very low [10(-5) (M)] analyte concentrations.

}, issn = {2041-6520}, doi = {10.1039/c5sc00512d}, author = {Das, Gobinda and Biswal, Bishnu P. and Kandambeth, Sharath and Venkatesh, V. and Kaur, Gagandeep and Addicoat, Matthew A. and Heine, Thomas and Verma, Sandeep and Banerjee, Rahul} } @article { ISI:000360934800005, title = {Chemoinformatics approach for building molecular networks from marine organisms}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {7}, year = {2015}, month = {JAN}, pages = {673-684}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, abstract = {

Natural products obtained from marine sources are considered to be a rich and diverse source of potential drugs. In the present work we demonstrate the use of chemoinformatics approach for the design of new molecules inspired by molecules from marine organisms. Accordingly we have assimilated information from two major scientific domains namely chemoinformatics and biodiversity informatics to develop an interactive marine database named MIMMO (Medicinally Important Molecules from Marine Organisms). The database can be queried for species, molecules, scaffolds, drugs, diseases and associated cumulative biological activity spectrum along with links to the literature resources. Molecular informatics analysis of the molecules obtained from MIMMO was performed to study their chemical space. The distinct skeletal features of the biologically active compounds isolated from marine species were identified. Scaffold molecules and species networks were created to identify common scaffolds from marine source and drug space. An analysis of the entire molecular data revealed a unique list of around 2000 molecules from which ten most frequently occurring distinct scaffolds were obtained.

}, keywords = {Chemoinformatics, Drug design, marine, virtual library}, issn = {1386-2073}, doi = {10.2174/1386207318666150703112950}, author = {Karthikeyan, Muthukumarasamy and Nimje, Deepika and Pahujani, Rakhi and Tyagi, Kushal and Bapat, Sanket and Vyas, Renu and Padmakumar, Krishna Pillai} } @article { ISI:000360934400003, title = {ChemScreener: a distributed computing tool for scaffold based virtual screening}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {6}, year = {2015}, month = {JAN}, pages = {544-561}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, abstract = {

In this work we present ChemScreener, a Java-based application to perform virtual library generation combined with virtual screening in a platform-independent distributed computing environment. ChemScreener comprises a scaffold identifier, a distinct scaffold extractor, an interactive virtual library generator as well as a virtual screening module for subsequently selecting putative bioactive molecules. The virtual libraries are annotated with chemophore-, pharmacophore- and toxicophore-based information for compound prioritization. The hits selected can then be further processed using QSAR, docking and other in silico approaches which can all be interfaced within the ChemScreener framework. As a sample application, in this work scaffold selectivity, diversity, connectivity and promiscuity towards six important therapeutic classes have been studied. In order to illustrate the computational power of the application, 55 scaffolds extracted from 161 anti-psychotic compounds were enumerated to produce a virtual library comprising 118 million compounds (17 GB) and annotated with chemophore, pharmacophore and toxicophore based features in a single step which would be non-trivial to perform with many standard software tools today on libraries of this size.

}, keywords = {Scaffold extraction, therapeutic category, virtual library generation, virtual screening}, issn = {1386-2073}, doi = {10.2174/1386207318666150703112242}, author = {Karthikeyan, Muthukumarasamy and Pandit, Deepak and Vyas, Renu} } @article { ISI:000360510700002, title = {Chiral aziridine ring opening: facile synthesis of (R)-modletine and (R)-phenoxybenzamine hydrochloride}, journal = {Tetrahedron Letters}, volume = {56}, number = {38}, year = {2015}, month = {SEP}, pages = {5269-5271}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

A simple and efficient synthesis of chiral drugs (R)-mexiletine 1, an anti-arrhythmic drug and (R)-phenoxybenzamine hydrochloride 2, an anti-hypertensive drug has been described via controlled reductive ring opening of chiral aziridine as a key step. The target compounds 1 and 2 were obtained in overall yields of 34\% and 10.5\%, respectively. (C) 2015 Elsevier Ltd. All rights reserved.

}, keywords = {Aziridine, Mexiletine, Phenoxybenzamine}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2015.07.032}, author = {Viswanadh, N. and Velayudham, R. and Jambu, S. and Sasikumar, M. and Muthukrishnan, Murugan} } @article { ISI:000358250800001, title = {Chromerid genomes reveal the evolutionary path from photosynthetic algae to obligate intracellular parasites}, journal = {Elife}, volume = {4}, year = {2015}, month = {JUL}, pages = {Article Number: e06974}, publisher = {ELIFE SCIENCES PUBLICATIONS LTD}, address = {SHERATON HOUSE, CASTLE PARK, CAMBRIDGE, CB3 0AX, ENGLAND}, abstract = {

The eukaryotic phylum Apicomplexa encompasses thousands of obligate intracellular parasites of humans and animals with immense socio-economic and health impacts. We sequenced nuclear genomes of Chromera velia and Vitrella brassicaformis, free-living non-parasitic photosynthetic algae closely related to apicomplexans. Proteins from key metabolic pathways and from the endomembrane trafficking systems associated with a free-living lifestyle have been progressively and non-randomly lost during adaptation to parasitism. The free-living ancestor contained a broad repertoire of genes many of which were repurposed for parasitic processes, such as extracellular proteins, components of a motility apparatus, and DNA-and RNA-binding protein families. Based on transcriptome analyses across 36 environmental conditions, Chromera orthologs of apicomplexan invasion-related motility genes were co-regulated with genes encoding the flagellar apparatus, supporting the functional contribution of flagella to the evolution of invasion machinery. This study provides insights into how obligate parasites with diverse life strategies arose from a once free-living phototrophic marine alga.

}, issn = {2050-084X}, doi = {10.7554/eLife.06974}, author = {Woo, Yong H. and Ansari, Hifzur and Otto, Thomas D. and Klinger, Christen M. and Kolisko, Martin and Michalek, Jan and Saxena, Alka and Shanmugam, Dhanasekaran and Tayyrov, Annageldi and Veluchamy, Alaguraj and Ali, Shahjahan and Bernal, Axel and del Campo, Javier and Cihlar, Jaromir and Flegontov, Pavel and Gornik, Sebastian G. and Hajduskova, Eva and Horak, Ales and Janouskovec, Jan and Katris, Nicholas J. and Mast, Fred D. and Miranda-Saavedra, Diego and Mourier, Tobias and Naeem, Raeece and Nair, Mridul and Panigrahi, Aswini K. and Rawlings, Neil D. and Padron-Regalado, Eriko and Ramaprasad, Abhinay and Samad, Nadira and Tomcala, Ales and Wilkes, Jon and Neafsey, Daniel E. and Doerig, Christian and Bowler, Chris and Keeling, Patrick J. and Roos, David S. and Dacks, Joel B. and Templeton, Thomas J. and Waller, Ross F. and Lukes, Julius and Obornik, Miroslav and Pain, Arnab} } @article { ISI:000349943000006, title = {Computational study of metal free alcohol dehydrogenation employing frustrated lewis pairs}, journal = {Journal of Organic Chemistry}, volume = {80}, number = {4}, year = {2015}, month = {FEB}, pages = {2081-2091}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The catalysis of acceptorless alcohol dehydrogenation (AAD) is an important area of research. Transition metal-based systems are known to be effective catalysts for this reaction, but developing metal free catalytic systems would lead to highly desirable cheaper and greener alternatives. With this in mind, this computational study investigates design strategies than can lead to metal free frustrated Lewis pairs (FLPs) that can be employed for AAD catalysis. A careful study of 36 different proposed FLP candidates reveals that several new FLPs can be designed from existing, experimentally synthesized FLPs that can rival or be even better than state-of-the-art transition metal-based systems in catalyzing the alcohol dehydrogenation process.

}, issn = {0022-3263}, doi = {10.1021/jo5023052}, author = {Mane, Manoj V. and Rizvi, Masood A. and Vanka, Kumar} } @article { ISI:000360112400004, title = {Concise synthesis of (+/-)-clopidogrel via carboxylation of benzylamine with CO2}, journal = {Synthetic Communications}, volume = {45}, number = {18}, year = {2015}, month = {JUN}, pages = {2099-2105}, publisher = {TAYLOR \& FRANCIS INC}, address = {530 WALNUT STREET, STE 850, PHILADELPHIA, PA 19106 USA}, abstract = {

A concise and efficient synthesis of (+/-)-clopidogrel, an antithrombotic agent, is achieved by inserting CO2 at the benzylic position as the key reaction without using any toxic transition metals. The overall yield of the synthetic process is 38\% and the salient features include operationally simple process chemistry and fewer steps.

}, keywords = {Antithrombatic agent, clopidogrel, CO2 insertion, Plavix}, issn = {0039-7911}, doi = {10.1080/00397911.2015.1061671}, author = {Venkataramasubramanian, V. and Sudalai, Arumugam} } @article { ISI:000363152800005, title = {Core-shell nanoparticles: synthesis and applications in catalysis and electrocatalysis}, journal = {Chemical Society Reviews}, volume = {44}, number = {21}, year = {2015}, month = {AUG}, pages = {7540-7590}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Core-shell nanoparticles (CSNs) are a class of nanostructured materials that have recently received increased attention owing to their interesting properties and broad range of applications in catalysis, biology, materials chemistry and sensors. By rationally tuning the cores as well as the shells of such materials, a range of core-shell nanoparticles can be produced with tailorable properties that can play important roles in various catalytic processes and offer sustainable solutions to current energy problems. Various synthetic methods for preparing different classes of CSNs, including the Stober method, solvothermal method, one-pot synthetic method involving surfactants, etc., are briefly mentioned here. The roles of various classes of CSNs are exemplified for both catalytic and electrocatalytic applications, including oxidation, reduction, coupling reactions, etc.

}, issn = {0306-0012}, doi = {10.1039/c5cs00343a}, author = {Gawande, Manoj B. and Goswami, Anandarup and Asefa, Tewodros and Guo, Huizhang and Biradar, Ankush V. and Peng, Dong-Liang and Zboril, Radek and Varma, Rajender S.} } @article { ISI:000353249500020, title = {Demonstration of synergistic catalysis in Au@Ni bimetallic core-shell nanostructures}, journal = {Journal of Physical Chemistry C}, volume = {119}, number = {15}, year = {2015}, month = {APR}, pages = {8138-8146}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Coreshell bimetallic nanoparticles comprised of gold core and varying nickel shell have been synthesized, and their synergistic effect in catalysis is explored through catalytic hydrogenation of p-nitrophenol and p-nitrothiophenol. A clear evidence for synergism in Au@Ni core-shell nanoparticles having an ultrathin Ni shell (1-2 nm) around a Au core (6-10 nm) resulting in enhanced catalytic activity is observed. The rates observed from a thin nickel shell are higher than monometallic Au or Ni nanoparticles of similar size or with a thicker Ni shell of 6-8 nm.

}, issn = {1932-7447}, doi = {10.1021/jp5128089}, author = {Vysakh, A. B. and Babu, Chinchu Lizen and Vinod, C. P.} } @article { ISI:000360934400007, title = {Design and development of cheminfocloud: an integrated cloud enabled platform for virtual screening}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {6}, year = {2015}, month = {JAN}, pages = {604-619}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, abstract = {

The power of cloud computing and distributed computing has been harnessed to handle vast and heterogeneous data required to be processed in any virtual screening protocol. A cloud computing platorm ChemInfoCloud was built and integrated with several chemoinformatics and bioinformatics tools. The robust engine performs the core chemoinformatics tasks of lead generation, lead optimisation and property prediction in a fast and efficient manner. It has also been provided with some of the bioinformatics functionalities including sequence alignment, active site pose prediction and protein ligand docking. Text mining, NMR chemical shift (1H, 13C) prediction and reaction fingerprint generation modules for efficient lead discovery are also implemented in this platform. We have developed an integrated problem solving cloud environment for virtual screening studies that also provides workflow management, better usability and interaction with end users using container based virtualization, OpenVz.

}, keywords = {Chemoinformatics, cloud computing, machine learning, Molecular docking, OpenVz, sequence alignment, spectra prediction, text mining, virtual screening}, issn = {1386-2073}, doi = {10.2174/1386207318666150703113656}, author = {Karthikeyan, Muthukumarasamy and Pandit, Deepak and Bhavasar, Arvind and Vyas, Renu} } @article { ISI:000360934400001, title = {Design and development of new chemoinformatics tools for virtual screening}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {6}, year = {2015}, month = {JAN}, pages = {526-527}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, issn = {1386-2073}, doi = {10.2174/138620731806150902190608}, author = {Karthikeyan, Muthukumarasamy and Vyas, Renu} } @article { ISI:000364803200005, title = {Design, synthesis, and identification of silicon incorporated oxazolidinone antibiotics with improved brain exposure}, journal = {ACS Medicinal Chemistry Letters}, volume = {6}, number = {11}, year = {2015}, month = {NOV}, pages = {1105-1110}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Therapeutic options for brain infections caused by pathogens with a reduced sensitivity to drugs are limited. Recent reports on the potential use of linezolid in treating brain infections prompted us to design novel compounds around this scaffold. Herein, we describe the design and synthesis of various oxazolidinone antibiotics with the incorporation of silicon. Our findings in preclinical species suggest that silicon incorporation is highly useful in improving brain exposures. Interestingly, three compounds from this series demonstrated up to a 30-fold higher brain/plasma ratio when compared to linezolid thereby indicating their therapeutic potential in brain associated disorders.

}, keywords = {Antibacterial, brain exposure, linezolid, oxazolidinone, sila analogue}, issn = {1948-5875}, doi = {10.1021/acsmedchemlett.5b00213}, author = {Seetharamsingh, B. and Ramesh, Remya and Dange, Santoshkumar S. and Khairnar, Pankaj V. and Singhal, Smita and Upadhyay, Dilip and Veeraraghavan, Sridhar and Viswanadha, Srikant and Vakkalanka, Swaroop and Reddy, D. Srinivasa} } @article { ISI:000358837400009, title = {Development of diagnostic fragment ion library for glycated peptides of human serum albumin: targeted quantification in prediabetic, diabetic, and microalbuminuria plasma by parallel reaction monitoring, SWATH, and MSE}, journal = {Molecular \& Cellular Proteomics}, volume = {14}, number = {8}, year = {2015}, month = {AUG}, pages = {2150-2159}, publisher = {AMER SOC BIOCHEMISTRY MOLECULAR BIOLOGY INC}, address = {9650 ROCKVILLE PIKE, BETHESDA, MD 20814-3996 USA}, abstract = {

Human serum albumin is one of the most abundant plasma proteins that readily undergoes glycation, thus glycated albumin has been suggested as an additional marker for monitoring glycemic status. Hitherto, only Amadori-modified peptides of albumin were quantified. In this study, we report the construction of fragment ion library for Amadori-modified lysine (AML), N(epsilon)-(carboxymethyl) lysine (CML)-, and N(epsilon)-(carboxyethyl) lysine (CEL)-modified peptides of the corresponding synthetically modified albumin using high resolution accurate mass spectrometry (HR/AM). The glycated peptides were manually inspected and validated for their modification. Further, the fragment ion library was used for quantification of glycated peptides of albumin in the context of diabetes. Targeted Sequential Window Acquisition of all THeoretical Mass Spectra (SWATH) analysis in pooled plasma samples of control, prediabetes, diabetes, and microalbuminuria, has led to identification and quantification of 13 glycated peptides comprised of four AML, seven CML, and two CEL modifications, representing nine lysine sites of albumin. Five lysine sites namely K549, K438, K490, K88, and K375, were observed to be highly sensitive for glycation modification as their respective m/z showed maximum fold change and had both AML and CML modifications. Thus, peptides involving these lysine sites could be potential novel markers to assess the degree of glycation in diabetes.

}, issn = {1535-9476}, doi = {10.1074/mcp.M115.050518}, author = {Korwar, Arvind M. and Vannuruswamy, Garikapati and Jagadeeshaprasad, Mashanipalya G. and Jayaramaiah, Ramesha H. and Bhat, Shweta and Regin, Bhaskaran S. and Ramaswamy, Sureshkumar and Giri, Ashok P. and Mohan, Viswanathan and Balasubramanyam, Muthuswamy and Kulkarni, Mahesh J.} } @article { ISI:000345895200048, title = {Effect of Pd and Ce on the enhancement of ethanol vapor response of SnO2 thick films}, journal = {Sensors and Actuators B-Chemical}, volume = {207}, number = {A}, year = {2015}, month = {FEB}, pages = {383-390}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

The undoped SnO2 and 4 wt\% Ce-doped SnO2 were successfully synthesized by a facile co-precipitation route. The ternary systems were prepared by Pd-loading (0.5, 1.5 and 3.0 wt\%) on the 4 wt\% Ce-doped SnO2 nanoparticles. The structure and morphology of the nanocrystalline powders were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy techniques. The nanocrystalline powders were screen printed on the alumina substrates to form thick films to investigate their gas response properties. The gas response studies reveal that 4 wt\% Ce-doped SnO2 with the loading of 3.0 wt\% Pd exhibits high response (88\%) towards ethanol (100 ppm) at an operating temperature of 250 degrees C with quick response (6 s) and rapid recovery (20 s). The high ethanol vapor response at lower operating temperature of this sensor is attributed to the spill-over mechanism of Pd particles present on the SnO2 surface and enhancement in alkalescence of SnO2 due to Ce-doping. (C) 2014 Elsevier B.V. All rights reserved.

}, keywords = {Ce-doped tin oxide, Gas sensor, Semiconductor, Thick film}, issn = {0925-4005}, doi = {10.1016/j.snb.2014.10.021}, author = {Bagal, L. K. and Patil, J. Y. and Vaishampayan, M. V. and Mulla, Imtiaz S. and Suryavanshi, S. S.} } @proceedings {43018, title = {Efficacy of food preservatives and volatile compounds in the control of ochratoxin a production by penicillium species}, volume = {85}, year = {2015}, month = {MAR}, abstract = {

In the present investigation different volatile compounds and food preservatives were tested for their efficiency in the control of growth and ochratoxin A (OTA) production by Penicillium verrucosum and Penicillium nordicum. Volatiles such as phenols and formic acid which have no residual effect were proved to be effective in checking the growth and OTA production by both the species of Penicillium under study. Vapours of phenols and formic acid significantly inhibited OTA produced by P. verrucosum, while aniline and toluene inhibited the OTA production by P. nordicum to a significant level. A positive correlation coefficient was observed between the growth and toxin production by P. verrucosum (0.55) and P. nordicum (0.66) against different volatile compounds tried. Among food preservatives, sodium acetate and sodium metabisulphate were responsible for total inhibition of OTA production by P. verrucosum at 150 lg/ml concentration. P. nordicum proved to be comparatively more resistant to these substances than P. verrucosum. In conclusion of present investigation, phenol, formic acid, amyl alcohol, propionic acid, sodium acetate and sodium metabisulphate were found to be effective in checking the growth and OTA production by both the species of Penicillium under investigation, and can be exploited in protecting the poultry feed from unwanted mould growth and mycotoxin production.

}, doi = {10.1007/s40011-015-0513-1}, author = {Vankudoth, Koteswara Rao and Rao, K. Narasimha and Sivadevuni, Girisham and Reddy, S. M.} } @article { ISI:000352546100012, title = {Efficient access to enantiopure 1,3-disubstituted isoindolines from selective catalytic fragmentation of an original desymmetrized rigid overbred template}, journal = {Organic \& Biomolecular Chemistry}, volume = {13}, number = {15}, year = {2015}, month = {MAR}, pages = {4438-4448}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

An efficient and scalable synthesis of various enantiopure 1,3-disubstituted isoindolines is reported. The base catalyzed nucleophilic fragmentation of a rigid overbred template is established with various substrates to afford the corresponding 1,3-disubstituted isoindoline ester, amide, thioate, 1,3-amino alcohol and isoindolylcarboxylic acid. The crucial rigid overbred template is synthesized in an optically pure form in multigram scale by asymmetric desymmetrization of the corresponding meso compound.

}, issn = {1477-0520}, doi = {10.1039/c5ob00229j}, author = {Pandey, Ganesh and Varkhedkar, Rajesh and Tiwari, Divya} } @article { ISI:000357587500011, title = {Efficient shoots regeneration and genetic transformation of bacopa monniera}, journal = {Physiology and Molecular Biology of Plants}, volume = {21}, number = {2}, year = {2015}, month = {APR}, pages = {261-267}, publisher = {SPRINGER}, type = {Article}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Bacopa monniera is an important source of metabolites with pharmaceutical value. It has been regarded as a valuable medicinal plant and its entire commercial requirement is met from wild natural population. Recently, metabolic engineering has emerged as an important solution for sustained supply of assured and quality raw material for the production of active principles. Present report describes efficient in vitro multiplication and transformation method for geneticmanipulation of this species. MS medium supplemented with 2 mgl(-1) BA and 0.2 mgl(-1) IAA was found optimum for maximum shoot regeneration (98.33 \%) from in vitro leaves with 2-3 longitudinal cuts. Agrobacterium tumefaciens-mediated transformation method was used for generating transgenic B. monniera plants. Putative transformants were confirmed by GUS assay and PCR based confirmation of hptII gene. DNA blot analysis showed single copy insertion of transgene cassette. An average of 87.5 \% of the regenerated shoots were found PCR positive for hptII gene and GUS activity was detected in leaves of transgenic shoots at a frequency of 82.5 \% The efficient multiple shoots regeneration system described herein may help in mass production of B. monniera plant. Also, the high frequency transformation protocol described here can be used for genetic engineering of B. monniera for enhancement of its pharmaceutically important metabolites.

}, issn = {0971-5894}, doi = {10.1007/s12298-015-0290-6}, author = {Kumari, Uma and Vishwakarma, Rishi K. and Gupta, Neha and Ruby and Shirgurkar, M. V. and Khan, Bashir Mohammad} } @article { ISI:000354238700002, title = {Electron attachment to DNA and RNA nucleobases: an EOMCC investigation}, journal = {International Journal of Quantum Chemistry}, volume = {115}, number = {12}, year = {2015}, month = {JUN}, pages = {753-764}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

We report a benchmark theoretical investigation of both vertical and adiabatic electron affinities of DNA and RNA nucleobases: adenine, guanine, cytosine, thymine, and uracil using equation of motion coupled cluster method. The vertical electron affinity (VEA) values of the first five states of the DNA and RNA nucleobases are computed. It is observed that the first electron attached state is energetically accessible in gas phase. Furthermore, an analysis of the natural orbitals exhibits that the first electron attached states of uracil and thymine are valence-bound in nature and undergo significant structural changes on attachment of an extra electron, which reflects in the deviation of the adiabatic electron affinity (AEA) than that of the vertical ones. Conversely, the first electron attached states of cytosine, adenine, and guanine are in the category of dipole-bound anions. Their structure, by and large, remain unaffected on attachment of an extra electron, which is evident from the observed small difference between the AEA and VEA values. VEA and AEA values of all the DNA and RNA nucleobases are found to be negative, which implies that the first electron attached states are not stable rather quasi bound. The results of all previous theoretical calculations are out of track and shows large deviation with respect to the experimentally measured values, whereas, our results are found to be in good agreement. Therefore, our computed values can be used as a reliable standard to calibrate new theoretical methods. (c) 2015 Wiley Periodicals, Inc.

}, keywords = {DNA-RNA bases, electron affinity, EOMCC}, issn = {0020-7608}, doi = {10.1002/qua.24892}, author = {Dutta, Achintya Kumar and Sengupta, Turbasu and Vaval, Nayana and Pal, Sourav} } @article { ISI:000355354100007, title = {Enantioselective synthesis of guggultetrol and D-ribo-phytosphingosine tetraacetate via L-proline catalyzed sequential alpha-aminooxylation/Horner-Wardsworth-Emmons olefination-Sharpless asymmetric dihydroxylation strategy}, journal = {Tetrahedron-Asymmetry}, volume = {26}, number = {10-11}, year = {2015}, month = {MAY}, pages = {571-576}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

An efficient enantioselective synthesis of two bioactive molecules, that is, guggultetrol and D-ribo-phytosphingosine, is described with high enantioselectivity (\>98\% ee) starting from commercially available 1-hexadecanol. The synthesis comprises organocatalyzed sequential alpha-aminooxylation of an aldehyde followed by Horner-Wardsworth-Emmons olefination and Sharp less asymmetric dihydroxylation as the key chiral inducing steps. For both syntheses, gamma-hydroxy-alpha,beta-unsaturated ester serves as the common intermediate obtained from proline catalysis. (C) 2015 Elsevier Ltd. All rights reserved.

}, issn = {0957-4166}, doi = {10.1016/j.tetasy.2015.04.004}, author = {Venkataramasubramanian, V. and Kumar, B. Senthil and Sudalai, Arumugam} } @article { ISI:000365220100089, title = {Ene-nucleic acids: a different paradigm to DNA chemistry}, journal = {RSC Advances}, volume = {5}, number = {118}, year = {2015}, month = {NOV}, pages = {97824-97830}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Acyclic prochiral nucleic acids such as FNA, UNA, GNA and cyclic chiral TNA are all considered as precursors of DNA and RNA in the chemical etiology of nucleic acids. The chemical reasoning would suggest that unsaturated precursors with constrained flexibility and selectivity based on cis/trans isomers could be the missing link between the prochiral-acyclic and chiral-cyclic structures mentioned above. We find that ene-nucleic acids derived from an isoprenoid skeleton possess requisite flexibility and rigidity while forming stable duplex structures with complementary DNA and RNA.

}, issn = {2046-2069}, doi = {10.1039/c5ra15673d}, author = {Varada, Manojkumar and Erande, Namrata D. and Kumar, Vaijayanti A.} } @article { ISI:000356201700008, title = {EOMIP-CCSD(2)*: an efficient method for the calculation of ionization potentials}, journal = {Journal of Chemical Theory and Computation}, volume = {11}, number = {6}, year = {2015}, month = {JUN}, pages = {2461-2472}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

A new approximation within the domain of EOMIP-CC method is proposed. The proposed scheme is based on the perturbative truncation of the similarity transformed effective Hamiltonian matrix. We call it the EOMIP-CCSD(2)* method, which scales as noniterative N-6 and its storage requirement is very less, compared to the conventional EOMIP-CCSD method. The existing EOMIP-CCSD(2) method has a tendency to overestimate the ionization potential (IP) values. On the other hand, our new strategy corrects for the problem of such an overestimation, which is evident from the excellent agreement achieved with the experimental values. Furthermore, not only the ionization potential but also geometry and IR frequencies of problematic double radicals are estimated correctly, and the results are comparable to the CCSD(T) method, obviously at lesser computational cost. The EOMIP-CCSD(2)* method works even for the core ionization and satellite IP, where the earlier EOMIP-CCSD(2) approximation dramatically fails.

}, issn = {1549-9618}, doi = {10.1021/ct500927h}, author = {Dutta, Achintya Kumar and Vaval, Nayana and Pal, Sourav} } @article { ISI:000361120000056, title = {Evaluation of imidazolium-based ionic liquids towards vermicidal activity: in vitro \& in silico studies}, journal = {RSC Advances}, volume = {5}, number = {92}, year = {2015}, month = {AUG}, pages = {75415-75424}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

A series of six different ionic liquids (ILs) of the kind 1-alkyl-3-methylimidazolium bromide/hydroxide (IL-Br and IL-OH) tailored with different N-alkyl side chains (ethyl, butyl, octyl) were synthesized and evaluated for their vermicidal activity against the Indian earthworm, Pheretima posthuma. The percentage of paralysis and mortality of earthworms against ILs were recorded in a dose dependent (at different concentrations 2, 4, 8 and 16 mM) and time dependent manner. The ILs with hydroxide as the counter anion (IL-OH) showed higher vermicidal activity compared to their bromide counterparts (IL-Br). Moreover, the ILs with the longest alkyl chain (octyl) were observed to have significant vermicidal activity compared to the rest (ethyl and butyl) as well as the standard drug, Albendazole. Furthermore, theoretical modeling was carried out to visualize the preferential docking positions of these ILs into the active site of beta-tubulin. Fascinatingly, it was found that the ILs with longest alkyl side chain showed remarkable vermicidal activity compared to the rest, and the molecular docking studies not only validated the experimental results, but also showed per-residue interaction analysis between the ILs and the different components of beta-tubulin.

}, issn = {2046-2069}, doi = {10.1039/c5ra13469b}, author = {Charan, K. T. Prabhu and Ranjan, Prabodh and Manojkumar, Kasina and Pothanagandhi, Nellepalli and Jha, Prakash C. and Khedkar, Vijay M. and Sivaramakrishna, Akella and Vijayakrishna, Kari} } @article { ISI:000361075900038, title = {Exiguobacterium enclense sp nov., isolated from sediment}, journal = {International Journal of Systematic and Evolutionary Microbiology}, volume = {65}, number = {5}, year = {2015}, month = {MAY}, pages = {1611-1616}, publisher = {SOC GENERAL MICROBIOLOGY}, address = {MARLBOROUGH HOUSE, BASINGSTOKE RD, SPENCERS WOODS, READING RG7 1AG, BERKS, ENGLAND}, abstract = {

A Gram-stain-positive bacterium, designated strain NIO-1109(T), was isolated from a marine sediment sample from Chorao Island, Goa, India. Phenotypic and chemotaxonomic characteristics and data from phylogenetic analysis based on 16S rRNA gene sequences indicated that strain NIO-1109(T) was related to the genus Exiguobacterium. Strain NIO-1109(T) exhibited \>98.0\% 16S rRNA gene sequence similarity with respect to Exiguobacterium indicum HHS 31(T) (99.5\%) and Exiguobacterium acetylicum NCIMB 9889(T) (99.1 \%); the type strains of other species showed \<98\% similarity. Levels of DNA DNA relatedness between strain NIO-1109(T) and E. acetylicum DSM 20416(T) and E indicum LMG 23471(T) were less than 70\% (33.0 +/- 2.0 and 37 +/- 32\%, respectively). Strain NIO-1109(T) also differed from these two closely related species in a number of phenotypic traits. Based on phenotypic, chemotaxonomic and phylogenetic data, strain NIO-1109(T) is considered to represent a novel species of the genus Exiguobacterium, for which the name Exiguobacterium enclense sp. nov. is proposed. The type strain is NIO-1109(T) (=NCIM 5457(T)= DSM 25128(T)=CCTCC AB 2011124(T)).

}, issn = {1466-5026}, doi = {10.1099/ijs.0.000149}, author = {Dastager, Syed Gulam and Mawlankar, Rahul R. and Sonalkar, Vidya V. and Thorat, Meghana N. and Mual, Poonam and Verma, Ashish and Krishnamurthi, Srinivasan and Tang, Shan-Kun and Li, Wen-Jun} } @article { ISI:000363839500017, title = {Exploring microstructural changes in structural analogues of ibuprofen-hosted in situ gelling system and its influence on pharmaceutical performance}, journal = {AAPS Pharmscitech}, volume = {16}, number = {5}, year = {2015}, month = {OCT}, pages = {1153-1159}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

The present work explores inner structuration of in situ gelling system consisting of glyceryl monooleate (GMO) and oleic acid (OA). The system under study involves investigation of microstructural changes which are believed to govern the pharmaceutical performance of final formulation. The changes which are often termed mesophasic transformation were analysed by small angle Xray scattering (SAXS), differential scanning calorimetry (DSC), rheology and plane polarised light (PPL) microscopy. The current work revealed transformation of blank system from W/O emulsion to reverse hexagonal structure upon addition of structural analogues of ibuprofen. Such transformations are believed to occur due to increased hydrophobic volume within system as probed by SAXS analysis. The findings of SAXS studies were well supported by DSC, rheology and PPL microscopy. The study established inverse relationship between log P value of structural analogues of ibuprofen and the degree of binding of water molecules to surfactant chains. Such relationship had pronounced effect on sol-gel transformation process. The prepared in situ gelling system showed sustained drug release which followed Higuchi model.

}, keywords = {flurbiprofen, hexagonal phase, ibuprofen, ketoprofen, liquid crystal, sustained drug release}, issn = {1530-9932}, doi = {10.1208/s12249-015-0308-y}, author = {Patil, Sharvil S. and Venugopal, Edakkal and Bhat, Suresh K. and Mahadik, Kakasaheb R. and Paradkar, Anant R.} } @article { ISI:000351969900008, title = {First naphthosemiquinone complex of K+ with vitamin K3 analog: experiment and density functional theory}, journal = {Journal of Molecular Structure}, volume = {1088}, year = {2015}, month = {MAY}, pages = {56-63}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Synthesis and characterization of potassium complex of 2-hydroxy-3-methyl-1,4-naphthoquinone (phthiocol), the vitamin K3 analog, has been carried out using FT-IR, UV-Vis, H-1 and C-13 NMR, EPR, cyclic voltammetry and single crystal X-ray diffraction experiments combined with the density functional theory. It has been observed that naphthosemiquinone binds to two K+ ions extending the polymeric chain through bridging oxygens O(2) and O(3). The crystal network possesses hydrogen bonding interactions from coordinated water molecules showing water channels along the c-axis. C-13 NMR spectra revealed that the complexation of phthiocol with potassium ion engenders deshielding of C(2) signals, which appear at delta = similar to 14.6 ppm whereas those of C(3) exhibit up-field signals near delta similar to 6.9 ppm. These inferences are supported by the M06-2x based density functional theory. Electrochemical experiments further suggest that reduction of naphthosemiquinone results in only a cathodic peak from catechol. A triplet state arising from interactions between neighboring phthiocol anion lead to a half field signal at g = 4.1 in the polycrystalline X-band EPR spectra at 133 K. (C) 2015 Elsevier B.V. All rights reserved.

}, keywords = {C-13 NMR, DFT, hydrogen bonding, Naphthosemiquinone, Phthiocol, Vitamin K3}, issn = {0022-2860}, doi = {10.1016/j.molstruc.2015.01.053}, author = {Kathawate, Laxmi and Gejji, Shridhar P. and Yeole, Sachin D. and Verma, Prakash L. and Puranik, Vedavati G. and Salunke-Gawali, Sunita} } @article { ISI:000365148500002, title = {Gelation landscape engineering using a multi-reaction supramolecular hydrogelator system}, journal = {Journal of the American Chemical Society}, volume = {137}, number = {45}, year = {2015}, month = {NOV}, pages = {14236-14239}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Simultaneous control of the kinetics and thermodynamics of two different types of covalent chemistry allows pathway selectivity in the formation of hydrogelating molecules from a complex reaction network. This can lead to a range of hydrogel materials with vastly different properties, starting from a set of simple starting compounds and reaction conditions. Chemical reaction between a trialdehyde and the tuberculosis drug isoniazid can form one, two, or three hydrazone connectivity products, meaning kinetic gelation pathways can be addressed. Simultaneously, thermodynamics control the formation of either a keto or an enol tautomer of the products, again resulting in vastly different materials. Overall, this shows that careful navigation of a reaction landscape using both kinetic and thermodynamic selectivity can be used to control material selection from a complex reaction network.

}, issn = {0002-7863}, doi = {10.1021/jacs.5b06988}, author = {Foster, Jamie S. and Zurek, Justyna M. and Almeida, Nuno M. S. and Hendriksen, Wouter E. and le Sage, Vincent A. A. and Lakshminarayanan, Vasudevan and Thompson, Amber L. and Banerjee, Rahul and Eelkema, Rienk and Mulvana, Helen and Paterson, Martin J. and van Esch, Jan H. and Lloyd, Gareth O.} } @article { ISI:000364264800011, title = {Genetic programming based quantitative structure-retention relationships for the prediction of Kovats retention indices}, journal = {Journal of Chromatography A}, volume = {1420}, year = {2015}, month = {NOV}, pages = {98-109}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The development of quantitative structure-retention relationships (QSRR) aims at constructing an appropriate linear/nonlinear model for the prediction of the retention behavior (such as Kovats retention index) of a solute on a chromatographic column. Commonly, multi-linear regression and artificial neural networks are used in the QSRR development in the gas chromatography (GC). In this study, an artificial intelligence based data-driven modeling formalism, namely genetic programming (GP), has been introduced for the development of quantitative structure based models predicting Kovats retention indices (KRI). The novelty of the GP formalism is that given an example dataset, it searches and optimizes both the form (structure) and the parameters of an appropriate linear/nonlinear data-fitting model. Thus, it is not necessary to pre-specify the form of the data-fitting model in the GP-based modeling. These models are also less complex, simple to understand, and easy to deploy. The effectiveness of GP in constructing QSRRs has been demonstrated by developing models predicting KRIs of light hydrocarbons (case study-I) and adamantane derivatives (case study-II). In each case study, two-, three- and four-descriptor models have been developed using the KRI data available in the literature. The results of these studies clearly indicate that the GP-based models possess an excellent KRI prediction accuracy and generalization capability. Specifically, the best performing four-descriptor models in both the case studies have yielded high (\>0.9) values of the coefficient of determination (R-2) and low values of root mean squared error (RMSE) and mean absolute percent error (MAPE) for training, test and validation set data. The characteristic feature of this study is that it introduces a practical and an effective GP-based method for developing QSRRs in gas chromatography that can be gainfully utilized for developing other types of data-driven models in chromatography science. (C) 2015 Elsevier B.V. All rights reserved.

}, keywords = {Artificial intelligence, Gas chromatography, genetic programming, Kovats retention index, Molecular descriptors, Quantitative structure-retention relationships}, issn = {0021-9673}, doi = {10.1016/j.chroma.2015.09.086}, author = {Goel, Purva and Bapat, Sanket and Vyas, Renu and Tambe, Amruta and Tambe, Sanjeev S.} } @article { ISI:000359962900040, title = {Glycine-linked nucleoside-beta-amino acids: polyamide analogues of nucleic acids}, journal = {Bioconjugate Chemistry}, volume = {26}, number = {8}, year = {2015}, month = {AUG}, pages = {1737-1742}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

3{\textquoteright}-5{\textquoteright}-Deoxyribose-sugar-phoshate backbone in DNA is completely replaced by 2{\textquoteright}-deoxyribonucleoside-based beta-amino acids interlinked by glycine to create uncharged polyamide DNA with 3{\textquoteright}-5{\textquoteright}-directionality. These oligomers as conjugates of alpha-amino acids and nucleoside-beta-amino acids bind strongly and sequence-specifically only to the antiparallel complementary RNA and DNA.

}, issn = {1043-1802}, doi = {10.1021/acs.bioconjchem.5b00296}, author = {Banerjee, Anjan and Seema Bagmare and Varada, Manojkumar and Kumar, Vaijayanti A.} } @article {42859, title = {Gold(I)/chiral br{\o}nsted acid catalyzed enantioselective hydroamination-hydroarylation of alkynes: effect of remote hydroxyl group in the reactivity and enantioselectivity}, journal = {Chemistry - A European Journal}, volume = {21}, year = {2015}, month = {JAN}, pages = {975-979}, doi = {10.1002/chem.201405061}, author = {Shinde, Valmik S. and Mane, Manoj V. and Vanka, Kumar and Mallick, Arijit and Patil, Nitin T.} } @article { ISI:000355925900027, title = {Highly efficient regioselective synthesis of pyrroles via a tandem enamine formation-Michael addition-cyclization sequence under catalyst- and solvent-free conditions}, journal = {Green Chemistry}, volume = {17}, number = {6}, year = {2015}, month = {APR}, pages = {3415-3423}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

A convenient catalyst-free, three-component procedure was developed for the synthesis of tetrasubstituted pyrroles under solvent-free conditions and in green solvents glycerol, PEG-200 and water. A sequential enamine-formation, Michael addition and intramolecular cyclization of primary amines, 1,3-dicarbonyl compounds and isatin-derived Michael acceptors afforded 3-(1H-pyrrol-3-yl)indolin-2-ones in excellent yields. In this simple one-pot transformation the requirement of column chromatography purification of the products was completely avoided. Besides, the method is highly environmentally benign and atom-economical, and the only side product of this reaction was two molecules of water. A comparative study for the four developed conditions showed that the solvent-free conditions were superior regardless of the nature of the starting materials, and the green solvents were effective for alkyl and benzylamines affording higher yields compared to arylamines. The preliminary in vitro cytotoxic studies of a representative compound against Ehrlich{\textquoteright}s ascites carcinoma (EAC) tumor cells showed significant activity with a CTC50 value of 15.64 mu M.

}, issn = {1463-9262}, doi = {10.1039/c5gc00365b}, author = {Vivekanand, Thavaraj and Vinoth, Perumal and Agieshkumar, B. and Sampath, Natarajan and Sudalai, Arumugam and Menendez, Carlos and Sridharan, Vellaisamy} } @article { ISI:000366006300012, title = {Hydrogen bond and ligand dissociation dynamics in fluoride sensing of Re(I)-polypyridyl complex}, journal = {Journal of Physical Chemistry B}, volume = {119}, number = {47}, year = {2015}, month = {NOV}, pages = {14952-14958}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Hydrogen bonding interaction plays an essential role in the early phases of molecular recognition and colorimetric sensing of various anions in aprotic media. In this work, the host-guest interaction between fac-[Re(CO)(3)Cl(L)] with L = 4-([2,2{\textquoteright}-bipyridin]-4-yl)phenol and fluoride ions is investigated for the hydrogen bond dynamics and the changing local coordination environment. The stoichiometric studies using H-1 NMR and ESI-MS spectroscopies have shown that proton transfer in the H-bonded phenol-fluoride complex activates the dissociation of the CO ligand in the Re(I) center. The phenol-to-phenolate conversion during formation of HF2- ion induces nucleophilic lability of the CO ligand which is probed by intraligand charge transfer (ILCT) and ligand-to-metal charge transfer (LMCT) transitions in transient absorption spectroscopy. After photoexcitation, phenol-phenoxide conversion rapidly equilibrates in 280 fs time scale and the ensuing excited state [ReII(bpy(center dot-)-phenolate(-))(CO)(3)Cl]* undergoes CO dissociation in the ultrafast time scale of similar to 3 ps. A concerted mechanism of hydrogen cleavage and coordination change is established in anion sensing studies of the rhenium complex.

}, issn = {1520-6106}, doi = {10.1021/acs.jpcb.5b09227}, author = {Verma, Sandeep and Aute, Sunil and Das, Amitava and Ghosh, Hirendra N.} } @article { ISI:000358370700007, title = {Identifying solid luminogens through gold-catalysed intramolecular hydroarylation of alkynes}, journal = {European Journal of Organic Chemistry}, number = {22}, year = {2015}, month = {AUG}, pages = {4860-4867}, publisher = {WILEY-V C H VERLAG GMBH}, address = {POSTFACH 101161, 69451 WEINHEIM, GERMANY}, abstract = {

The identification of a new class of luminogens based on pyrrolo-quinoxaline embedded coumarin (PQC) structures is reported. The reaction relies on the gold-catalyzed hydroarylation reaction of appropriately substituted aryl alkynoates that produces molecules that exhibit solvatochromism and aggregation-induced emission enhancement (AIEE) phenomena. The application of PQCs for live cell imaging has also been demonstrated.

}, keywords = {Cell imaging, Dyes/pigments, fluorescence, Gold, Luminescence, Solvatochromism}, issn = {1434-193X}, doi = {10.1002/ejoc.201500503}, author = {Shaikh, Aslam C. and Shalini, S. and Vaidhyanathan, Ramanathan and Mane, Manoj V. and Barui, Ayan Kumar and Patra, Chitta Ranjan and Venkatesh, Yeduru and Bangal, Prakriti Ranjan and Patil, Nitin T.} } @article { ISI:000352195500001, title = {Implementation of the Z-vector method in the relativistic-coupled-cluster framework to calculate first-order energy derivatives: Application to the SrF molecule}, journal = {Physical Review A}, volume = {91}, number = {3}, year = {2015}, month = {MAR}, pages = {030503}, publisher = {AMER PHYSICAL SOC}, address = {ONE PHYSICS ELLIPSE, COLLEGE PK, MD 20740-3844 USA}, abstract = {

The molecular dipole moment and magnetic hyperfine-structure constant demand an accurate wave function far from the nucleus and in the near nuclear region, respectively. We, therefore, employ the so-called Z-vector method in the domain of relativistic-coupled-cluster theory to calculate the first-order property of molecular systems in their open-shell ground-state configuration. The implemented method is applied to calculate the molecular dipole moment and parallel component of the magnetic hyperfine-structure constant of the SrF molecule. The results of our calculation are compared with the experimental and other available theoretically calculated values. We are successful in achieving good accordance with the experimental results. The result of our calculation of the molecular dipole moment is in the accuracy of similar to 0.5\%, which is clearly an improvement over the previous calculation based on the expectation value method in the four-component coupled-cluster framework [V. S. Prasannaa et al., Phys. Rev. A 90, 052507 (2014)]. Thus, it can be inferred that the Z-vector method can provide an accurate wave function in both the near and far nuclear region, which is evident from our calculated results.

}, issn = {2469-9926}, doi = {10.1103/PhysRevA.91.030503}, author = {Sasmal, Sudip and Pathak, Himadri and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article { ISI:000351354000028, title = {Investigation of antiglycation activity of isoprenaline}, journal = {RSC Advances}, volume = {5}, number = {32}, year = {2015}, month = {MAR}, pages = {25051-25058}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Advanced glycation end products (AGEs) are implicated in pathogenesis of diabetes and its complications. In this study, we report the ability of isoprenaline to inhibit the AGE modification of protein by fluorescence spectroscopy and western blotting. Isoprenaline was more effective in inhibiting AGE modification than aminoguanidine, a well known glycation inhibitor. Further, we show that isoprenaline inhibits at Amadori product formation during glycation reaction by various techniques such as MALDI-TOF-MS, LC-MS/MS, and fructosamine assay. Mass spectrometric analysis of the glycation reaction mixture incubated with isoprenaline suggested that it forms adducts with glucose and thus inhibits glycation. The finding of the additional property of isoprenaline of inhibiting glycation suggests that it is a potential candidate for drug repositioning for the treatment of diabetes and its complications, as it is an FDA approved drug.

}, issn = {2046-2069}, doi = {10.1039/c5ra01723h}, author = {Kolekar, Yogesh M. and Vannuruswamy, Garikapati and Bansode, Sneha B. and Santhakumari, B. and Thulasiram, Hirekodathakallu V. and Kulkarni, Mahesh J.} } @article {42627, title = {Lifetime of inner-shell hole states of Ar (2p) and Kr (3d) using equation-of-motion coupled cluster method}, journal = {Journal of Chemical Physics}, volume = {143}, year = {2015}, month = {JUL}, pages = {Article No. 024305}, doi = {10.1063/1.4926396}, author = {Ghosh, Aryya and Pal, Sourav and Vaval, Nayana} } @article { ISI:000368224600009, title = {Lithium-assisted proton conduction at 150 degrees C in a microporous triazine-phenol polymer}, journal = {Advanced Materials Interfaces}, volume = {2}, number = {16}, year = {2015}, month = {NOV}, pages = {1500301}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, keywords = {conduction, hydrophobic polar frameworks, lithiated polymers, proton conduction, triazine-phenol polymers}, issn = {2196-7350}, doi = {10.1002/admi.201500301}, author = {Nandi, Shyamapada and Dhavale, Vishal M. and Shalini, Sorout and Werner-Zwanziger, Ulrike and Singh, Harpreet and Kurungot, Sreekumar and Vaidhyanathan, Ramanathan} } @article { ISI:000357705800012, title = {Mechanism of oxygen atom transfer from Fe-V(O) to olefins at room temperature}, journal = {Inorganic Chemistry}, volume = {54}, number = {13}, year = {2015}, month = {JUL}, pages = {6112-6121}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

In biological oxidations, the intermediate Fe-V(0)(OH) has been proposed to be the active species for catalyzing the epoxidation of alkenes by nonheme iron complexes. However, no study has been reported yet that elucidates the mechanism of direct O-atom transfer during the reaction of Fe-V(0) with alkenes to form the corresponding epoxide. For the first time, we study the mechanism of O-atom transfer to alkenes using the Fe-V(0) complex of biuret-modified Fe-TAML at room temperature. The second-order rate constant (k(2)) for the reaction of different alkenes with Fe-V(0) was determined under single-turnover conditions. An 8000-fold rate difference was found between electron-rich (4-methoxystyrene; k(2) = 216 M-1 s(-1)) and electron-deficient (methyl transcinnamate; k(2) = 0.03 M-1 s(-1)) substrates. This rate difference indicates the electrophilic character of Fe-V(0). The use of cis-stilbene as a mechanistic probe leads to the formation of both cis- and trans-stilbene epoxides (73:27). This suggests the formation of a radical intermediate, which would allow C-C bond rotation to yield both stereoisomers of stilbene-epoxide. Additionally, a Hammett rho value of -0.56 was obtained for the para-substituted styrene derivatives. Detailed DFT calculations show that the reaction proceeds via a two-step process through a doublet spin surface. Finally, using biuret-modified Fe-TAML as the catalyst and NaOCl as the oxidant under catalytic conditions epoxide was formed with modest yields and turnover numbers.

}, issn = {0020-1669}, doi = {10.1021/ic503053q}, author = {Singh, Kundan K. and Tiwari, Mrityunjay K. and Dhar, Basab B. and Vanka, Kumar and Sen Gupta, Sayam} } @article { ISI:000360934400006, title = {MegaMiner: a tool for lead identification through text mining using chemoinformatics tools and cloud computing environment}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {6}, year = {2015}, month = {JAN}, pages = {591-603}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, abstract = {

Virtual screening is an indispensable tool to cope with the massive amount of data being tossed by the high throughput omics technologies. With the objective of enhancing the automation capability of virtual screening process a robust portal termed MegaMiner has been built using the cloud computing platform wherein the user submits a text query and directly accesses the proposed lead molecules along with their drug-like, lead-like and docking scores. Textual chemical structural data representation is fraught with ambiguity in the absence of a global identifier. We have used a combination of statistical models, chemical dictionary and regular expression for building a disease specific dictionary. To demonstrate the effectiveness of this approach, a case study on malaria has been carried out in the present work. MegaMiner offered superior results compared to other text mining search engines, as established by F score analysis. A single query term {\textquoteleft}malaria{\textquoteright} in the portlet led to retrieval of related PubMed records, protein classes, drug classes and 8000 scaffolds which were internally processed and filtered to suggest new molecules as potential anti-malarials. The results obtained were validated by docking the virtual molecules into relevant protein targets. It is hoped that MegaMiner will serve as an indispensable tool for not only identifying hidden relationships between various biological and chemical entities but also for building better corpus and ontologies.

}, keywords = {Chemoinformatics, cloud computing, malaria, text mining, virtual screening}, issn = {1386-2073}, doi = {10.2174/1386207318666150703113525}, author = {Karthikeyan, Muthukumarasamy and Pandit, Yogesh and Pandit, Deepak and Vyas, Renu} } @article { ISI:000360873600007, title = {Microbacterium enclense sp nov., isolated from sediment sample}, journal = {International Journal of Systematic and Evolutionary Microbiology}, volume = {65}, number = {7}, year = {2015}, month = {JUL}, pages = {2064-2070}, publisher = {SOC GENERAL MICROBIOLOGY}, address = {MARLBOROUGH HOUSE, BASINGSTOKE RD, SPENCERS WOODS, READING RG7 1AG, BERKS, ENGLAND}, abstract = {

A novel bacterium (strain NIO-1002(T)) belonging to the genus Microbacterium was isolated from a marine sediment sample in Chorao Island, Goa Province, India. Its morphology, physiology, biochemical features and 16S rRNA gene sequence were characterized. Cells of this strain were Gram-stain-positive, non-motile, non-spore-forming rods that formed yellow-pigmented colonies. It grew in 0-12 \% (w/v) NaCl and at 25-37 degrees C, with optimal growth at 30 degrees C. Phylogenetic analysis based on 16S rRNA gene sequences indicated that strain NIO-1002(T) is associated with members of the genus Microbacterium, with highest sequence similarity with Microbacterium hominis CIP 105731(T) (98.1\%) and Microbacterium testaceum KCTC 9103(T) (98.0 \%). Within the phylogenetic tree, this novel strain shared a branching point with M. hominis CIP 105731(T). The DNA G+C content was 66.5 mol\% and DNA DNA hybridization relatedness between NI-1002(T), M. hominis CIP 105731(T) and M. testaceum KCTC 9103(T) was 39.0 +/- 2.0 \% and 41.0 +/- 2.0 \%, respectively. The major fatty acids were ai-C-15:0, i-C-16:0 and al-C-17:0 and the diamino acid in the cell-wall peptidoglycan of NIO-1002(T) was lysine. Data obtained from DNA-DNA hybridization and chemotaxonomic phenotypic analysis support the conclusion that strain NIO-1002(T) represents a novel species within the genus Microbacterium. The name Microbacterium enclense sp. nov. is proposed, with NIO-1002(T) (=NCIM 5454(T)=DSM 25125(T)=CCTCC AB 2011120(T)) as the type strain.

}, issn = {1466-5026}, doi = {10.1099/ijs.0.000221}, author = {Mawlankar, Rahul R. and Mual, Poonam and Sonalkar, Vidya V. and Thorat, Meghana N. and Verma, Ashish and Srinivasan, Krishnamurthi and Dastager, Syed Gulam} } @article { ISI:000364521100015, title = {Microbial selenium nanoparticles (SeNPs) and their application as a sensitive hydrogen peroxide biosensor}, journal = {Applied Biochemistry and Biotechnology}, volume = {177}, number = {6}, year = {2015}, month = {NOV}, pages = {1386-1393}, publisher = {HUMANA PRESS INC}, address = {999 RIVERVIEW DRIVE SUITE 208, TOTOWA, NJ 07512 USA}, abstract = {

The cell-free extract, a crude enzyme (cytosolic and membrane fraction) obtained from an environmental isolate, Bacillus pumilus sp. BAB-3706 worked as excellent in reducing as well as stabilizing agent and facilitated the formation of stable colloidal selenium nanoparticles (SeNPs). Resulting nanoparticles were characterized using UV-vis spectrophotometer, TEM, EDAX, FT-IR and XRD, respectively. A working electrode was modified by coating the surface of indium tin oxide (ITO) with colloidal SeNPs. Successive additions of H2O2 (100 to 600 mu M) in conventional three electrodes system, cyclic voltammeter with potential scan rate 25.0 mV/s, in 0.1 M phosphate buffer solution (PBS) yielded increase in current. A perpetual amperometric response at fixed potential (-1.0 V) and at selected time interval of 100 s showed different magnitude of current at every addition of H2O2. The linear range of detection of H2O2 was from 5 to 600 mM (R (2) = 0.9965), while the calculated limit of detection was found to be 3.00 mu M. The current study suggested that microbial SeNPs can be used for fabrication of low cost, sensitive H2O2 biosensor.

}, keywords = {Biosensor, EDAX, Hydrogen peroxide, Selenium nanoparticles, TEM, UV-vis spectroscopy}, issn = {0273-2289}, doi = {10.1007/s12010-015-1814-9}, author = {Prasad, Kumar Suranjit and Vaghasiya, Jayraj V. and Soni, Saurabh S. and Patel, Jitesh and Patel, Rinkesh and Kumari, Madhu and Jasmani, Falguni and Selvaraj, Kaliaperumal} } @conference {45949, title = {Molecular sieves and ultrasound-assisted synthesis of novel 1,3,4-oxadiazole-2-thiones derivatives as potential antifungal agents}, booktitle = {19TH INTERNATIONAL ELECTRONIC CONFERENCE ON SYNTHETIC ORGANIC CHEMISTRY}, year = {2015}, publisher = {MDPI; Univ Sanitiago Compostila; SES; Flow Chemistry; REGAL S; Molecules}, organization = {MDPI; Univ Sanitiago Compostila; SES; Flow Chemistry; REGAL S; Molecules}, address = {ST. ALBAN-ANLAGE 66, BASEL, CH-4052, SWITZERLAND}, abstract = {

In the category of microorganism, fungi are considered as the special class of microbes responsible for opportunistic pathogenic infections in humans species. Due to the side effects of commercially available antifungal drugs and the emergence of new drug resistant fungal species in the past few years, has forced the researchers to search for novel and efficient antifungal drug molecules. The 1,3,4-oxadiazoles scaffold is associated with diverse biological activities. The multipurpose use of the Mannich bases in pharmaceutical chemistry promote us to prepare a new series of 5-(4-(benzyloxy)substituted phenyl)-3-((phenyl amino)methyl)-1,3,4oxadiazole-2(3H)-thione as antifungal agents. Herein, we report molecular sieves and ultrasound assisted synthesis of novel series of Mannich bases of the 5-substituted 1,3,4-oxadiazole-2-thiones by amino methylation with paraformaldehyde and substituted primary / secondary amines and their evaluation for antifungal activity. The structures of the newly synthesized compounds were determined by IR, NMR and Mass spectral study. The synthesized compounds exhibited interesting moderate to excellent antifungal activity against Candida albicans (NCIM 3557), Candida albicans(NCIM3471), Candida glabrata(NCIM3237), Cryptococcus neoformans (NCIM 3542), Cryptococcus neoformans(NCIM 3378), Aspergillus fumigates(NCIM 902), Aspergillus niger(NCIM 628) using Flucanazole as a standard reference drug. The synthesised compounds 6d, 6f,6g, 6h and 6j exhibited promising antifungal activity as antifungal agents.

}, keywords = {1, 3, 4-oxadiazoles, Antifungal activity, Mannich reaction, Molecular sieves, Ultrasound -assisted}, doi = {10.3390/ecsoc-19-b008}, author = {Nikalje, Anna Pratima G. and Nimbalkar, Ms Urja D. and Tupe, Santosh and Vazquez, Julio A. Seijas and Tato, Maria Pilar Vazquez}, editor = {Seijas, JA and Tato, MPV and Lin, SK} } @article { ISI:000349018100016, title = {New scheme for perturbative triples correction to (0,1) sector of Fock space multi-reference coupled cluster method: Theory, implementation, and examples}, journal = {Journal of Chemical Physics}, volume = {142}, number = {4}, year = {2015}, month = {JAN}, pages = {Article No. 044113}, publisher = {AMER INST PHYSICS}, address = {1305 WALT WHITMAN RD, STE 300, MELVILLE, NY 11747-4501 USA}, abstract = {

We propose a new elegant strategy to implement third order triples correction in the light of many-body perturbation theory to the Fock space multi-reference coupled cluster method for the ionization problem. The computational scaling as well as the storage requirement is of key concerns in any many-body calculations. Our proposed approach scales as N-6 does not require the storage of triples amplitudes and gives superior agreement over all the previous attempts made. This approach is capable of calculating multiple roots in a single calculation in contrast to the inclusion of perturbative triples in the equation of motion variant of the coupled cluster theory, where each root needs to be computed in a state-specific way and requires both the left and right state vectors together. The performance of the newly implemented scheme is tested by applying to methylene, boron nitride (B2N) anion, nitrogen, water, carbon monoxide, acetylene, formaldehyde, and thymine monomer, a DNA base. (C) 2015 AIP Publishing LLC.

}, issn = {0021-9606}, doi = {10.1063/1.4906233}, author = {Dutta, Achintya Kumar and Vaval, Nayana and Pal, Sourav} } @article { ISI:000367421500014, title = {Novel 2,6-diformyl-4-methyl phenol based chemosensor for Zn-II ion by ratiometric displacement of Cd-II ion and its application for cell imaging on human melanoma cancer cells}, journal = {Journal of the Indian Chemical Society}, volume = {92}, number = {11}, year = {2015}, month = {NOV}, pages = {1729-1745}, publisher = {SCIENTIFIC PUBL-INDIA}, address = {5-A, NEW PALI RD, PO BOX 91, NEAR HOTEL TAJ HARI MAHAL, JODHPUR, 342 003, INDIA}, abstract = {

A new chelating ligand [4-methyl-2,6-bis-(pyridin-2-yl-hydrazonomethyl)-phenol] (1) was prepared by the condensation of 2-hydrazinylpyridine with 2,6-diformyl-p-cresol. Compound 1 exhibits weak fluorescence due to intramolecular photoinduced electron transfer (PET). The sensor (1) demonstrates Zn2+-specific emission enhancement due to {\textquoteleft}{\textquoteleft}PET off{\textquoteright}{\textquoteright} process through a 1 : 1 binding mode with the metal ion. The fluorescence quantum yield of the chemosensor 1 is only 0.020, and it increases more than 14-fold (0.280) in the presence of one equivalent of the zinc ion. Interestingly, the introduction of other metal ions causes the fluorescence intensity to remain either unchanged or weakened except for Cd2+. Ratiometric displacement of Cd2+ ion from the complex by Zn2+ ion supports the formation of more stable sensor-Zn2+ complex over the sensor-Cd2+ complex. The experimental findings have been correlated with theoretical results using B3LYP functional and 6-31G(d,p), LANL2DZ basis set for Cd2+ (2) and Zn2+ (3) complex, respectively, by Density Functional Theory (DFT) method. Moreover, the ability of probe 1 to sense Zn2+ within human melanoma cancer cells has been explored, and the Zn2+-probing process in living cells was reversible. [Mn-2(PHMP)(2)](ClO4)(2) (4) and [Ni-2(PHMP)(H2O)(5)](NO3)(3) (5) have been also synthesized and characterized crystallographically and spectroscopically to understand the ligating behavior of the ligand PHMP.

}, keywords = {Cd-II ion, Chemosensor, Density functional theory, human melanoma cancer cells, photoinduced electron transfer, Zn-II ion}, issn = {0019-4522}, author = {Mitra, Debarshan and Venkatathari, N. and Sabharwal, S. C. and Godbole, S. V. and Tyagi, A. K. and Das, Sangbrita} } @article { ISI:000349088000020, title = {Oxidation catalysis by large trisoctahedral gold nanoparticles: Mind the step!}, journal = {Catalysis Today}, volume = {244}, year = {2015}, month = {APR}, pages = {177-183}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

To understand the origin of catalysis by gold and to probe the role of defects and interfaces, benchmark reactions namely CO oxidation and benzyl alcohol oxidation were carried out on supported trisoctahedral gold nanoparticles and on the inverse catalyst system. The sizes of these particles which are between 45 nm and 110 nm, are well beyond the quantum size regime and well above the optimum size range where gold is considered to be catalytically active. The periodic steps sites in contact with oxide support interface were able to promote the reaction. (C) 2014 Elsevier B.V. All rights reserved.

}, keywords = {CO oxidation, Defects, Gold catalysis, Inverse catalysta, Steps and kinks}, issn = {0920-5861}, doi = {10.1016/j.cattod.2014.02.049}, author = {Sreedhala, S. and Sudheeshkumar, V. and Vinod, C. P.} } @conference { ISI:000354845400032, title = {Partial triples excitation to the fock space multi-reference singles and doubles: dipole moment of doublet radicals}, booktitle = {Proceedings of the International Conference of Computational Methods in Sciences and Engineering 2010 (ICCMSE-2010)}, series = {AIP Conference Proceedings}, volume = {1642}, year = {2015}, note = {International Conference of Computational Methods in Sciences and Engineering (ICCMSE), Kos, GREECE, OCT 03-08, 2010}, month = {FEB}, pages = {223-226}, publisher = {European Soc Computat Methods Sci, Engn \& Technol}, organization = {European Soc Computat Methods Sci, Engn \& Technol}, address = {2 Huntington Quadrangle, STE 1NO1, Melville, NY 11747-4501 USA}, abstract = {

We present the partial triples effect on the dipole moment of doublet radicals in Lagrangian formulation of Fockspace multi-reference coupled cluster response method(A FSMRCC). This specific scheme uses non-iterative triples, in addition to singles and doubles excitations(A FSMRCCSD(T*)), which accounts for the effects appearing at least at the third order in dipole moment. This method is applied to the ground states of small radicals.

}, keywords = {Dipole moment, Multi-reference, Triples}, isbn = {978-0-7354-1282-8}, issn = {0094-243X}, doi = {10.1063/1.4906657}, author = {Ravichandran, Lalitha and Vaval, Nayana and Pal, Sourav}, editor = {Simos, TE and Maroulis, G} } @article {45882, title = {Pd loaded amphiphilic COF as catalyst for multi-fold Heck reactions, C-C couplings and CO oxidation}, journal = {Scientific Reports}, volume = {5}, year = {2015}, month = {JUN }, pages = {10876}, type = {Article}, abstract = {

COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd-0 nanoparticles into it. An 18-20\% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) \< 0.05 mol\%, average TON 1500) catalyzing simultaneous multiple site Heck couplings and C-C couplings using {\textquoteleft}non-boronic acid{\textquoteright} substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100\% conversion of CO to CO2 at 150 degrees C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable.

}, issn = {2045-2322}, doi = {10.1038/srep10876}, author = {Mullangi, Dinesh and Nandi, Shyamapada and Shalini, Sorout and Sreedhala, Sheshadri and Vinod, Chathakudath P. and Vaidhyanathan, Ramanathan} } @article { ISI:000360934800002, title = {Pharmacophore and docking based virtual screening of validated mycobacterium tuberculosis targets}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {7}, year = {2015}, month = {AUG}, pages = {624-637}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, abstract = {

Target based virtual screening has surpassed ligand based virtual screening methods in the recent past mainly as it provides more clues regarding intermolecular interactions and takes into consideration the flexible receptor as well. The current methodology describes a computational strategy of predicting Mycobacterium tuberculosis (M. tuberculosis) binders for five well studied targets representing M. tuberculosis proteome encompassing most of the known mechanisms of action. The diversity of the targets was affirmed by their active site analysis and structural studies. The current approach employed pharmacophore searching, docking and clustering techniques in tandem and was validated by enrichment studies using the available Schrodinger data set consisting of 1000 decoys. The application of this methodology was demonstrated by predicting potential molecular targets for fifty newly synthesized compounds. Cross docking studies on the targets were carried out with 4512 known inhibitors utilizing a high performance computing platform to reveal underlying affinity and promiscuity patterns. Optimum binding energy range for all targets as determined by high throughput docking was found to be -3 to -13 kcal/mol.

}, keywords = {Binding energy, docking, Mycobacterium tuberculosis, open source drug discovery (OSDD), pharmacophore, structure based drug design (SBDD)}, issn = {1386-2073}, doi = {10.2174/1386207318666150703112759}, author = {Vyas, Renu and Karthikeyan, Muthukumarasamy and Nainaru, Ganesh and Muthukrishnan, Murugan} } @article { ISI:000360934400004, title = {Prediction of bioactive compounds using computed NMR chemical shifts}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {6}, year = {2015}, month = {JAN}, pages = {562-576}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, abstract = {

NMR based chemical shifts are an important diagnostic parameter for structure elucidation as they capture rich information related to conformational, electronic and stereochemical arrangement of functional groups in a molecule which is responsible for its activity towards any biological target. The present work discusses the importance of computing NMR chemical shifts from molecular structures. The NMR chemical shift data (experimental or computed) was used to generate fingerprints in binary formats for mapping molecular fragments (as descriptors) and correlating with the bioactivity classes. For this study, chemical shift data derived binary fingerprints were computed for 149 classes and 4800 bioactive molecules. The sensitivity and selectivity of fingerprints in discriminating molecules belonging to different therapeutic categories was assessed using a LibSVM based classifier. An accuracy of 82\% for proton and 94\% for carbon NMR fingerprints were obtained for anti-psoriatic and anti-psychotic molecules demonstrating the effectiveness of this approach for virtual screening.

}, keywords = {Chemical shift, fingerprints, NMR, similarity searching, virtual screening}, issn = {1386-2073}, doi = {10.2174/1386207318666150703113312}, author = {Karthikeyan, Muthukumarasamy and Rajamohanan, Pattuparambil Ramanpillai and Vyas, Renu} } @article { ISI:000364032500052, title = {Preparation of mesoporous titanosilicate with isolated Ti active centers for cyclohexene oxidation}, journal = {RSC Advances}, volume = {5}, number = {112}, year = {2015}, month = {OCT}, pages = {92371-92377}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

We report the preparation of mesoporous titanosilicate with active Ti centres using CTAB as the structure directing agent and ethylenediamine as the complexing agent (TSC-ED). The finalmaterial contained isolated Ti4+ centres substituting Si4+ in the mesoporous silica framework. The crucial role played by ethylenediamine in complexing with Ti4+ during the sol-gel process and preventing the phase segregation of TiO2 was studied systematically. The textural parameters, structural order, morphology, nature and co-ordination of Ti species were analyzed using various techniques such as X-ray diffraction (XRD), UV-vis diffused reflectance spectroscopy (UV-vis DRS), UV resonance Raman spectroscopy, Fourier transformed Infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transition electron microscopy (TEM), and X-ray photoelectron spectroscopy. Finally, the catalysts were tested for catalytic activity in the oxidation of cyclohexene using various oxidants.

}, issn = {2046-2069}, doi = {10.1039/c5ra18044a}, author = {Gupta, S. and Vinod, C. P. and Jagadeesan, Dinesh} } @article { ISI:000350056800015, title = {Proline-catalyzed alpha-aminooxylation of beta-amino aldehydes: access to enantiomerically pure syn- and anti-3-amino-3-aryl-1,2-alkanediols}, journal = {Synlett}, volume = {26}, number = {3}, year = {2015}, month = {FEB}, pages = {355-358}, publisher = {GEORG THIEME VERLAG KG}, address = {RUDIGERSTR 14, D-70469 STUTTGART, GERMANY}, abstract = {

A new synthetic method for enantioselective synthesis of syn 3-amino-3-aryl-1,2-alkanediols via praline catalyzed alpha-aminaoxn y ylation of beta-amino aldehydes des are described. This methodology is successfully applied to a concise and protecting group-free asymmetric synthesis of (-)-cytoxazone (+)-epi-cytoxazone and formal synthesis of N-thiolated 2-oxazolidinone.

}, keywords = {amino aldehydes, Asymmetric synthesis, catalysis, diastereoselectivity, Enantioselectivity, Natural product}, issn = {0936-5214}, doi = {10.1055/s-0034-1379735}, author = {Venkataramasubramanian, V. and Kiran, I. N. Chaithanya and Sudalai, Arumugam} } @article { ISI:000360934400005, title = {Protein ligand complex guided approach for virtual screening}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {6}, year = {2015}, month = {JAN}, pages = {577-590}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, abstract = {

The target ligand association data is a rich source of information which is not exploited enough for drug design efforts in virtual screening. A java based open-source toolkit for Protein Ligand Network Extraction (J-ProLiNE) focused on protein-ligand complex analysis with several features integrated in a distributed computing network has been developed. Sequence alignment and similarity search components have been automated to yield local, global alignment scores along with similarity and distance scores. 10000 proteins with co-crystallized ligands from pdb and MOAD databases were extracted and analyzed for revealing relationships between targets, ligands and scaffolds. Through this analysis, we could generate a protein ligand network to identify the promiscuous and selective scaffolds for multiple classes of proteins targets. Using J-ProLiNE we created a 507 x 507 matrix of protein targets and native ligands belonging to six enzyme classes and analyzed the results to elucidate the protein-protein, protein-ligand and ligand-ligand interactions. In yet another application of the J-ProLiNE software, we were able to process kinase related information stored in US patents to construct disease-gene-ligand-scaffold networks. It is hoped that the studies presented here will enable target ligand knowledge based virtual screening for inhibitor design.

}, keywords = {Complexes, ligand, protein, scaffolds, sequences, similarity score, virtual screening}, issn = {1386-2073}, doi = {10.2174/1386207318666150703112620}, author = {Karthikeyan, Muthukumarasamy and Pandit, Deepak and Vyas, Renu} } @article { ISI:000354188800009, title = {Relativistic equation-of-motion coupled-cluster investigation of the trends of single and double ionization potentials in the He and Be isoelectronic systems}, journal = {Journal of Physics B-Atomic Molecular and Optical Physics}, volume = {48}, number = {11}, year = {2015}, month = {JUN}, pages = {115009}, publisher = {IOP PUBLISHING LTD}, address = {TEMPLE CIRCUS, TEMPLE WAY, BRISTOL BS1 6BE, ENGLAND}, abstract = {

We employ a four-component spinor relativistic equation-of-motion coupled-cluster (EOMCC) method within the single-and double-excitation approximation to calculate the single ionization potentials (IPs) and double ionization potentials (DIPs) of the He and Be isoelectronic sequences up to Ne. The obtained results are compared with the available results from the National Institute of Standards and Technology (NIST) database to test the performance of the EOMCC method. We also present intermediate results at different levels of approximations in the EOMCC framework to gain insight of the effect of electron correlation. Furthermore, we investigate the dependence of the IPs and DIPs of these ions on the ionic charge and observe that these follow parabolic trends. Similarities between the trends of IPs and DIPs in both the classes of considered systems are categorically demonstrated.

}, keywords = {coupled-cluster method, double ionization potentials, equation-of-motion theory}, issn = {0953-4075}, doi = {10.1088/0953-4075/48/11/115009}, author = {Pathak, Himadri and Sahoo, B. K. and Sengupta, Turbasu and Das, B. P. and Vaval, Nayana and Pal, Sourav} } @article {42629, title = {Relativistic extended coupled cluster method for magnetic hyperfine structure constant}, journal = {Physical Review A}, volume = {91}, year = {2015}, month = {FEB}, pages = {Article No. 022512}, type = {Article}, doi = {10.1103/PhysRevA.91.022512}, author = {Sasmal, Sudip and Pathak, Himadri and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article { ISI:000350685400013, title = {Renewable fuels from biomass-derived compounds: Ru-containing hydrotalcites as catalysts for conversion of HMF to 2,5-dimethylfuran}, journal = {Catalysis Science \& Technology}, volume = {5}, number = {3}, year = {2015}, month = {MAR}, pages = {1463-1472}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Production of transportation fuels from renewable biomass is hugely important considering the current ecological concerns over CO2 built up in the atmosphere. Ruthenium-containing hydrotalcite (HT) catalysts were applied for the selective hydrogenolysis of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF). Structural and morphological features of the catalysts were examined using various physico-chemical characterization techniques. The influence of various reaction parameters, such as reaction temperature, solvent, Ru content of the catalyst, etc., was investigated with respect to HMF conversion and DMF yield. The study clearly shows that well-dispersed Ru nanoparticles are highly active and selective in the conversion of HMF to DMF. A catalyst containing only 0.56 wt\% Ru converted 100 mol\% HMF to yield 58 mol\% DMF. This catalyst was found to be recyclable as the activity was retained even after five cycles of reaction. 2-Propanol was found to be a good solvent as it helped to improve DMF yield through transfer hydrogenation. Based on the results of the investigations, a reaction pathway for the conversion of HMF to DMF was proposed for the present Ru-based catalyst system.

}, issn = {2044-4753}, doi = {10.1039/c4cy01376j}, author = {Nagpure, Atul S. and Venugopal, Ashok Kumar and Lucas, Nishita and Manikandan, Marimuthu and Thirumalaiswamy, Raja and Chilukuri, Satyanarayana V.} } @article { ISI:000350674400031, title = {Reversal of H-bonding direction by N-sulfonation in a synthetic reverse-turn peptide motif}, journal = {Organic \& Biomolecular Chemistry}, volume = {13}, number = {10}, year = {2015}, month = {MAR}, pages = {3064-3069}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

This communication depicts an intriguing example of hydrogen-bonding reversal upon introduction of a sulfonamide linkage at the N-terminus of a synthetic reverse-turn peptide motif. The ready availability of two sulfonyl oxygen atoms, as hydrogen-bonding acceptors, combined with the inherent twisted conformation of sulfonamides are seen to act as switches that engage/disengage the hydrogen-bond at the sticky ends/termini.

}, issn = {1477-0520}, doi = {10.1039/c4ob02438a}, author = {Vijayadas, Kuruppanthara N. and Kotmale, Amol S. and Thorat, Shridhar H. and Gonnade, Rajesh G. and Nair, Roshna V. and Rajamohanan, Pattuparambil R. and Sanjayan, Gangadhar J.} } @article { ISI:000360934800003, title = {Role of chemical reactivity and transition state modeling for virtual screening}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {7}, year = {2015}, month = {JAN}, pages = {638-657}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, abstract = {

Every drug discovery research program involves synthesis of a novel and potential drug molecule utilizing atom efficient, economical and environment friendly synthetic strategies. The current work focuses on the role of the reactivity based fingerprints of compounds as filters for virtual screening using a tool ChemScore. A reactant-like (RLS) and a product-like (PLS) score can be predicted for a given compound using the binary fingerprints derived from the numerous known organic reactions which capture the molecule-molecule interactions in the form of addition, substitution, rearrangement, elimination and isomerization reactions. The reaction fingerprints were applied to large databases in biology and chemistry, namely ChEMBL, KEGG, HMDB, DSSTox, and the Drug Bank database. A large network of 1113 synthetic reactions was constructed to visualize and ascertain the reactant product mappings in the chemical reaction space. The cumulative reaction fingerprints were computed for 4000 molecules belonging to 29 therapeutic classes of compounds, and these were found capable of discriminating between the cognition disorder related and anti-allergy compounds with reasonable accuracy of 75\% and AUC 0.8. In this study, the transition state based fingerprints were also developed and used effectively for virtual screening in drug related databases. The methodology presented here provides an efficient handle for the rapid scoring of molecular libraries for virtual screening.

}, keywords = {fingerprints, intermediates, metabolic pathways, product-like score, reactant-like score, reaction, screening, synthesis, virtual screening}, issn = {1386-2073}, doi = {10.2174/1386207318666150703113135}, author = {Karthikeyan, Muthukumarasamy and Vyas, Renu and Tambe, Sanjeev S. and Radhamohan, Deepthi and Kulkarni, Bhaskar D.} } @article { ISI:000360934800001, title = {Role of data and methods in chemoinformatics for virtual screening}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {7}, year = {2015}, month = {JAN}, pages = {622-623}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, issn = {1386-2073}, doi = {10.2174/138620731807150903101821}, author = {Karthikeyan, Muthukumarasamy and Vyas, Renu} } @article { ISI:000360934400002, title = {Role of open source tools and resources in virtual screening for drug discovery}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {6}, year = {2015}, month = {JUL}, pages = {528-543}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, abstract = {

Advancement in chemoinformatics research in parallel with availability of high performance computing platform has made handling of large scale multi-dimensional scientific data for high throughput drug discovery easier. In this study we have explored publicly available molecular databases with the help of open-source based integrated in-house molecular informatics tools for virtual screening. The virtual screening literature for past decade has been extensively investigated and thoroughly analyzed to reveal interesting patterns with respect to the drug, target, scaffold and disease space. The review also focuses on the integrated chemoinformatics tools that are capable of harvesting chemical data from textual literature information and transform them into truly computable chemical structures, identification of unique fragments and scaffolds from a class of compounds, automatic generation of focused virtual libraries, computation of molecular descriptors for structure-activity relationship studies, application of conventional filters used in lead discovery along with in-house developed exhaustive PTC (Pharmacophore, Toxicophores and Chemophores) filters and machine learning tools for the design of potential disease specific inhibitors. A case study on kinase inhibitors is provided as an example.

}, keywords = {Chemoinformatics, kinases, open source, scaffold, virtual screening}, issn = {1386-2073}, doi = {10.2174/1386207318666150703111911}, author = {Karthikeyan, Muthukumarasamy and Vyas, Renu} } @article { ISI:000359951700161, title = {RXR-carbamate - a novel molecular transporter for skin}, journal = {Molecular Therapy}, volume = {23}, number = {1}, year = {2015}, note = {18th Annual Meeting of the American-Society-of-Gene-and-Cell-Therapy (ASGCT), New Orleans, LA, MAY 13-16, 2015}, month = {MAY}, pages = {S64-S64}, publisher = {Amer Soc Gene \& Cell Therapy}, address = {75 VARICK ST, 9TH FLR, NEW YORK, NY 10013-1917 USA}, issn = {1525-0016}, author = {Natarajan, Poornemaa and Patil, Kiran M. and Vij, Manika and Yadav, Amit K. and Kumar, Vaijayanti A. and Ganguli, Munia and Fernandes, Moneesha} } @article { ISI:000353702500026, title = {Self-templated chemically stable hollow spherical covalent organic framework}, journal = {Nature Communications}, volume = {6}, year = {2015}, month = {APR}, pages = {6786}, publisher = {NATURE PUBLISHING GROUP}, address = {MACMILLAN BUILDING, 4 CRINAN ST, LONDON N1 9XW, ENGLAND}, abstract = {

Covalent organic frameworks are a family of crystalline porous materials with promising applications. Although active research on the design and synthesis of covalent organic frameworks has been ongoing for almost a decade, the mechanisms of formation of covalent organic frameworks crystallites remain poorly understood. Here we report the synthesis of a hollow spherical covalent organic framework with mesoporous walls in a single-step template-free method. A detailed time-dependent study of hollow sphere formation reveals that an inside-out Ostwald ripening process is responsible for the hollow sphere formation. The synthesized covalent organic framework hollow spheres are highly porous (surface area similar to 1,500m(2) g(-1)), crystalline and chemically stable, due to the presence of strong intramolecular hydrogen bonding. These mesoporous hollow sphere covalent organic frameworks are used for a trypsin immobilization study, which shows an uptake of 15.5 mu mol g(-1) of trypsin.

}, issn = {2041-1723}, doi = {10.1038/ncomms7786}, author = {Kandambeth, Sharath and Venkatesh, V. and Shinde, Digambar B. and Kumari, Sushma and Halder, Arjun and Verma, Sandeep and Banerjee, Rahul} } @article { ISI:000350221600066, title = {Silica microspheres containing high density surface hydroxyl groups as efficient epoxidation catalysts}, journal = {RSC Advances}, volume = {5}, number = {27}, year = {2015}, month = {FEB}, pages = {21125-21131}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Uniformly sized silica microspheres were synthesized by a hydrolysis-condensation method. The obtained material was etched with a mild aqueous potassium hydroxide solution for different periods of time to break their Si-O-Si bonds and increases the density of hydroxyl groups on their surfaces. The resulting materials were then used as transition metal-free catalysts for oxidation of olefins in the presence of hydrogen peroxide as a green oxidant. The materials were thoroughly characterized using various physicochemical techniques. These highly populated hydroxyl groups on the surface of silica microspheres were proven to be responsible for excellent conversion (up to 93\%) and epoxide selectivity (up to 100\%) for various olefins. Quantum mechanical calculations also corroborate the experimental findings. Furthermore, both experimental and theoretical studies show that tertiary silanols were present at the active sites of the catalyst surface and were responsible for olefin epoxidation.

}, issn = {2046-2069}, doi = {10.1039/c5ra00374a}, author = {Chandra, Prakash and Doke, Dhananjay S. and Shubhangi B. Umbarkar and Vanka, Kumar and Biradar, Ankush V.} } @article {43027, title = {Spirochromone-chalcone conjugates as antitubercular agents: synthesis, bio evaluation and molecular modeling studies}, journal = {RSC Advances}, volume = {5}, year = {2015}, month = {DEC}, abstract = {

A new series of spirochromone annulated chalcone conjugates were synthesized and evaluated for their antitubercular activity against Mycobacterium tuberculosis H37Rv strain. These compounds were subjected to molecular modeling studies using docking and chemoinformatics based approaches. The docking simulations were performed against a range of known receptors for chalcone derived compounds to reveal MTB phosphotyrosine phosphatase B [MtbPtpB] protein as the most probable target based on the high binding affinity scores. Five compounds exhibit significant inhibition, showing minimum inhibitory concentration values i.e. MIC values ranging from 3.13{\textendash}12.5 μg mL-1. Further analysis of the synthesized compounds with known and in-house developed chemoinformatics tools unequivocally established their potential as anti-tubercular compounds. QSAR modeling revealed a quantitative relationship between biological activities and frontier molecular orbital energies of synthesized compounds. The predictive model can be employed further for virtual screening of new compounds in this series.

}, doi = {10.1039/C5RA21737G}, author = {Mujahid, Mohammad and Perumal, Yogeeswari and Sriram, D. and Basavanag, U. M. V. and D{\i}az-Cervantes, Erik and Cordoba-Bahena, Luis and Robles, Juvencio and Gonnade, Rajesh Ghanshyam and Karthikeyan, Muthukumarasamy and Vyas, Renu and Krishnan, M. Muthu} } @article { ISI:000361935600025, title = {Star telechelic poly(L-lactide) ionomers}, journal = {Macromolecules}, volume = {48}, number = {18}, year = {2015}, month = {SEP}, pages = {6580-6588}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Poly(L-lactide) (PLA), a biodegradable and biorenewable polymer, has many excellent properties that are equivalent to those of petroleum-derived plastics such as polystyrene, aromatic polyesters, etc. However, a major disadvantage of PLA which limits its processability is its poor melt elasticity. In this work we explore the possibility of improving the viscoelastic properties of PLA melt by incorporating ionic groups on the polymer. Specifically, we demonstrate the synthesis of star telechelic PLA anionomers by a three-step procedure involving synthesis of Star PIA, converting the hydroxyl end groups into carboxylic acid end groups, and finally converting these into ionic groups. Rheology data showed a dramatic increase in the elasticity of the star telechelic ionomer melts relative to the Star PLA melts. The viscoelasticity of star telechelic ionomers melts could be modulated by varying the number of ionic groups per molecule.

}, issn = {0024-9297}, doi = {10.1021/acs.macromol.5b01854}, author = {Kulkarni, Amruta and Lele, Ashish K. and Sivaram, Swaminathan and Rajamohanan, P. R. and Velankar, Sachin and Chatterji, Apratim} } @article { ISI:000363727100011, title = {Structure mediation in substrate binding and post-translational processing of penicillin acylases: Information from mutant structures of Kluyvera citrophila penicillin G acylase}, journal = {Protein Science}, volume = {24}, number = {10}, year = {2015}, month = {OCT}, pages = {1660-1670}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

Penicillin acylases are industrially important enzymes for the production of 6-APA, which is used extensively in the synthesis of secondary antibiotics. The enzyme translates into an inactive single chain precursor that subsequently gets processed by the removal of a spacer peptide connecting the chains of the mature active heterodimer. We have cloned the penicillin G acylase from Kluyvera citrophila (KcPGA) and prepared two mutants by site-directed mutagenesis. Replacement of N-terminal serine of the beta-subunit with cysteine (Ser beta 1Cys) resulted in a fully processed but inactive enzyme. The second mutant in which this serine is replaced by glycine (Ser beta 1Gly) remained in the unprocessed and inactive form. The crystals of both mutants belonged to space group P1 with four molecules in the asymmetric unit. The three-dimensional structures of these mutants were refined at resolutions 2.8 and 2.5 angstrom, respectively. Comparison of these structures with similar structures of Escherichia coli PGA (EcPGA) revealed various conformational changes that lead to autocatalytic processing and consequent removal of the spacer peptide. The large displacements of residues such as Arg168 and Arg477 toward the N-terminal cleavage site of the spacer peptide or the conformational changes of Arg145 and Phe146 near the active site in these structures suggested probable steps in the processing dynamics. A comparison between the structures of the processed Serb1Cys mutant and that of the processed form of EcPGA showed conformational differences in residues Arg alpha 145, Phe alpha 146, and Phe beta 24 at the substrate binding pocket. Three conformational transitions of Arg alpha 145 and Phe alpha 146 residues were seen when processed and unprocessed forms of KcPGA were compared with the substrate bound structure of EcPGA. Structure mediation in activity difference between KcPGA and EcPGA toward acyl homoserine lactone (AHL) is elucidated.

}, keywords = {acyl homoserine lactone, autocatalytic processing, conformational changes, KcPGA_Ser beta 1Cys, KcPGA_Ser beta 1Gly, Ntn hydrolase}, issn = {0961-8368}, doi = {10.1002/pro.2761}, author = {Chand, Deepak and Varshney, NishantKumar and Ramasamy, Sureshkumar and Panigrahi, Priyabrata and Brannigan, James A. and Wilkinson, Anthony J. and Suresh, C. G.} } @article { ISI:000364885800006, title = {Studies toward the total synthesis of cytospolide E}, journal = {Tetrahedron}, volume = {71}, number = {48}, year = {2015}, month = {DEC}, pages = {9088-9094}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

In this manuscript, we describe various approaches that we have examined towards the total synthesis of Cytospolide E. We initially attempted the RCM approach employing first and second generation Grubbs and Grubbs-Hoyeda catalysts resulting in the exclusive synthesis of the Z-isomer of Cytospolide E. With the Furstner catalyst, the dimerization involving the less hindered olefin was the exclusive event. Alternative approach documented is a successful cross-metathesis leading to a seco-acid with the requisite E-configuration and undesired macrodiolide formation during the attempted Shiina{\textquoteright}s lactonization. (C) 2015 Elsevier Ltd. All rights reserved.

}, keywords = {20-Membered macrodiolide, Nonenolide, Ring closing metathesis, Shiina lactonization, Yamaguchi esterification}, issn = {0040-4020}, doi = {10.1016/j.tet.2015.10.018}, author = {Vadhadiya, Paresh M. and Rout, Jeetendra K. and Ramana, C. V.} } @article { ISI:000360934800004, title = {Study of applications of machine learning based classification methods for virtual screening of lead molecules}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {18}, number = {7}, year = {2015}, month = {AUG}, pages = {658-672}, publisher = {BENTHAM SCIENCE PUBL LTD}, address = {EXECUTIVE STE Y-2, PO BOX 7917, SAIF ZONE, 1200 BR SHARJAH, U ARAB EMIRATES}, abstract = {

The ligand-based virtual screening of combinatorial libraries employs a number of statistical modeling and machine learning methods. A comprehensive analysis of the application of these methods for the diversity oriented virtual screening of biological targets/drug classes is presented here. A number of classification models have been built using three types of inputs namely structure based descriptors, molecular fingerprints and therapeutic category for performing virtual screening. The activity and affinity descriptors of a set of inhibitors of four target classes DHFR, COX, LOX and NMDA have been utilized to train a total of six classifiers viz. Artificial Neural Network (ANN), k nearest neighbor (k-NN), Support Vector Machine (SVM), Naive Bayes (NB), Decision Tree - (DT) and Random Forest - (RF). Among these classifiers, the ANN was found as the best classifier with an AUC of 0.9 irrespective of the target. New molecular fingerprints based on pharmacophore, toxicophore and chemophore (PTC), were used to build the ANN models for each dataset. A good accuracy of 87.27\% was obtained using 296 chemophoric binary fingerprints for the COX-LOX inhibitors compared to pharmacophoric (67.82 \%) and toxicophoric (70.64 \%). The methodology was validated on the classical Ames mutagenecity dataset of 4337 molecules. To evaluate it further, selectivity and promiscuity of molecules from five drug classes viz. anti-anginal, anti-convulsant, anti-depressant, anti-arrhythmic and anti-diabetic were studied. The TPC fingerprints computed for each category were able to capture the drug-class specific features using the k-NN classifier. These models can be useful for selecting optimal molecules for drug design.

}, keywords = {Anti-anginal, anti-arrythmic, anti-bacterial, anti-convulsant, anti-depressant anti-diabetic, binary QSAR, chemophore, machine learning, pharmacophore, toxicophore}, issn = {1386-2073}, doi = {10.2174/1386207318666150703112447}, author = {Vyas, Renu and Bapat, Sanket and Jain, Esha and Tambe, Sanjeev S. and Karthikeyan, Muthukumarasamy and Kulkarni, Bhaskar D.} } @article { ISI:000356021300023, title = {Surfactant assisted formation of ruthenium nanochains under mild conditions and their catalytic CO oxidation activity}, journal = {Chemical Communications}, volume = {51}, number = {50}, year = {2015}, month = {MAY}, pages = {10178-10181}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Spontaneous formation of ruthenium nanochains is accomplished in aqueous medium under mild conditions using a seed mediated protocol with cetyl trimethylammonium bromide (CTAB) as the capping agent. They are formed due to the random self-assembly of Ru seeds of similar to 3.5 nm size. These 1D nanostructures exhibit better catalytic activity towards the oxidation of CO relative to the similar to 3.5 nmseeds and 6 nm Ru nanospheres. The synthesis strategy adopted here is found to be simple, facile and environmentally friendly.

}, issn = {1359-7345}, doi = {10.1039/c4cc09430a}, author = {Sreedhala, S. and Vinod, C. P.} } @article { ISI:000354910500021, title = {Switching closed-shell to open-shell phenalenyl: toward designing electroactive materials}, journal = {Journal of the American Chemical Society}, volume = {137}, number = {18}, year = {2015}, month = {MAY}, pages = {5955-5960}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Open-shell phenalenyl chemistry started more than half a century back, and the first solid-state phenalenyl radical was realized only 15 years ago highlighting the synthetic challenges associated in stabilizing carbon-based radical chemistry, though it has great promise as building blocks for molecular electronics and multifunctional materials. Alternatively; stable closed-shell phenalenyl has tremendous potential as it can be utilized, to create an in situ open-shell state by external spin injection. In the present study, we have designed a closed-shell phenalenyl-based iron(III) complex, Fe-III(PLY)(3) (PLY-H = 9-hydroxyphenalenone) displaying an excellent electrocatalytic property as cathode material for one compartment membraneless H2O2 fuel cell. The power density output Of Fe-III(PLY)(3) is nearly 15-fold higher than the structurally related model compound Fe-III(acac)(3) (acac = acetylacetonate) and nearly 140-fold higher than an earlier reported mononuclear Fe(III) complex; Fe-III(Pc)Cl (Pc = pthalocyaninate), highlighting the role of switchable closed-shell phenalenyl moiety for electron-transfer process in designing electroactive materials.

}, issn = {0002-7863}, doi = {10.1021/jacs.5b00272}, author = {Pariyar, Anand and Vijaykumar, Gonela and Bhunia, Mrinal and Dey, Suman Kr. and Singh, Santosh K. and Kurungot, Sreekumar and Mandal, Swadhin K.} } @article {45939, title = {Synthesis and evaluation of thieno[2,3-d]pyrimidin-4(3H)-ones as potential antitubercular agents}, journal = {MedChemComm}, volume = {6}, year = {2015}, month = {AUG}, pages = {2209-2215}, type = {Article}, abstract = {

A number of thieno[2,3-d]pyrimidin-4(3H)-ones were designed, synthesized and screened against Mycobacteria as a part of our program to develop new antitubercular agents. It was observed that some of the compounds have significant antimycobacterial activity against Mycobacterium tuberculosis H37Ra (ATCC 25177) and Mycobacterium bovis BCG (ATCC 35743). The active compounds were studied for cytotoxicity against four cell lines and were found to be non-cytotoxic. The results showed that compounds 13b and 29e were found to exhibit very good antimycobacterial activity (MIC in the range of 6-8 mu M) and the thienopyrimidinones as a class have potential to be developed as antitubercular agents.

}, issn = {2040-2503}, doi = {10.1039/c5md00404g}, author = {Borate, Hanumant B. and Annadate, Ritesh A. and Vagh, Sandip S. and Pisal, Mahesh M. and Deokate, Sagar B. and Arkile, Manisha A. and Jadhav, Nandadeep J. and Nawale, Laxman U. and Sarkar, Dhiman} } @article {43035, title = {Synthesis of N, F and S co-doped graphene quantum dots}, journal = {Nanoscale}, volume = {7}, year = {2015}, month = {MAY}, pages = {11515-11519}, abstract = {

Graphene quantum dots (GQDs) are a promising category of materials with remarkable size dependent properties like tunable bandgap and photoluminescence along with the possibility of effective chemical functionalization. Doping of GQDs with heteroatoms is an interesting way of regulating their properties. Herein, we report a facile and scalable one-step synthesis of luminescent GQDs, substitutionally co-doped with N, F and S, of similar to 2 nm average size by a microwave treatment of multi-walled carbon nanotubes in a customized ionic liquid medium. The use of an ionic liquid coupled with the use of a microwave technique enables not only an ultrafast process for the synthesis of co-doped GQDs, but also provides excellent photoluminescence quantum yield (70\%), perhaps due to the interaction of defect clusters and dopants.

}, author = {Kundu, Sumana and Yadav, Ram Manohar and Narayanan, T. N. and Shelke, Manjusha V. and Vajtai, Robert and Ajayan, Pulickel M. and Pillai, Vijayamohanan K.} } @article { ISI:000362239300030, title = {Systematic comparison of DFT and CCSD dipole moments, polarizabilities and hyperpolarizabilities}, journal = {Chemical Physics Letters}, volume = {635}, year = {2015}, month = {AUG}, pages = {168-173}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

A comparative study of dipole moments, polarizabilities and hyperpolarizabilities of 16 different molecules is performed employing two completely different theoretical approaches namely, density functional theory (DFT) and coupled cluster singles and doubles (CCSD). Both methods include electron correlation. The CCSD method is more accurate but highly expensive. DFT with auxiliary density allows non-iterative solutions which is computational advantage and useful for large molecules. Dipole moments and polarizability calculations from DFT are in very good agreement with CCSD calculations. However, negative hyperpolarizability values from DFT differ significantly from their CCSD counterparts, whereas positive hyperpolarizabilities show reasonable agreement between these methodologies. (C) 2015 Elsevier B.V. All rights reserved.

}, issn = {0009-2614}, doi = {10.1016/j.cplett.2015.06.046}, author = {Karne, Anagha S. and Vaval, Nayana and Pal, Sourav and Vasquez-Perez, Jose M. and Koester, Andreas M. and Calaminici, Patrizia} } @article { ISI:000361649900037, title = {Systematic comparison of DFT and CCSD dipole moments, polarizabilities and hyperpolarizabilities (vol 635, pg 168, 2015)}, journal = {Chemical Physics Letters}, volume = {636}, year = {2015}, month = {SEP}, pages = {228-229}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, issn = {0009-2614}, doi = {10.1016/j.cplett.2015.08.034}, author = {Karne, Anagha S. and Vaval, Nayana and Pal, Sourav and Vasquez-Perez, Jose M. and Koester, Andreas M. and Calaminici, Patrizia} } @article { ISI:000364355500044, title = {Temperature-dependent raman spectroscopy of titanium trisulfide (TiS3) nanoribbons and nanosheets}, journal = {ACS Applied Materials \& Interfaces}, volume = {7}, number = {43}, year = {2015}, month = {NOV}, pages = {24185-24190}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Titanium trisulfide (TiS3) has recently attracted the interest of the 2D community because it presents a direct bandgap of similar to 1.0 eV, shows remarkable photoresponse, and has a predicted carrier mobility up to 10000 cm(2) V-1 s(-1). However, a study of the vibrational properties of TiS3, relevant to understanding the electron-phonon interaction that can be the main mechanism limiting the charge carrier mobility, is still lacking. In this work, we take the first steps to study the vibrational properties of TiS3 through temperature-dependent Raman spectroscopy measurements of TiS3 nanoribbons and nanosheets. Our investigation shows that all the Raman modes linearly soften (red shift) as the temperature increases from 88 to 570 K due to anharmonic vibrations of the lattice, which also includes contributions from the lattice thermal expansion. This softening with the temperature of the TiS3 modes is more pronounced than that observed in other 2D semiconductors, such as MoS2, MoSe2, WSe2, and black phosphorus (BP). This marked temperature dependence of the Raman spectra could be exploited to determine the temperature of TiS3 nanodevices by using Raman spectroscopy as a noninvasive and local thermal probe. Interestingly, the TiS3 nanosheets show a stronger temperature dependence of the Raman modes than the nanoribbons, which we attribute to lower interlayer coupling in the nanosheets.

}, keywords = {2D semiconductors, layered materials, Raman spectroscopy, thermal effect, TiS3 nanoribbons, TiS3 nanosheets}, issn = {1944-8244}, doi = {10.1021/acsami.5b07492}, author = {Pawbake, Amit S. and Island, Joshua O. and Flores, Eduardo and Ramon Ares, Jose and Sanchez, Carlos and Ferrer, Isabel J. and Jadkar, Sandesh R. and van der Zant, Herre S. J. and Castellanos-Gomez, Andres and Late, Dattatray J.} } @article { ISI:000352463200027, title = {Total synthesis of sinenside A}, journal = {Organic Letters}, volume = {17}, number = {7}, year = {2015}, month = {APR}, pages = {1724-1727}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The first total synthesis of norlignan glucoside sinenside A has been accomplished. An intramolecular acetalization reaction has been employed as the key skeletal construct to forge the central cyclic disaccharide core. The trans-1,2-diol configuration present in the cyclic disaccharide of this natural product is unique and has been addressed by setting this configuration at the beginning. A 1,2-orthoester group has been selected as a handle for both sp glycosidation and for differentiation of the C2{\textquoteright}-OH (that participates in the key acetalization reaction) of the sugar unit.

}, issn = {1523-7060}, doi = {10.1021/acs.orglett.5b00505}, author = {Vadhadiya, Paresh M. and Ramana, Chepuri V.} } @article { ISI:000360677400002, title = {Triterpenoid profiling and functional characterization of the initial genes involved in isoprenoid biosynthesis in neem (Azadirachta indica)}, journal = {BMC Plant Biology}, volume = {15}, year = {2015}, month = {SEP}, pages = {Article Number: 214}, publisher = {BIOMED CENTRAL LTD}, address = {236 GRAYS INN RD, FLOOR 6, LONDON WC1X 8HL, ENGLAND}, abstract = {

Background: Neem tree (Azadirachta indica) is one of the richest sources of skeletally diverse triterpenoids and they are well-known for their broad-spectrum pharmacological and insecticidal properties. However, the abundance of Neem triterpenoids varies among the tissues. Here, we delineate quantitative profiling of fifteen major triterpenoids across various tissues including developmental stages of kernel and pericarp, flower, leaf, stem and bark using UPLC-ESI (+)-HRMS based profiling. Transcriptome analysis was used to identify the initial genes involved in isoprenoid biosynthesis. Based on transcriptome analysis, two short-chain prenyltransferases and squalene synthase (AiSQS) were cloned and functionally characterized. Results: Quantitative profiling revealed differential abundance of both total and individual triterpenoid content across various tissues. RNA from tissues with high triterpenoid content (fruit, flower and leaf) were pooled to generate 79.08 million paired-end reads using Illumina GA.. platform. 41,140 transcripts were generated by d e novo assembly. Transcriptome annotation led to the identification of the putative genes involved in isoprenoid biosynthesis. Two short-chain prenyltransferases, geranyl diphosphate synthase (AiGDS) and farnesyl diphosphate synthase (AiFDS) and squalene synthase (AiSQS) were cloned and functionally characterized using transcriptome data. RT-PCR studies indicated five-fold and ten-fold higher relative expression level of AiSQS in fruits as compared to leaves and flowers, respectively. Conclusions: Triterpenoid profiling indicated that there is tissue specific variation in their abundance. The mature seed kernel and initial stages of pericarp were found to contain the highest amount of limonoids. Furthermore, a wide diversity of triterpenoids, especially C-seco triterpenoids were observed in kernel as compared to the other tissues. Pericarp, flower and leaf contained mainly ring-intact triterpenoids. The initial genes such as AiGDS, AiFDS and AiSQS involved in the isoprenoids biosynthesis have been functionally characterized. The expression levels of AiFDS and AiSQS were found to be in correlation with the total triterpenoid content in individual tissues.

}, keywords = {Azadirachta indica, Quantitative profiling, Transcriptome, Triterpenoids}, issn = {1471-2229}, doi = {10.1186/s12870-015-0593-3}, author = {Pandreka, Avinash and Dandekar, Devdutta S. and Haldar, Saikat and Uttara, Vairagkar and Vijayshree, Shinde G. and Mulani, Fayaj A. and Aarthy, Thiagarayaselvam and Thulasiram, Hirekodathakallu V.} } @article { ISI:000358237400019, title = {Tunable acid-base bifunctional catalytic activity of FeOOH in an orthogonal tandem reaction}, journal = {Catalysis Science \& Technology}, volume = {5}, number = {8}, year = {2015}, month = {MAY}, pages = {4029-4038}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

In this report, we have explored the acid-base bifunctional catalytic activity of iron oxohydroxides (FeOOH) by catalyzing deacetalization and Henry condensation reactions successively in a single pot. The crystalline polymorphs of FeOOH, namely goethite (alpha FeOOH), akaganeite (beta FeOOH), lepidocrocite (gamma FeOOH) and delta FeOOH, were chemically prepared and tested for the catalytic activity. All the polymorphs of FeOOH exhibited acid-base bifunctional catalytic activity. The relative selectivity for products varied with the polymorphs of FeOOH. Whereas alpha FeOOH produced benzaldehyde in high yield, the polymorphs beta FeOOH, gamma FeOOH and delta FeOOH showed high selectivity for trans-beta-nitrostyrene. In addition, beta FeOOH also exhibited a unique activity towards the formation of 1,3-dinitro-2-phenylpropane. The difference in the catalytic activity of FeOOH polymorphs was explained based on the strength and density of acidic and basic active sites on the surface. Selectivity for the products was tuned by changing the synthesis parameters of the catalysts and reaction conditions.

}, issn = {2044-4753}, doi = {10.1039/c5cy00361j}, author = {Vernekar, D. and Jagadeesan, Dinesh} } @article {43598, title = {10000-Fold enhancement in proton conduction by doping of cesium ions in a proton-conducting zwitterionic metal-organic framework}, journal = {European Journal of Inorganic Chemistry}, year = {2016}, month = {SEP}, pages = {4382-4386}, abstract = {Developing metal-organic framework (MOF)-based proton-conducting electrolytes for fuel-cell applications is an important target that has drawn a lot of attention. A key approach involves the selective replacement of the guest species within the pores to enhance performance. The modular and crystalline nature of the MOF permits controlled introduction of such species and characterization of their compositions with high precision, a task which is very difficult to achieve in amorphous polymers. Herein, we partially replaced the protons of a zwitterionic pyridinol in Mg(terephthalate)(pyridinol) MOF 1 with Cs+ ions, which brought about a 10000-fold increase in the proton conductivity (10(-6) to 10(-2) S cm(-1)). Interestingly, Li+ ions could not be loaded, whereas Cs+ ions with smaller hydrated ionic radii could be loaded, and the loading was controlled as a function of time. The Cs+ loading nearly halved the activation energy (from 0.35 for 1 to 0.19 eV for _Cs). The highest conductivities were realized for an optimal loading of Cs+ ions, which was found to be about 10 \% in this case.}, doi = {10.1002/ejic.201600364}, author = {Shalini, Sorout and Aggarwal, Shubhangi and Singh, Santosh K. and Dutt, Malvika and Ajithkumar, Thallaseril G. and Vaidhyanathan, Ramanathan} } @article { ISI:000382246400001, title = {1000-fold enhancement in proton conductivity of a MOF using post-synthetically anchored proton transporters}, journal = {Scientific Reports}, volume = {6}, year = {2016}, month = {AUG}, pages = {32489}, publisher = {NATURE PUBLISHING GROUP}, address = {MACMILLAN BUILDING, 4 CRINAN ST, LONDON N1 9XW, ENGLAND}, abstract = {

Pyridinol, a coordinating zwitter-ionic species serves as stoichiometrically loadable and non-leachable proton carrier. The partial replacement of the pyridinol by stronger hydrogen bonding, coordinating guest, ethylene glycol (EG), offers 1000-fold enhancement in conductivity (10(-6) to 10(-3) Scm(-1)) with record low activation energy (0.11 eV). Atomic modeling coupled with C-13-SSNMR provides insights into the potential proton conduction pathway functionalized with post-synthetically anchored dynamic proton transporting EG moieties.

}, issn = {2045-2322}, doi = {10.1038/srep32489}, author = {Shalini, Sorout and Dhavale, Vishal M. and Eldho, Kavalakal Mathai and Kurungot, Sreekumar and Ajithkumar, Thalasseril G. and Vaidhyanathan, Ramanathan} } @article { ISI:000373747700077, title = {Additive mediated syn-anti conformational tuning at nucleation to capture elusive polymorphs: remarkable role of extended pi-stacking interactions in driving the self-assembly}, journal = {Crystal Growth \& Design}, volume = {16}, number = {4}, year = {2016}, month = {APR}, pages = {2416-2428}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Understanding the process of prenucleation clustering at supersaturating stage is of significant importance to envisage the polymorphism in crystalline materials. Preferential formation of a thermodynamically stable crystal form suggests energetically favored patterns of interactions which control molecular aggregation during nucleation. Introduction of additives during crystallization is sometimes used as a suitable strategy to obtain metastable polymorphs in cases where it is not easy to capture the same by conventional crystallization methods. Comparative analysis of energy relationships and intermolecular interactions between thermodynamically stable and metastable crystal forms provides valuable clues about the nature of growth synthons at prenucleation clustering and preferential crystallization of the thermodynamic form. Conformationally flexible sulfonamide/sulfoester derivatives constituting electron rich and electron deficient aromatic rings were synthesized to study the interplay between pi-stacking and hydrogen bonding synthons. We have identified and characterized the thermodynamically stable and metastable elusive polymorphs of aromatic sulfonamides 1 and 2 and sulfoesters 3 and 4. However, these compounds eluded polymorphism during crystallisation from various common solvents/conditions and only produced thermodynamically stable crystals forms (form I crystals). Surprisingly, exploitation of pyrazinamide as an additive in different stoichiometric ratios during crystallization gave elusive polymorphs [three for 1 (form 1II, form 1III, and form 1IV) and one each for 2 (form 2II), 3 (form 3II), and 4 (form 4II)]. Molecules in stable crystal forms of these compounds are linked via extended chains of parallel displaced pi...pi stacking interactions that seem to play a vital role in driving the self-assembly of molecules and subsequently governing the nucleation process. In contrast, molecules in metastable polymorphs are devoid of such extended pi-stacking assemblies. Interestingly, differential scanning calorimetry, hot stage microscopy, and X-ray crystallographic studies confirmed the thermal crystal-to-crystal transition of all three metastable polymorphs of 1 (form 1II, form 1III, and form 1IV) to its thermodynamically stable crystal form (form 1I). Conformational analysis of molecule 1 using density functional theory calculations also validated higher stability for syn conformation (observed in Form 1I crystals) over anti and midway conformations (seen in metastable polymorphs). Melt crystallization of form 1I crystals of 1 on the larger face (001) of delta-pyrazinamide and lattice matching analysis (GRACE) revealed that the layered arrangement of molecules of delta-pyrazinamide (on 001 face) during heterogeneous nucleation acts as a template (heteroepitaxy) to provide a preferential site for the nucleation of new metastable polymorphs by selectively inhibiting the most preferred crystal form from growing into the nucleus. Solution state one- and two-dimensional (NOESY) H-1 NMR, scanning electron microscopy, and a Cambridge Structural Database survey were conducted to substantiate the role of additives during crystallization.

}, issn = {1528-7483}, doi = {10.1021/acs.cgd.6b00204}, author = {Gawade, Rupesh L. and Chakravarty, Debamitra K. and Kotmale, Amol and Sangtani, Ekta and Joshi, Pranaya V. and Ahmed, Awais and Mane, Manoj V. and Das, Susanta and Vanka, Kumar and Rajamohanan, Pattuparambil R. and Puranik, Vedavati G. and Gonnade, Rajesh G.} } @article {43569, title = {Alkyl-chain-separated triphenybenzene - carbazole conjugates and their derived polymers: candidates for sensory, electrical and optical materials}, journal = {Chemistry Select}, volume = {1}, year = {2016}, month = {DEC}, pages = {6649-6657}, abstract = {Four new triphenylbenzene based carbazoles (THPBCz4, THPBCz6, THPBCz8 and THPBCz10) and polycarbazoles (polyTHPBCz4, polyTHPBCz6, polyTHPBCz8 and polyTHPBCz10), have been synthesized. Photoluminescence spectra of the monomers in dichloromethane exhibit two intense bands at 353 and 369 nm. Two additional bands (410 and 435 nm) are also observed due to intermolecular interactions. These bands are more intense in the case of thin films, indicating stronger pp stacking interactions in the solid state. Due to the extended p-conjugation, the polycarbazoles display two main emission bands (495 and 520 nm) which are red shifted as compared to the monocarbazoles. Due to the presence of emissive platforms such as triarylbenzene and carbazole, both monomers and polymers, function as efficient sensors for the detection of polynitroaromatic analytes (PA, DNT, rho-DNB and m-DNB). The electrochemically polymerized carbazole derivatives showed maximum capacitance of 41 F/g for polyTHPBCz6. The SCLC measurement reveals a maximum mobility of 6 x 10(-6) cm(2)/Vs for polyTHPBCz4 that showed better packing due to flexible alkyl chains that connect the conjugated moieties.}, doi = {10.1002/slct.201601428}, author = {Kaleeswaran, D. and Vishnoi, Pratap and Kumar, Subramani and Chithiravel, Sundaresan and Walawalkar, Mrinalini G. and Krishnamoorthy, Kothandam and Murugavel, Ramaswamy} } @article { ISI:000370307800008, title = {Alternate synthesis of appetite suppressant (R)-2-benzylmorpholine employing Sharpless asymmetric epoxidation strategy}, journal = {Tetrahedron Letters}, volume = {57}, number = {8}, year = {2016}, month = {FEB}, pages = {861-863}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

An alternate synthesis of (R)-2-benzylmorpholine 1, an appetite suppressant agent has been accomplished starting from readily available trans-cinnamyl alcohol employing Sharpless asymmetric epoxidation strategy as a key step, with an overall yield of 24\%. (C) 2016 Elsevier Ltd. All rights reserved.

}, keywords = {(R)-2-Benzylmorpholine, Appetite suppressant, Sharpless asymmetric epoxidation}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2016.01.032}, author = {Viswanadh, N. and Mujumdar, P. and Sasikumar, M. and Kunte, S. S. and Muthukrishnan, Murugan} } @article {42844, title = {Au(I)/Ag(I) co-operative catalysis: interception of Ag-bound carbocations with α-gold(I) enals in the imino-alkyne cyclizations with N-allenamides}, journal = {Chemical Communications}, volume = {52}, year = {2016}, month = {NOV}, pages = {14462-14465}, doi = {10.1039/C6CC08385D}, author = {Bagle, Pradip N. and Mane, Manoj V. and Vanka, Kumar and Shinde, Dinesh R. and Shaikh, Samir R. and Gonnade, Rajesh G. and Patil, Nitin T.} } @article {43410, title = {Building and analysis of protein-protein interactions related to diabetes mellitus using support vector machine, biomedical text mining and network analysis}, journal = {Computational Biology and Chemistry}, volume = {65}, year = {2016}, month = {DEC}, pages = {37-44}, abstract = {In order to understand the molecular mechanism underlying any disease, knowledge about the interacting proteins in the disease pathway is essential. The number of revealed protein-protein interactions (PPI) is still very limited compared to the available protein sequences of different organisms. Experiment based high-throughput technologies though provide some data about these interactions, those are often fairly noisy. Computational techniques for predicting protein protein interactions therefore assume significance. 1296 binary fingerprints that encode a combination of structural and geometric properties were developed using the crystallographic data of 15,000 protein complexes in the pdb server. In a case study, these fingerprints were created for proteins implicated in the Type 2 diabetes mellitus disease. The fingerprints were input into a SVM based model for discriminating disease proteins from non disease proteins yielding a classification accuracy of 78.2\% (AUC value of 0.78) on an external data set composed of proteins retrieved via text mining of diabetes related literature. A PPI network was constructed and analysed to explore new disease targets. The integrated approach exemplified here has a potential for identifying disease related proteins, functional annotation and other proteomics studies. (C) 2016 Elsevier Ltd. All rights reserved.}, doi = {10.1016/j.compbiolchem.2016.09.011}, author = {Vyas, Renu and Bapat, Sanket and Jain, Esha and Karthikeyan, Muthukumarasamy and Tambe, Sanjeev and Kulkarni, Bhaskar D.} } @article {43584, title = {Calculation of hyperfine structure constants of small molecules using Z-vector method in the relativistic coupled-cluster framework}, journal = {Journal of Chemical Sciences}, volume = {128}, year = {2016}, month = {OCT}, pages = {1671-1675}, abstract = {The Z-vector method in the relativistic coupled-cluster framework is employed to calculate the parallel and perpendicular components of the magnetic hyperfine structure constant of a few small alkaline earth hydrides (BeH, MgH, and CaH) and fluorides (MgF and CaF). We have compared our Z-vector results with the values calculated by the extended coupled-cluster (ECC) method reported in Phys. Rev. A 91 022512 (2015). All these results are compared with the available experimental values. The Z-vector results are found to be in better agreement with the experimental values than those of the ECC values.}, doi = {10.1007/s12039-016-1174-1}, author = {Sasmal, Sudip and Talukdar, Kaushik and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article { ISI:000373630800014, title = {Can main group systems act as superior catalysts for dihydrogen generation reactions? A computational investigation}, journal = {Dalton Transactions}, volume = {45}, number = {14}, year = {2016}, month = {JUN}, pages = {5968-5977}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

The protolytic cleavage of the O-H bond in water and alcohols is a very important reaction, and an important method for producing dihydrogen. Full quantum chemical studies with density functional theory (DFT) reveal that germanium based complexes, such as HC{CMeArB}(2)GeH (Ar = 2,6-(Pr2C6H3)-Pr-i), with the assistance of silicon based compounds such as SiF3H, can perform significantly better than the existing state-of-the-art post-transition metal based systems for catalyzing dihydrogen generation from water and alcohols through the protolysis reaction.

}, issn = {1477-9226}, doi = {10.1039/c5dt01058f}, author = {Kuriakose, Nishamol and Vanka, Kumar} } @article { ISI:000372169700020, title = {Characteristics of precipitation pattern in the Arabian Peninsula and its variability associated with ENSO}, journal = {Arabian Journal of Geosciences}, volume = {9}, number = {3}, year = {2016}, month = {MAR}, pages = {186}, publisher = {SPRINGER HEIDELBERG}, address = {TIERGARTENSTRASSE 17, D-69121 HEIDELBERG, GERMANY}, abstract = {

A detailed analysis of the precipitation pattern of the Arabian Peninsula and its temporal and spatial variability were investigated in connection with ENSO. Also, the variability of precipitable water and circulation characteristics was examined for a better understanding. The study was carried out utilizing TRMM rainfall, NOAA OLR, precipitable water, wind, and humidity data sets. It is evident that Northern Arabian Peninsula receives high amount of rainfall mainly during winter and early summer (November to April) in connection with the passage of mid tropospheric westerly troughs and Mediterranean low-pressure systems. But the precipitation pattern over the Southern Arabian Peninsula reveals that it is mainly during summer (May to October) due to the Arabian Sea branch of monsoon and moisture laden cross equatorial LLJ flow. Further, analysis was carried out to assess the influence of ENSO on the precipitation pattern. Thorough analysis was carried out on the circulation pattern using velocity potential in the lower troposphere to understand the features of variability on Hadley/Walker circulation in relation with organized convection. El Nino and La Nina have profound influence on the rainfall pattern in a different manner in the Northern and Southern Arabian Peninsula. Large-scale circulation pattern as derived from velocity potential indicates that shifting of the rising/sinking limb of Hadley/Walker circulation associated with the ENSO causes variability in precipitation.

}, keywords = {Arid region, Circulation, El Nino and La Nina, Precipitation pattern}, issn = {1866-7511}, doi = {10.1007/s12517-015-2265-x}, author = {Babu, C. A. and Jayakrishnan, P. R. and Varikoden, Hamza} } @conference {45847, title = {Characterizing flow and solid suspension in optimax crystallization workstation}, booktitle = {North American Mixing Forum 2016 - Core Programming Area at the 2016 AIChE Annual Meeting}, year = {2016}, month = {NOV}, publisher = {AIChE}, organization = {AIChE}, address = {San Francisco; United States}, isbn = {978-151083442-2}, url = {https://www.scopus.com/record/display.uri?eid=2-s2.0-85019102692\&origin=inward\&txGid=820eae9eac7a8eac5ea31078647c0e4f}, author = {Sardeshpande, M. and Pandit, A. and Vedantam, S. and Ranade, V. V.} } @article {43400, title = {ChemEngine: harvesting 3D chemical structures of supplementary data from PDF files}, journal = {Journal of Cheminformatics}, volume = {8}, year = {2016}, month = {DEC}, pages = {Article Number: 73}, abstract = {Digital access to chemical journals resulted in a vast array of molecular information that is now available in the supplementary material files in PDF format. However, extracting this molecular information, generally from a PDF document format is a daunting task. Here we present an approach to harvest 3D molecular data from the supporting information of scientific research articles that are normally available from publisher{\textquoteright}s resources. In order to demonstrate the feasibility of extracting truly computable molecules from PDF file formats in a fast and efficient manner, we have developed a Java based application, namely ChemEngine. This program recognizes textual patterns from the supplementary data and generates standard molecular structure data (bond matrix, atomic coordinates) that can be subjected to a multitude of computational processes automatically. The methodology has been demonstrated via several case studies on different formats of coordinates data stored in supplementary information files, wherein ChemEngine selectively harvested the atomic coordinates and interpreted them as molecules with high accuracy. The reusability of extracted molecular coordinate data was demonstrated by computing Single Point Energies that were in close agreement with the original computed data provided with the articles. It is envisaged that the methodology will enable large scale conversion of molecular information from supplementary files available in the PDF format into a collection of ready-to-compute molecular data to create an automated workflow for advanced computational processes.}, doi = {10.1186/s13321-016-0175-x}, author = {Karthikeyan, Muthukumarasamy and Vyas, Renu} } @article { ISI:000374920400016, title = {CO oxidation on large high-index faceted Pd nanostructures}, journal = {Journal of Catalysis}, volume = {337}, year = {2016}, month = {MAY}, pages = {138-144}, publisher = {ACADEMIC PRESS INC ELSEVIER SCIENCE}, address = {525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USA}, abstract = {

The structure sensitivity of CO oxidation has been investigated on oxide-supported palladium nanoparticles of different morphologies. The reactivity of concave nanocubes and nanoflowers that expose {3 1 0} and {3 1 1} high-index facets showed a lower onset temperature for CO oxidation than Pd nanospheres of size around 6 nm. These concave nanocubes and nanoflowers were also found to catalyze the CO oxidation reaction more efficiently than simple cubes and spheres of similar size that exposed low-index facets. The enhanced activity of these nanoparticles compared with other morphologies are attributed to the presence of sites of under-coordination on the exposed high-index facets. The larger nanoparticles were also found to be more stable in the reaction environment. (C) 2016 Elsevier Inc. All rights reserved.

}, keywords = {CO oxidation, High-index facets, Pd nanoparticles, structure sensitivity}, issn = {0021-9517}, doi = {10.1016/j.jcat.2016.01.017}, author = {Sreedhala, S. and Sudheeshkumar, V. and Vinod, C. P.} } @article {43425, title = {CO2 Laser direct written MOF-based metal-decorated and heteroatom-doped porous graphene for flexible all-solid-state microsupercapacitor with extremely high cycling stability}, journal = {ACS Applied Materials \& Interfaces}, volume = {8}, year = {2016}, month = {NOV}, pages = {31841-31848}, abstract = {Over the past decade, flexible and wearable microelectronic devices and systems have gained significant importance. Because portable power source is an essential need of such wearable devices, currently there is considerable research emphasis on the development of planar interdigitated micro energy-torage devices by employing diverse precursor materials to obtain functional materials (functional carbon, oxides, etc.) with the desirable set of properties. Herein we report for the first time the use of metal organic framework (MOF) and zeolitic imidazolate framework (ZIF-67) for high-wavelength photothermal laser direct writing of metal-decorated, heteroatom-doped, porous few-layer graphene electrodes for microsupercapacitor application. We argue that the specific attributes of MOF as a precursor and the high-wavelength laser writing approach (which creates extremely high localized and transient temperature (>2500 degrees C) due to strong absorption by lattice vibrations) are together responsible for the peculiar interesting properties of the carbon material thus synthesized, thereby rendering extremely high cycling stability to the corresponding microsupercapacitor device. Our device exhibits near 100\% retention after 200 000 cycles as well as stability under 150 degrees bending.}, doi = {10.1021/acsami.6b10193}, author = {Basu, Aniruddha and Roy, Kingshuk and Sharma, Neha and Nandi, Shyamapada and Vaidhyanathan, Ramanathan and Rane, Sunit and Rode, Chandrashekhar V. and Ogale, Satishchandra B.} } @article { ISI:000373408800021, title = {Concise enantioselective synthesis of (+)-sertraline and (-)-CP-52002 using proline catalysis}, journal = {Tetrahedron Letters}, volume = {57}, number = {9}, year = {2016}, month = {MAR}, pages = {1053-1055}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

A short enantioselective synthesis of (+)-sertraline and its C-4 epimer (-)-CP-52002 with an overall yield of 30\%, respectively, as its hydrochloride has been described. The key steps are the proline catalyzed Mannich reaction of acetaldehyde and acid catalyzed intramolecular Friedel-Crafts{\textquoteright} alkylation reaction of olefin proceeding with high optical purities. (C) 2016 Elsevier Ltd. All rights reserved.

}, keywords = {Indatraline, Mannich reaction, Proline catalysis, Sertraline, Tametraline}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2016.01.085}, author = {Kalshetti, Rupali G. and Venkataramasubramanian, V. and Kamble, Sanjay P. and Sudalai, Arumugam} } @article { ISI:000373408600014, title = {Correlating the role of hydrophilic/hydrophobic nature of Rh(I) and Ru(II) supported organosilica/silica catalysts in organotransformation reactions}, journal = {Applied Catalysis A-General}, volume = {513}, year = {2016}, month = {MAR}, pages = {138-146}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Highly reactive and hydrophobic triphenyl phosphine based rhodium(I) and ruthenium(II) organometallic complexes over benzene containing periodic mesoporous organosilica (PMOB) have been synthesized. This has been achieved by the immobilization of neat metal complexes like RhCl(PPh3)(3) [Wilkinson catalyst], RuHCl(CO)(PPh3)(3) and RuCl2(PPh3)(3) over aminofunctionalized PMOB to get RhCl(PPh3)(2)-PrNH2PMOB, RuHCl(CO)(PPh3)(2)-PrNH2PMOB and RuCl2(PPh3)(3)-PrNH2PMOB, respectively. The physico-chemical properties of the functionalized catalysts were analyzed by elemental analysis, ICP-OES, XRD, N-2 sorption analyses, FT-IR, solid state C-13 and Si-29 NMR spectra, XPS, SEM, TEM and contact angle measurements. The XRD and N-2 sorption analyses showed excellent textural properties with ordered mesoporous channel structure of all synthesized catalysts. The organic moieties anchored in PMOB were confirmed by C-13 CPMAS NMR and Fr-IR spectroscopy with Si-29 CPMAS NMR spectroscopy providing the information about the degree of functionalization of surface silanol groups with organic moiety. The Rh(I) and Ru(II) complexes supported on MCM-41/SBA-15/PMOE (ethane-PMO) were synthesized, and their catalytic activities in hydrogenation and sulfoxidation reactions were compared with Rh(I) and Ru(II) complexes supported on PMOB. The results show that PMOB based catalysts exhibit higher activities and selectivities than MCM-41/SBA-15/PMOB supported catalysts, neat homogeneous complexes and without catalyst. The better catalytic performance of PMOB based catalyst is attributed to the hydrophobic nature and high surface area of the PMOB support. The recycling studies of anchored catalysts show no major deactivation of the catalyst. (C) 2015 Elsevier B.V. All rights reserved.

}, keywords = {Heterogeneous catalysts, Hydrogenation and sulfoxidation, Hydrophobic, Periodic mesoporous organosilica}, issn = {0926-860X}, doi = {10.1016/j.apcata.2015.12.026}, author = {Lazar, Anish and George, Shoy C. and Jithesh, P. R. and Vinod, C. P. and Singh, A. P.} } @article {43014, title = {Culture conditions for the production of thermostable lipase by thermomyces lanuginosus}, journal = {Journal of Basic and Applied Sciences}, year = {2016}, month = {NOV}, abstract = {

In the present investigation lipase production by three strains of thermophilic Thermomyces lanuginosus (GSLMBKU-10, GSLMBKU-13 and GSLMBKU-14) was carried out in submerged fermentation process. Olive oil and triacetin (0.1\%) were added to the basal medium, which stimulated the lipase production. The maximum lipase was produced by GSLMBKU-10 and GSLMBKU-13 in yeast extract starch medium supplemented with triacetin (0.1\%). The optimum pH was recorded at 6.0, 6.5 and 7.0 by GSLMBKU-10, GSLMBKU-13 and GSLMBKU-14 respectively. T. lanuginosus GSLMBKU-10 strains failed to produce lipase at pH 8.0. The optimum temperature for lipase production was observed at 45 {\textdegree}C by GSLMBKU-14 and GSLMBKU-10, while that for GSLMBKU-13 was at 50 {\textdegree}C. The marginal temperature ranged from 45 {\textdegree}C to 50 {\textdegree}C for both lipase production and vegetative growth by the three strains of T. lanuginosus under study. In conclusion, the GSLMBKU-13 strain was comparatively superior in the production of lipase than the other two strains under investigation.

}, doi = {10.1016/j.bjbas.2016.11.010}, author = {Sreelatha, B. and Vankudoth, Koteswara Rao and Kumar, R. Ranjith and Girisham, Sivadevuni and Reddy, S. M.} } @article {43622, title = {Cutaneous exposure to clinically-relevant pigeon pea (Cajanus cajan) proteins promote T(H)2-dependent sensitization and IgE-mediated anaphylaxis in Balb/c mice}, journal = {Journal of Immunotoxicology}, volume = {13}, year = {2016}, month = {JAN}, pages = {827-841}, abstract = {Epicutaneous (EC) sensitization to food allergens may occur when the skin has been lightly damaged. The study here tested whether cutaneous exposure to pigeon pea protein(s) may cause allergic sensitization. BALB/c mice were either orally gavaged or epicutaneously sensitized by repeated application of pigeon pea crude protein extract (CPE) on undamaged areas of skin without any adjuvant; afterwards, both groups were orally challenged with the pigeon pea CPE. Anaphylactic symptoms along with measures of body temperature, MCPT-1, TSLP, pigeon pea-specific IgE and IgG(1), myeloperoxidase (MPO) activity, T(H)2 cytokines, T(H)2 transcription factors (TFs) and filaggrin expression were determined. Mast cell staining, eosinophil levels and histopathological analysis of the skin and intestines were also performed. In the epicutaneously-sensitized mice, elevated levels of specific IgE and IgG(1), as well as of MCPT-1, TSLP, T(H)2 cytokines and TFs, higher anaphylactic scores and histological changes in the skin and intestine were indicative of sensitization ability via both routes in the pigeon pea CPE-treated hosts. Elevated levels of mast cells were observed in both the skin and intestine; increased levels of eosinophils and MPO activity were noted only in the skin. Decreased levels of filaggrin in skin may have played a key role in the skin barrier dysfunction, increasing the chances of sensitization. Therefore, the experimental data support the hypothesis that in addition to oral exposure, skin exposure to food allergens can promote T(H)2-dependent sensitization, IgE-mediated anaphylaxis and intestinal changes after oral challenge. Based on this, an avoidance of cutaneous exposures to allergens might prevent development of food anaphylaxis.}, doi = {10.1080/1547691X.2016.1205159}, author = {Gupta, Rinkesh Kumar and Kumar, Sandeep and Gupta, Kriti and Sharma, Akanksha and Roy, Ruchi and Verma, Alok Kumar and Chaudhari, Bhushan P. and Das, Mukul and Ansari, Irfan Ahmad and Dwivedi, Premendra D.} } @article {43030, title = {Decoding the morphological diversity in two dimensional crystalline porous polymers by core planarity modulation}, journal = {Angewandte Chemie - International Edition}, volume = {55}, year = {2016}, month = {JUN}, pages = {7806-7810}, doi = {10.1002/anie.201600087}, author = {Halder, Arjun and Kandambeth, Sharath and Biswal, Bishnu P. and Kaur, Gagandeep and Roy, Neha Chaki and Addicoat, Matthew A. and Salunke, Jagadish K. and Banerjee, Subhrashis and Vanka, Kumar and Heine, Thomas and Verma, Sandeep and Banerjee, Rahul} } @article {42942, title = {Design, synthesis and biological evaluation of novel azaspiro analogs of linezolid as antibacterial and antitubercular agents}, journal = {European Journal of Medicinal Chemistry}, volume = {122}, year = {2016}, month = {OCT}, pages = {475-487}, abstract = {

The design, synthesis and antimicrobial evaluation of a novel series of azaspiro analogues of linezolid (1) have been described. Linezolid comprises of a morpholine ring which is known for its metabolism related liabilities. Therefore, the key modification made in the linezolid structure was the replacement of morpholine moiety with its bioisostere, 2-oxa-6-azaspiro[3.3]heptane. Furthermore, the replacement of N-acetyl terminal of 1 with various aromatic or aliphatic functionalities was carried out. The title compounds were evaluated against a panel of Gram-positive and Gram-negative bacteria and Mycobacterium tuberculosis. Subsequent structure-activity relationship (SAR) studies identified several compounds with mixed antibacterial and antitubercular profiles. Compound 22 (IC50 0.72, 0.51, 0.88, 0.49 mu g/mL for Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus subtilis, respectively) exhibited similar antibacterial profile as I. The N-acetyl derivative 18 was similar to 1 in antitubercular profile. Thus, the present study successfully demonstrated the use of azaspiro substructure in the medicinal chemistry of antibacterial and antitubercular agents. (C) 2016 Elsevier Masson SAS. All rights reserved.

}, doi = {10.1016/j.ejmech.2016.07.001}, author = {Gadekar, Pradip K. and Roychowdhury, Abhijit and Kharkar, Prashant S. and Khedkar, Vijay M. and Arkile, Manisha A. and Manek, Hardik and Sarkar, Dhiman and Sharma, Rajiv and Vijayakumar, V. and Sarveswari, S.} } @article { ISI:000372848000021, title = {Disruption of native beta-turns: consequence of folding competition between native and orthanilic acid proline-based pseudo beta-turn}, journal = {European Journal of Organic Chemistry}, number = {7}, year = {2016}, month = {MAR}, pages = {1380-1388}, publisher = {WILEY-V C H VERLAG GMBH}, address = {POSTFACH 101161, 69451 WEINHEIM, GERMANY}, abstract = {

Five tetrapeptides comprising beta-turn-forming elements and a pseudo beta-turn (C9 H-bonding) based on an SAntPro (orthanilic acid - proline) motif were designed and synthesized. Their extensive conformational investigation by single-crystal X-ray crystallography, solution-state 2D NMR spectroscopic, and nOe-restrained MD simulation studies revealed the formation of C14 or C9 folding and disruption of the native beta-turn (C10 H-bonding) architecture. The striking difference between the psi(psi(2)) angle of {\textquoteleft}{\textquoteleft}i + 2{\textquoteright}{\textquoteright} residues of native beta-turn and designed peptides suggest that formation of the native beta-turn is not favored. The results suggest that other turn-forming motifs can dramatically modulate the stability of the native beta-turn structure.

}, keywords = {Conformation analysis, hydrogen bonds, Peptidomimetics, structure elucidation}, issn = {1434-193X}, doi = {10.1002/ejoc.201501558}, author = {Ingole, Tukaram S. and Vijayadas, Kuruppanthara N. and Chaitanya, K. N. and Kotmale, Amol S. and Gawade, Rupesh L. and Gonnade, Rajesh G. and Rajamohanan, P. R. and Sanjayan, Gangadhar J.} } @article {43389, title = {Dynamic, reversible oxidative addition of highly polar bonds to a transition metal}, journal = {Journal of the American Chemical Society}, volume = {138}, year = {2016}, month = {DEC}, pages = {16140-16147}, abstract = {The combination of Pt complexes and indium trihalides leads to compounds that form equilibria in solution between their In X oxidative addition (OA) products (Pt indyl complexes) and their metal-only Lewis pair (MOLP) isomers (LnPt -> InX3). The position of the equilibria can be altered reversibly by changing the solvent, while the equilibria can be reversibly and irreversibly driven toward the MOLP products by addition of further donor ligands. The results mark the first observation of an equilibrium between MOLP and OA isomers, as well as the most polar bond ever observed to undergo reversible oxidative addition to a metal complex. In addition, we present the first structural characterization of MOLP and oxidative addition isomers of the same compound. The relative energies of the MOLP and OA isomers were calculated by DFT methods, and the possibility of solvent-mediated isomerization is discussed.}, doi = {10.1021/jacs.6b10609}, author = {Bertermann, Ruediger and Boehnke, Julian and Braunschweig, Holger and Dewhurst, Rian D. and Kupfer, Thomas and Muessig, Jonas H. and Pentecost, Leanne and Radacki, Krzysztof and Sen, Sakya S. and Vargas, Alfredo} } @article { ISI:000376330800049, title = {Earth abundant iron-rich N-doped graphene based spacer and cavity materials for surface plasmon-coupled emission enhancements}, journal = {ACS Applied Materials \& Interfaces}, volume = {8}, number = {19}, year = {2016}, month = {MAY}, pages = {12324-12329}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

We demonstrate for the first time the use of Fe based nanoparticles on N-doped graphene as spacer and cavity materials and study their plasmonic effect on the spontaneous emission of a radiating dipole. Fe-C-MF was produced by pyrolizing FeOOH and melamine formaldehyde precursor on graphene, while Fe-C-PH was produced by pyrolizing the Fe-phenanthroline complex on graphene. The use of the Fe-C-MF composite consisting of Fe-rich crystalline phases supported on N-doped graphene presented a spacer material with 116-fold fluorescence enhancements. On the other hand, the Fe-C-PH/Ag based cavity resulted in an 82-fold enhancement in Surface Plasmon-Coupled Emission (SPCE), with high directionality and polarization of Rhodamine 6G (Rh6G) emission owing to Casimir and Purcell effects. The use of a mobile phone as a cost-effective fluorescence detection device in the present work opens up a flexible perspective for the study of different nanomaterials as tunable substrates in cavity mode and spacer applications.

}, keywords = {Casimir effect, fluorescence enhancements, iron carbides, N-doped graphene, Purcell factor, surface plasmon-coupled emission}, issn = {1944-8244}, doi = {10.1021/acsami.5b12038}, author = {Srinivasan, Venkatesh and Vernekar, Dnyanesh and Jaiswal, Garima and Jagadeesan, Dinesh and Ramamurthy, Sai Sathish} } @article { ISI:000379531300011, title = {Effect of donors on the activation mechanism in ziegler-natta catalysis: a computational study}, journal = {Chemcatchem}, volume = {8}, number = {10}, year = {2016}, month = {MAY}, pages = {1809-1818}, publisher = {WILEY-V C H VERLAG GMBH}, address = {POSTFACH 101161, 69451 WEINHEIM, GERMANY}, abstract = {

Full quantum chemical calculations, using density functional theory (DFT), have been conducted to explain the effect of donors on the {\textquoteleft}{\textquoteleft}activation mechanism{\textquoteright}{\textquoteright} in the Ziegler-Natta (Z-N) catalyst system. In the activation mechanism, the inactive (TiCl4)-Cl-IV catalyst converts into the active (TiCl2Et)-Cl-III catalyst with the help of the AlEt3 present in the system. The donors that have been considered in this study are: ethyl benzoate (eb), two representative diether cases, a phthalate donor, and a silyl ester donor. The results indicate that eb and the diether donor cases donor have a negative effect on the barriers for the activation mechanism. However, the eb donor can be displaced from the MgCl2 surface by AlEt3, which matches experimental observations. For the phthalate, silyl ester and TiCl3-OC4H8Cl cases, the results indicate that a significant induction period would be present in Z-N systems employing such donors or having such a catalytic center, before catalysis could commence.

}, keywords = {Alkylation, aluminum, Density functional calculations, surface chemistry, titanium}, issn = {1867-3880}, doi = {10.1002/cctc.201600281}, author = {Kumawat, Jugal and Gupta, Virendra Kumar and Vanka, Kumar} } @article {43394, title = {Effect of mixed acid catalysis on pretreatment and enzymatic digestibility of sugar cane bagasse}, journal = {Energy \& Fuels}, volume = {30}, year = {2016}, month = {SEP}, pages = {7310-7318}, abstract = {Aqueous pretreatment using homogeneous acid catalyst is considered as a low-cost technology in the production of lignocellulosic bioethanol. To establish the synergism of mixed acids, pilot-level aqueous pretreatments of bagasse covering a wide range of combined severity (CS) were carried out. To investigate the effect of application of mixture of acids on xylose hydrolysis as well as glucose hydrolysis via pretreatment and enzymatic hydrolysis, the following three combinations of acids were explored: (1) oxalic acid + sulfuric acid (organic + mineral acid), (2) phosphoric + sulfuric acid (mineral acids), and (3) ferric chloride + sulfuric acid (Lewis acid with a mineral acid). Of the pretreatments evaluated, the synergism was most pronounced for the combination of sulfuric and phosphoric acid, which resulted in more than 90\% conversion of hemicellulose to xylose and 70\% conversion of cellulose to glucose through enzymatic hydrolysis. Fourier transform infrared (FTIR) studies of pretreated samples showed higher syringyl/guaiacyl (S/G) ratio for sulfuric and phosphoric acid combination pretreatment, leading to higher enzymatic conversion. FTIR and dynamic light scattering (DLS) experiments conducted on pretreated sugar cane bagasse provided useful correlation with regard to the pretreatment type, particle size, and enzymatic hydrolysis.}, doi = {10.1021/acs.energyfuels.6b01011}, author = {Pal, Siddhartha and Joy, Shereena and Kumbhar, Pramod and Trimukhe, K. D. and Varma, Anjanikumar and Padmanabhan, Sasisanker} } @article {43311, title = {Effect of out-of-plane alkyl group{\textquoteright}s position in dye-sensitized solar cell efficiency: a structure-property relationship utilizing indoline-based unsymmetrical squaraine dyes}, journal = {ACS Applied Materials \& Interfaces}, volume = {8}, year = {2016}, month = {DEC}, pages = {35353-35367}, abstract = {

Squaraine dyes are promising chromophores to harvest visible and near-infrared (NIR) photons. A series of indoline-based unsymmetrical squaraine (SQ) dyes that contain alkyl chains at sp(3) C- and N- atoms of indoline moieties with a carboxylic acid anchoring group were synthesized. The optical and electrochemical properties of the SQ dyes in solution were nearly identical as there was no change in the D-A-D SQ framework; however, remarkable changes with respect to the power conversion efficiencies (PCE) were observed depending upon the position of alkyl groups in the dye. Introduction of alkyl groups to the indoline unit that was away from anchoring unit were helped in more dye loading with controlled organization of dyes on surface, increased charge transfer resistance, long electron lifetime, and hence higher PCE than that of the corresponding isomer in which the alkyl groups funtionalized indoline unit contains the carboxylic acid anchoring group. Careful analysis of incident photon-to current conversion efficiency (IPCE) profiles indicated the presence of aggregated structure on the TiO2 surface that contributes to the charge injection in the presence of a coadsorbent. A dye-sensitized solar cell (DSSC) device made out of SQ5 was achieved an efficiency of 9.0\%, with an open-circuit potential (V-oc) of 660 mV and short-circuit current density (J(sc)) of 19.82 mA/cm 2, under simulated AM 1.5G illumination (100 mW/cm(2)). The IPCE profile of SQ5 shows an onset near to 750 nm with a good quantum efficiency (\>80\%) in the range of 550-700 nm, indicating the importance of self-organization of dyes on the TiO2 surface for an efficient charge injection. This present investigation revealed the importance of position of alkyl groups in the squaraine-based dyes for the better PCE.

}, doi = {10.1021/acsami.6b12730}, author = {Alagumalai, Ananthan and Fairoos, Munavvar M. K. and Vellimalai, Punitharasu and Sil, Manik Chandra and Nithyanandhan, Jayaraj} } @article {42853, title = {Effective and selective oxidation of 2-butanol over Mn supported catalyst systems}, journal = {Applied Catalysis A-General}, volume = {525}, year = {2016}, month = {SEP}, pages = {237-246}, abstract = {

Oxidation of alcohols to their corresponding aldehydes/ketones is an important reaction in industries as well as in academic perspective. Selective oxidation (Selox) of alcohols like methanol, ethanol and propanol are well studied in literature; however, alcohols like butanol, pentanol, octanol is a challenging task. Selective oxidation of 2-butanol to methyl ethyl ketone (MEK) is an important reaction due to its wide range of applications. Herein, we demonstrated the selective oxidation of 2-butanol to MEK over Mn supported on different oxide supports. A series of MnxOy-Al2O3 (MA), MnxOy-CeO2 (MC), MnxOy-ZrO2 (MZ) and MnxOy-SiO2 (MS) catalysts were prepared by co-precipitation followed by hydrothermal method. As synthesised catalysts were characterised by various physico-chemical characterisation techniques. It was found that the presence of Mn3O4 species in MA and MZ catalysts is responsible for maximum catalytic activity towards 2-butanol oxidation. MA catalyst conferred a maximum 2-butanol conversion of 51\% and 88\% selectivity towards MEK. XPS analysis revealed that Mn in MA catalyst exists in +2 and +3 oxidation states and responsible for 2-butanol oxidation. Moreover it was found that the acidity of the catalyst also plays an important role in catalytic activity. (C) 2016 Published by Elsevier B.V.

}, doi = {10.1016/j.apcata.2016.08.005}, author = {Prabu, Kandasamy and Prabu, Marimuthu and Venugopal, Ashok Kumar and Venugopalan, Aswathy Thareparambil and Sandilya, W. V. Y. Sai and Gopinath, Chinnakonda S. and Raja, Thirumalaiswamy} } @article {43395, title = {Effects of thermal treatment of ZnO-ZnCr2O4 catalyst on the particle size and product selectivity in dehydrocyclization of crude glycerol and ethylenediamine}, journal = {Kinetics and Catalysis}, volume = {57}, year = {2016}, month = {SEP}, pages = {602-609}, abstract = {The ZnO-ZnCr2O4 (Zn-Cr-O) sample obtained by decomposition of Zn-Cr hydrotalcite precursor was subjected to the thermal treatment at different temperatures and the physico-chemical properties of the Zn-Cr-O system were compared with its catalytic behavior in dehydrocyclization of crude glycerol and ethylenediamine (EDA). Upon high temperature treatment of Zn-Cr-O the Cr6+ ions underwent autoreduction to form stable Cr3+ species and the particle size of both ZnO and ZnCr2O4 increased dramatically. Thermal effect did not influence the intermolecular cyclisation of EDA to form pyrazine. By contrast, an inversely proportional dependence was found between the rate of formation of 2-methylpyrazine and the particle size of Zn-Cr-O whereas the rate of 2-pyrazinylmethanol was directly proportional to the particle size.}, doi = {10.1134/S0023158416050177}, author = {Sarkari, Reema and Krishna, Vankudoth and Sudhakar, Medak and Rao, Tumula Venkateshwar and Padmasri, Aytam Hari and Srinivas, Darbha and Venugopal, Akula} } @article { ISI:000377424600004, title = {Efficient cellular entry of (r-x-r)-type carbamate-plasmid DNA complexes and its implication for noninvasive topical DNA delivery to skin}, journal = {Molecular Pharmaceutics}, volume = {13}, number = {6}, year = {2016}, month = {JUN}, pages = {1779-1790}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Arginine-rich cell penetrating peptides are powerful tools for in vitro as well as in vivo delivery of a wide plethora of biomolecules. However, presence of consecutive arginine residues leads to enhanced amenability for proteolytic degradation as well as steric hindrances for membrane interactions which compromise its bioavailability. In order to overcome these limitations we previously reported a safe and stable octaarginine based oligomer, i.e., (r-x-r)4-carbamate, where the backbone amide linkages were replaced by carbamate linkages and 6-aminohexanoic acid based spacer moieties were incorporated for better flexibility, hydrophobicity, optimal spacing of guanidinium groups, and protection against proteolytic cleavage; resulting in improved transfection efficiency over its amide counterpart. In the present work we have investigated the mechanism behind this enhanced transfection efficiency and, based on our observations, demonstrate how the synergistic effect of rationalized oligomer designing, complex characteristics, and cell type contributes to overall effective intracellular delivery. Our results indicate that the (r-x-r)4-carbamate plasmid DNA complexes primarily utilize lipid raft dependent pathway of cellular entry more than other pathways, and this possibly facilitates their increased entry in the lipid raft rich milieu of skin cells. We also emphasize the utility of oligomer (r-x-r)4-carbamate as an efficient carrier for topical delivery of nucleic acids in skin tissue. This carrier can be utilized for safe, efficient, and noninvasive delivery of therapeutically relevant macromolecular hydrophilic cargo like nucleic acids to skin.

}, keywords = {Cell penetrating peptides, endocytosis, nucleic acid delivery, skin penetration, transfection}, issn = {1543-8384}, doi = {10.1021/acs.molpharmaceut.5b00915}, author = {Vij, Manika and Natarajan, Poornemaa and Yadav, Amit K. and Patil, Kiran M. and Pandey, Tanuja and Gupta, Nidhi and Santhiya, Deenan and Kumar, Vaijayanti A. and Fernandes, Moneesha and Ganguli, Munia} } @article { ISI:000379102600099, title = {Enhanced clathrate hydrate formation kinetics at near ambient temperatures and moderate pressures: Application to natural gas storage}, journal = {Fuel}, volume = {182}, year = {2016}, month = {OCT}, pages = {907-919}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

SNG (solidified natural gas) technology via clathrate hydrates is a potential method for large scale stationary storage of natural gas. Clathrate hydrate formation kinetics in presence of methane and 5.6 mol\% tetrahydrofuran (THF) was investigated in an unstirred reactor configuration at moderate pressure and temperature conditions. It is well known that the presence of THF generally improves the thermodynamic stability of the resulting hydrate. In order to study the scale-up potential of this approach, kinetics of hydrate growth at temperatures close to ambient conditions and moderate pressures is required. Hydrate formation experiments were performed at three different temperatures - 283.2 K, 288.2 K and 293.2 K and at experimental pressures of 7.2 MPa, 5.0 and 3.0 MPa. Further, we report a synergistic effect of kinetic promotion of mixed methane hydrate formation by coupling THF and sodium dodecyl sulfate (SDS) at 293.2 K. For the first time, we observe rapid mixed methane/THF hydrate formation kinetics at 293.2 K in presence of just 100 ppm sodium dodecyl sulfate surfactant with methane gas uptake of 3.45 (+/- 0.17) kmol/m(3) of water in 1 h. This is also the first study to demonstrate such rapid hydrate formation kinetics with significant methane storage capacity at temperature of 293.2 K (closer to the ambient temperature). Further, substantial methane gas uptake of 3.52 (+/- 0.13) kmol/m(3) of water is possible even at reduced experimental pressure of 3.0 MPa and 283.2 K in 2 h. Minimal energy requirement in an unstirred reactor for mixed methane/THF hydrate formation storage can propel the SNG technology for large scale commercial deployment. Further improvement in the process can be achieved by optimizing the cooling requirement through innovative reactor design and operating the process in a semi-batch or continuous mode. (C) 2016 Elsevier Ltd. All rights reserved.

}, keywords = {Methane hydrates, Natural gas storage, Rapid kinetics, surfactant, Tetrahydrofuran, Unstirred reactor}, issn = {0016-2361}, doi = {10.1016/j.fuel.2016.05.068}, author = {Veluswamy, Hari Prakash and Kumar, Sharad and Kumar, Rajnish and Rangsunvigit, Pramoch and Linga, Praveen} } @article {43434, title = {Evaluation of uttroside B, a saponin from Solanum nigrum Linn, as a promising chemotherapeutic agent against hepatocellular carcinoma}, journal = {Scientific Reports}, volume = {6}, year = {2016}, month = {NOV}, pages = {Article Number: 36318}, abstract = {We report, for the first time, the remarkable efficacy of uttroside B, a potent saponin from Solanum nigrum Linn, against liver cancer. The compound has been isolated and characterized from the leaves of Solanum nigrum Linn, a plant widely used in traditional medicine and is a rich resource of several anticancer molecules. Uttroside B, that comprises of beta-D-glucopyranosyl unit at C-26 of the furostanol and beta-lycotetraosyl unit at C-3, is ten times more cytotoxic to the liver cancer cell line, HepG2 (IC50: 0.5 mu M) than sorafenib (IC50: 5.8 mu M), the only FDA-approved drug for liver cancer. Moreover, it induces cytotoxicity in all liver cancer cell lines, irrespective of their HBV status, while being non-toxic to normal immortalized hepatocytes. It induces apoptosis in HepG2 cells by down-regulating mainly the activation of MAPK and mTOR pathways. The drastic reduction in HepG2-xenograft tumor size achieved by uttroside B in NOD-SCID mice and substantiation of its biological safety through both acute and chronic toxicity studies in Swiss albino mice warrants clinical validation of the molecule against hepatic cancer, for which, the chemotherapeutic armamentarium currently has limited weapons.}, doi = {10.1038/srep36318}, author = {Nath, Lekshmi R. and Gorantla, Jaggaiah N. and Thulasidasan, Arun Kumar T. and Vijayakurup, Vinod and Shah, Shabna and Anwer, Shabna and Joseph, Sophia M. and Antony, Jayesh and Veena, Kollery Suresh and Sundaram, Sankar and Marelli, Udaya K. and Lankalapalli, Ravi S. and Anto, Ruby John} } @article { ISI:000377515200041, title = {Exploration of the diastereoselectivity in an unusual Grignard reaction and its application towards the synthesis of styryl lactones 7-epi-(+)-goniodiol and 8-epi-(-)-goniodiol}, journal = {RSC Advances}, volume = {6}, number = {56}, year = {2016}, month = {MAY}, pages = {50721-50725}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

An unusual diastereoselective Grignard reaction is explored, where the Grignard reagents are derived from 1,n-dihaloalkanes. A steric bias due to the presence of a quaternary centre adjacent to the acetonide ester at the benzylic position is responsible for the formation of an intramolecularly reduced product in almost quantitative yield. This steric hindrance is responsible for the diastereoselectivity observed with a variety of aromatic as well as aliphatic esters. The unusual Grignard reaction furnishes long chain secondary alcohols possessing a terminal olefin, which are synthetically important intermediates. As an application of this method, the diastereoselective synthesis of styryl lactones viz. 7-epi-(+)-goniodiol (29) and 8-epi(-)-goniodiol (30) has been achieved.

}, issn = {2046-2069}, doi = {10.1039/c6ra03192g}, author = {Chavan, Subhash P. and Khatod, Harshali S. and Das, Tamal and Vanka, Kumar} } @article { ISI:000366590300006, title = {Exploring activity differences between the hydroformylation catalysts: Insights from theory}, journal = {Journal of Organometallic Chemistry}, volume = {801}, year = {2016}, month = {JAN}, pages = {30-41}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

Hydroformylation catalysis is the most important homogeneous catalysis process of the current day. The current computational investigation aims to understand the nature of the hydroformylation process when monodentate ligands are employed. The complete catalytic cycle for different monodentate ligands bound to the rhodium center has been studied with full quantum chemical calculations, with density functional theory (DFT). To the best of our knowledge, this is the first systematic investigation of the relative free energy surfaces for mono-coordinate monodentate and bi-coordinated monodentate ligands in hydroformylation catalysis. The results indicate that the barriers are lower for the mono-coordinate monodentate species in comparison to the bi-coordinate monodentate, for all the ligand cases studied, indicating higher activity for the mono-coordinate monodentate active species. (C) 2015 Elsevier B.V. All rights reserved.

}, keywords = {Density functional theory (DFT) calculations, Hydroformylation, Monodentate, Rhodium}, issn = {0022-328X}, doi = {10.1016/j.jorganchem.2015.10.015}, author = {Dangat, Yuvraj B. and Rizvi, Masood Ahmad and Pandey, Pippalad and Vanka, Kumar} } @article { ISI:000373630800015, title = {Exploring the reducing role of boron: added insights from theory}, journal = {Dalton Transactions}, volume = {45}, number = {14}, year = {2016}, month = {NOV}, pages = {5978-5988}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Carbon-carbon coupling in CO molecules is a challenging proposition, and very few main group complexes have been shown to effect this process. A recently reported triply bonded diboryne system (1) is notable for coupling four CO molecules to produce a (bis) boralactone species. The current full quantum chemical computational investigation with density functional theory (DFT) provides important insights into the nature of the CO coupling process by triply bonded diboryne systems. The complete reaction pathway leading to the formation of the (bis) boralactone has been determined. Factors that make this system so successful in coupling CO groups have been elucidated, and pertinent issues, such as why the coupling process stops after four CO additions, have been explored. Also, importantly, insights have been gained through the natural bond orbital (NBO) analysis into how the back-donation from diboryne activates CO.

}, issn = {1477-9226}, doi = {10.1039/c5dt03799a}, author = {Dangat, Yuvraj B. and Vanka, Kumar} } @article { ISI:000378295200030, title = {Facile access to a Ge(II) dication stabilized by isocyanides}, journal = {Chemical Communications}, volume = {52}, number = {50}, year = {2016}, month = {MAY}, pages = {7890-7892}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Herein, we introduce isocyanide as a ligand in main group chemistry and describe the facile isolation of a Ge(II) dication. The reaction of 2,6-dimethylphenylisocyanide with GeCl2 leads to the formation of a Ge(II) dication with two [GeCl3](-) molecules as counter anions. The dicationic Ge(II) center is bound to four isocyanide ligands and also holds a lone pair of electrons. DFT calculations reveal that the dication is stabilized only by sigma-donation from the four isocyanide ligands. Natural population analysis gives a charge of +0.74 on the Ge(II) center, indicating that the positive charge is shared by the isocyanide substituents.

}, issn = {1359-7345}, doi = {10.1039/c6cc03789e}, author = {Swamy, V. S. V. S. N. and Yadav, Sandeep and Pal, Shiv and Das, Tamal and Vanka, Kumar and Sen, Sakya S.} } @article { ISI:000380241600129, title = {Gold incorporated mesoporous silica thin film model surface as a robust SERS and catalytically active substrate}, journal = {Molecules}, volume = {21}, number = {5}, year = {2016}, month = {MAY}, pages = {667}, publisher = {MDPI AG}, address = {ST ALBAN-ANLAGE 66, CH-4052 BASEL, SWITZERLAND}, abstract = {

Ultra-small gold nanoparticles incorporated in mesoporous silica thin films with accessible pore channels perpendicular to the substrate are prepared by a modified sol-gel method. The simple and easy spin coating technique is applied here to make homogeneous thin films. The surface characterization using FESEM shows crack-free films with a perpendicular pore arrangement. The applicability of these thin films as catalysts as well as a robust SERS active substrate for model catalysis study is tested. Compared to bare silica film our gold incorporated silica, GSM-23F gave an enhancement factor of 10(3) for RhB with a laser source 633 nm. The reduction reaction of p-nitrophenol with sodium borohydride from our thin films shows a decrease in peak intensity corresponding to -NO2 group as time proceeds, confirming the catalytic activity. Such model surfaces can potentially bridge the material gap between a real catalytic system and surface science studies.

}, keywords = {gold nanoparticles, model catalysis, SERS, Thin films}, issn = {1420-3049}, doi = {10.3390/molecules21050667}, author = {Sekhar, Anandakumari Chandrasekharan Sunil and Vinod, Chathakudath Prabhakaran} } @article {45637, title = {Highly stable In-SBA-15 catalyst for vapor phase Beckmann rearrangement reaction}, journal = {Microporous and Mesoporous Materials}, volume = {234}, year = {2016}, month = {NOV }, pages = {293-302}, type = {Article}, abstract = {

The Indium doped SBA-15 material was prepared by sol-gel method and tested for vapor phase Beckman rearrangement reaction. Among three indium loading, In/Si ratio of 2/100 was found as an optimum composition in terms of caprolactam selectivity (100\%) and cyclohexanone oxime conversion (100\%). The catalysts were characterized by N-2 adsorption, small-angle X-rays/neutron scattering (SAXS/SANS), XRD, FESEM, HRTEM, EDX, UV, FTIR and NH3-TPD techniques. In-situ SANS experiment was performed on the adsorption of CO2 to detect the micropores in the mesopore wall. All catalysts samples have highly ordered hexagonal structure with well dispersed indium in the silica matrix. The fine tuning of weak and strong acid sites were found in indium doped SBA-15 (In/Si = 2/100) catalyst. The same catalyst showed optimum catalytic performance, high space time yield 114.4 mol/h/g(cat) and high stability till 6 h of reaction without deactivation. The micro-kinetic analysis showed that there were no external and internal diffusion limitations in the SBA-15 catalyst. The reaction mechanism of Beckmann rearrangement over In-SBA-15 has been elucidated. (C) 2016 Elsevier Inc. All rights reserved.

}, keywords = {e-Caprolactam, In-situ SANS, indium, SAXS, SBA-15}, issn = {1387-1811}, doi = {10.1016/j.micromeso.2016.07.024}, author = {Kumar, Rawesh and Shah, Sneha and Bahadur, Jitendra and Melnichenko, Yuri B. and Sen, Debasis and Mazumder, S. and Vinod, Chathakudath P. and Chowdhury, Biswajit} } @article { ISI:000368651100021, title = {High-Performance flexible solid-state supercapacitor with an extended nanoregime interface through in situ polymer electrolyte generation}, journal = {ACS Applied Materials \& Interfaces}, volume = {8}, number = {2}, year = {2016}, month = {JAN}, pages = {1233-1241}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

{Here, we report an efficient strategy by which a significantly enhanced electrodeelectrolyte interface in an electrode for supercapacitor application could be accomplished by allowing in situ polymer gel electrolyte generation inside the nanopores of the electrodes. This unique and highly efficient strategy could be conceived by judiciously maintaining ultraviolet-triggered polymerization of a monomer mixture in the presence of a high-surface-area porous carbon. The method is very simple and scalable, and a prototype, flexible solid-state supercapacitor could even be demonstrated in an encapsulation-free condition by using the commercial-grade electrodes (thickness = 150 mu m

}, keywords = {cyclic voltametry, impedance analysis, in situ polymer generation, interface, polymer electrolyte, supercapacitor}, issn = {1944-8244}, doi = {10.1021/acsami.5b09677}, author = {Anothumakkool, Bihag and Torris, Arun A. T. and Veeliyath, Sajna and Vijayakumar, Vidyanand and Badiger, Manohar V. and Kurungot, Sreekumar} } @article { ISI:000379456500042, title = {Intramolecular dehydrogenative coupling of 2,3-diaryl acrylic compounds: access to substituted phenanthrenes}, journal = {Journal of Organic Chemistry}, volume = {81}, number = {13}, year = {2016}, month = {JUL}, pages = {5663-5669}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

A simple, facile, and environmentally benign intramolecular dehydrogenative coupling of various 1,2-diarylethylenes for the synthesis of phenanthrenes in excellent yield has been described. This new methodology uses ceric ammonium nitrate (CAN) as a promoter at room temperature and has been extended to intermolecular synthesis of biaryl compounds. The electron transfer from methoxyarene to cerium leads to cationic radical formation, which further proceeds to intramolecular coupling. Preliminary mechanistic investigation by EPR spectroscopy and density functional theory calculation suggested a similar view.

}, issn = {0022-3263}, doi = {10.1021/acs.joc.6b00507}, author = {Gupta, Vijay and Rao, V. U. Bhaskara and Das, Tamal and Vanka, Kumar and Singh, Ravi P.} } @article { ISI:000382349600001, title = {Large trisoctahedral Au nanoparticles encapsulated inside porous silica catalyses CO oxidation at room temperature: probing the effect of encapsulation and the role of step atoms and interfaces}, journal = {Applied Catalysis A-General}, volume = {524}, year = {2016}, month = {AUG}, pages = {1-7}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

As envisaged, a synthesis strategy is reported for encapsulating high index faceted trisoctahedral Au nanoparticles inside porous silica to preserve nanoparticle size by preventing sintering. Further, to probe the role of interfaces an active metal oxide junction was created by decorating trisoctahedral (TOH) Au nanoparticle with nano oxides before silica encapsulation. The activity of these catalysts was tested for CO oxidation reaction. The reaction was found to be facile on these encapsulated large structured Au nanoparticles showing appreciable activity at room temperature compared to non encapsulated counterparts. Apart from preventing sintering, the improved activity is demonstrated due to the retention of morphology and thereby the active centres due to encapsulation. (C) 2016 Elsevier B.V. All rights reserved.

}, keywords = {Defect sites, Encapsulation, High index facets, Metal-oxide active perimeter, Trisoctahedral Au nanoparticles}, issn = {0926-860X}, doi = {10.1016/j.apcata.2016.05.023}, author = {Sreedhala, S. and Maheshwari, Shruti and Betsy, K. J. and Vinod, C. P.} } @article {45630, title = {Low band gap benzimidazole COF supported Ni3N as highly active OER catalyst}, journal = {Advanced Energy Materials}, volume = {6}, year = {2016}, month = {DEC }, pages = {Article No:1601189}, abstract = {

Covalent organic frameworks (COFs) have structures and morphologies closely resembling graphenes, whose modular construction permits atomiclevel manipulations. This, combined with their porous structure, makes them excellent catalyst supports. Here, the high electrocatalytic activity of a composite, formed by supporting Ni3N nanoparticles on a benzimidazole COF, for oxygen evolution reaction is shown. The composite oxidizes alkaline water with a near-record low overpotential of 230 mV @ 10 mA cm(-2) (eta(10)). This high activity is attributed to the ability of the COF to confine the Ni3N nanoparticles to size regimes otherwise difficult to obtain and to its low band gap character (1.49 eV) arising from the synergy between the conducting Ni3N nanoparticles and the pi-conjugated COF. The COF itself, as a metalfree self-standing framework, has an oxygen evolution reaction activity with 10 of 400 mV. The periodic structure of the COF makes it serve as a matrix to disperse the catalytically active Ni3N nanoparticles favoring their high accessibility and thereby good charge-transport within the composite. This is evident from the amount of O-2 evolved (230 mmol h(-1) g(-1)), which, to the best of our knowledge, is the highest reported. The work reveals the emergence of COF as supports for electrocatalysts.

}, issn = {1614-6832}, doi = {10.1002/aenm.201601189}, author = {Nandi, Shyamapada and Singh, Santosh Kumar and Mullangi, Dinesh and Illathvalappil, Rajith and George, Leena and Vinod, Chathakudath P. and Kurungot, Sreekumar and Vaidhyanathan, Ramanathan} } @article { ISI:000379314700006, title = {Low-overpotential electrocatalytic water splitting with noble-metal-free nanoparticles supported in a sp(3) n-rich flexible COF}, journal = {Advanced Energy Materials}, volume = {6}, number = {13}, year = {2016}, month = {JUL}, pages = {Article No. 1600110}, publisher = {WILEY-V C H VERLAG GMBH}, type = {Article}, address = {POSTFACH 101161, 69451 WEINHEIM, GERMANY}, abstract = {

Covalent organic frameworks (COFs) are crystalline organic polymers with tunable structures. Here, a COF is prepared using building units with highly flexible tetrahedral sp(3) nitrogens. This flexibility gives rise to structural changes which generate mesopores capable of confining very small (\<2 nm sized) non-noble-metal-based nanoparticles (NPs). This nanocomposite shows exceptional activity toward the oxygen-evolution reaction from alkaline water with an overpotential of 258 mV at a current density of 10 mA cm(-2). The overpotential observed in the COF-nanoparticle system is the best in class, and is close to the current record of approximate to 200 mV for any noble-metalfree electrocatalytic water splitting system-the Fe-Co-Ni metal-oxide-film system. Also, it possesses outstanding kinetics (Tafel slope of 38.9 mV dec(-1)) for the reaction. The COF is able to stabilize such small-sized NP in the absence of any capping agent because of the COF-Ni(OH)(2) interactions arising from the N-rich backbone of the COF. Density-functional-theory modeling of the interaction between the hexagonal Ni(OH)(2) nanosheets and the COF shows that in the most favorable configuration the Ni(OH)(2) nanosheets are sandwiched between the sp(3) nitrogens of the adjacent COF layers and this can be crucial to maximizing their synergistic interactions.

}, issn = {1614-6832}, doi = {10.1002/aenm.201600110}, author = {Mullangi, Dinesh and Dhavale, Vishal M. and Shalini, Sorout and Nandi, Shyamapada and Collins, Sean and Woo, Tom and Kurungot, Sreekumar and Vaidhyanathan, Ramanathan} } @article {42739, title = {Mechanistic insights into pincer-ligated palladium-catalyzed arylation of azoles with aryl Iodides: evidence of a Pd-II-Pd-IV-Pd-II pathway}, journal = {Organometallics}, volume = {35}, year = {2016}, month = {MAR}, pages = {875{\textendash}886}, abstract = {

Pincer-based (R2POCNR'2)PdCl complexes along with CuI cocatalyst catalyze the arylation of azoles with aryl iodides to give the 2-arylated azole products. Herein, we report an extensive mechanistic investigation for the direct arylation of azoles involving a well-defined and highly efficient (iPr2POCNEt2)PdCl (2a) catalyst, which emphasizes a rare PdII{\textendash}PdIV{\textendash}PdII redox catalytic pathway. Kinetic studies and deuterium labeling experiments indicate that the C{\textendash}H bond cleavage on azoles occurs via two distinct routes in a reversible manner. Controlled reactivity of the catalyst 2a underlines the iodo derivative (iPr2POCNEt2)PdI (3a) to be the resting state of the catalyst. The intermediate species (iPr2POCNEt2)Pd-benzothiazolyl (4a) has been isolated and structurally characterized. A determination of reaction rates of compound 4a with electronically different aryl iodides has revealed the kinetic significance of the oxidative addition of the C(sp2){\textendash}X electrophile, aryl iodide, to complex 4a. Furthermore, the reactivity behavior of 4a suggests that the arylation of benzothiazole proceeds via an oxidative addition/reductive elimination pathway involving a (iPr2POCNEt2)PdIV(benzothiazolyl)(Ar)I species, which is strongly supported by DFT calculations.

}, doi = {10.1021/acs.organomet.6b00003}, author = {Khake, Shrikant M. and Jagtap, Rahul A. and Dangat, Yuvraj B. and Gonnade, Rajesh G. and Vanka, Kumar and Punji, Benudhar} } @inbook {45865, title = {Memory booster plant Bacopa monniera (brahmi): biotechnology and molecular aspects of bacoside biosynthesis}, booktitle = {Medicinal plants - recent advances in research and development}, year = {2016}, pages = {167-189}, publisher = {Springer }, organization = {Springer }, address = {Singapore}, abstract = {Bacopa monniera (Brahmi) has been used in the Ayurvedic system of medicine as a brain tonic, memory enhancer, antianxiety, cardiotonic, anticancer, anti-inflammatory, analgesic, and anticonvulsant agent since ancient times. These pharmacological properties are mainly attributed to the triterpenoid saponins present in the extracts of the plant. Biosynthesis of triterpenoid saponins starts from the isoprenoid pathway through farnesyl pyrophosphate by cyclization of 2,3-oxidosqualene, resulting in the formation of triterpenoid backbones. The plant produces relatively smaller amounts of bacosides, and to overcome this shortage, a large amount of biomass is used in the pharmaceutical preparations. Despite a wealth of medicinal importance, the molecular characterization and pathway engineering of bacoside biosynthesis in Bacopa remain unexplored. In this chapter, we have briefly discussed the research findings on in vitro plant regeneration, genetic transformation, and molecular characterization of some of the genes involved in the biosynthesis of bacosides.}, isbn = {978-981101085-9}, issn = {978-981101084-2}, doi = {10.1007/978-981-10-1085-9_6}, author = {Vishwakarma, R. K. and Kumari, U. and Khan, B. M.} } @article { ISI:000379577800033, title = {Molecules with O-acetyl group protect protein glycation by acetylating lysine residues}, journal = {RSC Advances}, volume = {6}, number = {70}, year = {2016}, month = {JUL}, pages = {65572-65578}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Pharmaceutical intervention for reduction of advanced glycation end products (AGEs) is considered as a therapeutic strategy to attenuate the pathogenesis of diabetes. Many molecules have been reported to possess antiglycation activity, one such example is acetylsalicylic acid (aspirin). It protects proteins from glycation by acetylating the lysine residues. Therefore, in this study we have synthesized and screened molecules containing free N-acetyl, O-acetyl and acetophenone groups. All the selected molecules in this study showed glycation inhibition but interestingly, only molecules with O-acetyl but not N-acetyl and acetophenone groups were capable of acetylating lysine residue. Furthermore, we have demonstrated that pre-acetylation or aspirin treatment prior to the induction of diabetes helps in reducing HbA1c and AGE formation in the streptozotocin induced diabetic mice. Hence pre-acetylation may have an additional therapeutic efficacy of reducing AGE levels in vivo. Incorporation of O-acetyl group into anti-diabetic molecules could be a useful strategy, as it may have an additive effect in reducing AGEs. Identification of such novel acetylating agents represents a new area in the drug discovery process.

}, issn = {2046-2069}, doi = {10.1039/c6ra11313c}, author = {Vannuruswamy, Garikapati and Jagadeeshaprasad, Mashanipalya G. and Kashinath, K. and Kesavan, Suresh K. and Bhat, Shweta and Korwar, Arvind M. and Chougale, Ashok D. and Boppana, Ramanamurthy and Reddy, D. Srinivasa and Kulkarni, Mahesh J.} } @article {42936, title = {Naturally occurring anti-TB agents: isolation, chemical transformations and in vitro antitubercular activities of secondary metabolites of rhizomes of alpinia galanga}, journal = {Planta Medica International Open}, volume = {3}, year = {2016}, month = {SEP}, pages = {e55-e59}, abstract = {

A bioactivity-guided chemical examination of the acetone extract of the rhizomes of Alpinia galanga led to the isolation of six sec-ondary metabolites, eucalyptol derivative (1)andphenylpropa-noids (2{\textendash}6). The structures of all of the isolated compounds (1{\textendash}6)wereelucidatedonthebasisoftheirspectraldata.Theisolatedcompounds (1{\textendash}6)werein vitro assayed against active and dor-mant phenotypes of Mycobacterium tuberculosis H37Ra, respec-tively. Interestingly, 1'S-1'-acetoxychavicol acetate (2)showedgood antitubercular activities against both active and dormantphenotypes of M. tuberculosis with IC50 values of 1.04 {\textmu}M and2.69 {\textmu}M, respectively. Tsuji-Trost and homodimerization reac-tions of the active compound (2)respectivelyresultedinthefor-mation of two analogues, 7and 8.Bothofthesesynthesizedana-logues were also found to be active in vitro against active [IC50 sof3.24 and 3.87 {\textmu}M, respectively, for compounds 7and 8]anddor-mant [IC50 sof8.33and2.41{\textmu}M,respectively,forcompounds7and 8]phenotypesofM. tuberculosis H37Ra, respectively.

}, doi = {10.1055/s-0042-112226}, author = {Valkute, Tushar R. and Arkile, Manisha A. and Sarkar, Dhiman and Bhattacharya, Asish K.} } @article {43624, title = {Nevirapine loaded core shell gold nanoparticles by double emulsion solvent evaporation: invitro and in vivo evaluation}, journal = {Current Drug Delivery}, volume = {13}, year = {2016}, month = {JAN}, pages = {1071-1083}, abstract = {Background: HIV/AIDS is a macrophage resident infection localized in the reticuloendothelial system and remote locations of brain and bone marrow. We present core shell nanoparticles of gold(AuNPs) and nevirapine(NVP) for targeted delivery to the multiple HIV reservoirs. The aim of the study was to design core shell NVP loaded AuNPs with high drug loading and to evaluate biodistribution of the nanoparticles in possible HIV reservoirs in vivo. A specific objective was to assess the possible synergy of AuNPs with NVP on anti-HIV activity in vitro. Method: Core shell nanoparticles were prepared by double emulsion solvent evaporation method and characterized. Results: Glyceryl monostearate-nevirapine-gold nanoparticles(GMS-NVP-AuNPs) revealed high entrapment efficiency (> 70\%), high loading (similar to 40\%), particle size < 250 nm and zeta potential -35.9 +/- 1.41mv and exhibited sustained release with good stability. Surface plasmon resonance indicated shell formation while SEM coupled EDAX confirmed the presence of Au. TEM confirmed formation of spherical core shell nanoparticles. GMS-NVP-AuNPs revealed low hemolysis (< 10 \%) and serum stability upto 6 h. GMS-NVP-AuNPs exhibited rapid, high and sustained accumulation in the possible HIV reservoir organs, including the major organs of liver, spleen, lymph nodes, thymus and also remote locations of brain, ovary and bone marrow. High cell viability and enhanced uptake in PBMC{\textquoteright}s and TZM-bl cells were observed. While uptake in PBMC{\textquoteright}s proposed monocytes/macrophages enabled brain delivery. GMS-NVP-AuNPs demonstrated synergistic anti-HIV activity. Conclusion: The superior anti-HIV activity in vitro coupled with extensive localization of the nanoparticles in multiple HIV reservoirs suggests great promise of the core shell GMS-NVP-AuNPs for improved therapy of HIV.}, doi = {10.2174/1567201813666160114093005}, author = {Dalvi, Bhagyashree R. and Siddiqui, Ejaz A. and Syed, Asad S. and Velhal, Shilpa M. and Ahmad, Absar and Bandivdekar, Atmaram B. and Devarajan, Padma V.} } @article { ISI:000380182400035, title = {Palladium-catalyzed internal nucleophile-assisted hydration-olefin insertion cascade: diastereoselective synthesis of 2,3-dihydro-1H-inden-1-ones}, journal = {Organic Letters}, volume = {18}, number = {14}, year = {2016}, month = {JUL}, pages = {3442-3445}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

A novel palladium-catalyzed hydration-olefin insertion cascade assisted by internal nucleophiles was developed for the synthesis of biologically significant 2,3-dihydro-1H-inden-1-ones under mild conditions. A detailed mechanistic study revealed that the assistance of the internal nucleophiles is crucial to trigger the cascade reaction via nucleopalladation of the alkyne moiety. The overall reaction is equivalent to regioselective hydration of alkynes followed by intramolecular Michael addition. This highly efficient and 100\% atom-economical domino sequence afforded cis-2,3-disubstituted 2,3-dihydro-1H-inden-1-ones in excellent yields (up to 99\%) with complete diastereoselectivity.

}, issn = {1523-7060}, doi = {10.1021/acs.orglett.6b01623}, author = {Vinoth, Perumal and Nagarajan, Subbiah and Maheswari, C. Uma and Sudalai, Arumugam and Pace, Vittorio and Sridharan, Vellaisamy} } @article {42606, title = {Passive microrheology in the effective time domain: analysing time dependent colloidal dispersions}, journal = {Soft Matter}, volume = {12}, year = {2016}, month = {AUG}, pages = {8167-8176}, abstract = {

We studied the aging dynamics of an aqueous suspension of LAPONITE (R), a model time dependent soft glassy material, using a passive microrheology technique. This system is known to undergo physical aging during which its microstructure evolves progressively to explore lower free energy states. Optical microscopy is used to monitor the motion of micron-sized tracer probes embedded in a sample kept between two glass plates. The mean square displacements (MSD) obtained from the motion of the tracer particles show a systematic change from a purely diffusive behavior at short aging times to a subdiffusive behavior as the material ages. Interestingly, the MSDs at all the aging times as well as different LAPONITE (R) concentrations superpose remarkably to show a time-aging time master curve when the system is transformed from the real time domain to the effective time domain, which is obtained by rescaling the material clock to account for the age dependent relaxation time. The transformation of the master curve from the effective time domain to the real time domain leads to the prediction of the MSD in real time over a span of 5 decades when the measured data at individual aging times are only over 2 decades. Since the MSD obtained from microrheology is proportional to the creep compliance of a material, by using the Boltzmann superposition principle along with the convolution relation in the effective time domain, we predict the stress relaxation behavior of the system in real time. This work shows that the effective time approach applied to microrheology facilitates the prediction of long time creep and relaxation dynamics of a time dependent soft material by carrying out short time experiments at different aging times.

}, doi = {10.1039/c6sm00829a}, author = {Vyas, Bhavna M. and Orpe, Ashish V. and Kaushal, Manish and Joshi, Yogesh M.} } @article { ISI:000369533400015, title = {Phenylacetylene hydrogenation on Au@Ni bimetallic core-shell nanoparticles synthesized under mild conditions}, journal = {Catalysis Science \& Technology}, volume = {6}, number = {3}, year = {2016}, month = {JAN}, pages = {708-712}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

The synthesis of Au@Ni bimetallic core-shell nanoparticles through an energy efficient (lower temperature) route in oleylamine following a sequential reduction strategy is reported. The method is found to be useful for the synthesis of a very thin nickel shell (2 nm) over a gold core (15 nm). Synergistic effects are observed in catalyzing phenylacetylene hydrogenation under different solvent conditions.

}, issn = {2044-4753}, doi = {10.1039/c5cy02005k}, author = {Vysakh, A. B. and Lazar, Anish and Yadukiran, V. and Singh, A. P. and Vinod, C. P.} } @article {42861, title = {Porous thin films towards bridging the material gap in heterogeneous catalysis}, journal = {Catalysis, Structure \& Reactivity}, volume = {2}, year = {2016}, month = {MAR}, pages = {1-12}, type = {Article}, abstract = {

An attempt has been made to bridge the material gap, existing between ideal single crystals and real-world powder nanocatalyst employed in surface science and heterogeneous catalysis, respectively. Simple wet chemical method (sol{\textendash}gel and spin-coating deposition) has been applied to make continuous Ce1 - xZrxO2 (x = 0{\textendash}1) (CZ) thin films with uniform thickness (~40 nm) and smooth surface characteristics. Uniform thickness and surface smoothness of the films over a large area was supported by a variety of measurements. Molecular beam (MB) studies of O2 adsorption on CZ surfaces reveals the oxygen storage capacity (OSC), and sticking coefficient increases from 400 to 800 K. Porous nature of Ce-rich CZ compositions enhances O2 adsorption and OSC, predominantly due to O-diffusion and redox nature, even at 400 K. A good correlation exists between MB measurements made on CZ films for oxygen adsorption, and OSC, and ambient pressure CO oxidation on powder form of CZ; this demonstrates the large potential to bridge the material gap. CZ was particularly chosen as a model system for the present studies, since it has been well-studied and a correlation between surface science properties made on thin films and catalysis on powder CZ materials could be a litmus test. Ambient catalysis on ceria-zirconia nanocatalyst correlates well with surface properties measured through molecular beam on thinfilm and close the material gap.

}, doi = {10.1080/2055074X.2015.1133269}, author = {Dubey, Anjani and Kolekar, Sadhu K. and Gnanakumar, Edwin S. and Roy, Kanak and Vinod, C. P. and Gopinath, Chinnakonda S.} } @article { ISI:000368189500001, title = {Potential dual role of eugenol in inhibiting advanced glycation end products in diabetes: proteomic and mechanistic insights}, journal = {Scientific Reports}, volume = {6}, year = {2016}, month = {JAN}, publisher = {NATURE PUBLISHING GROUP}, address = {MACMILLAN BUILDING, 4 CRINAN ST, LONDON N1 9XW, ENGLAND}, abstract = {

Medicinally important genus Ocimum harbors a vast pool of chemically diverse metabolites. Current study aims at identifying anti-diabetic candidate compounds from Ocimum species. Major metabolites in O. kilimandscharicum, O. tenuiflorum, O. gratissimum were purified, characterized and evaluated for anti-glycation activity. In vitro inhibition of advanced glycation end products (AGEs) by eugenol was found to be highest. Preliminary biophysical analysis and blind docking studies to understand eugenol-albumin interaction indicated eugenol to possess strong binding affinity for surface exposed lysines. However, binding of eugenol to bovine serum albumin (BSA) did not result in significant change in secondary structure of protein. In vivo diabetic mice model studies with eugenol showed reduction in blood glucose levels by 38\% likely due to inhibition of alpha-glucosidase while insulin and glycated hemoglobin levels remain unchanged. Western blotting using anti-AGE antibody and mass spectrometry detected notably fewer AGE modified peptides upon eugenol treatment both in vivo and in vitro. Histopathological examination revealed comparatively lesser lesions in eugenol-treated mice. Thus, we propose eugenol has dual mode of action in combating diabetes; it lowers blood glucose by inhibiting a-glucosidase and prevents AGE formation by binding to epsilon-amine group on lysine, protecting it from glycation, offering potential use in diabetic management.

}, issn = {2045-2322}, doi = {10.1038/srep18798}, author = {Singh, Priyanka and Jayaramaiah, Ramesha H. and Agawane, Sachin B. and Vannuruswamy, Garikapati and Korwar, Arvind M. and Anand, Atul and Dhaygude, Vitthal S. and Shaikh, Mahemud L. and Joshi, Rakesh S. and Boppana, Ramanamurthy and Kulkarni, Mahesh J. and Thulasiram, Hirekodathakallu V. and Giri, Ashok P.} } @article { ISI:000371228200032, title = {Prediction of reactivity ratios in free radical copolymerization from monomer resonance-polarity (Q-e) parameters: genetic programming-based models}, journal = {International Journal of Chemical Reactor Engineering}, volume = {14}, number = {1}, year = {2016}, month = {FEB}, pages = {361-372}, publisher = {WALTER DE GRUYTER GMBH}, address = {GENTHINER STRASSE 13, D-10785 BERLIN, GERMANY}, abstract = {

The principal deficiency of the widely utilized Alfrey-Price (AP) scheme for computing reactivity ratios in the widely used free radical copolymerization is that it ignores important factors, such as the steric effects. This often leads to inaccurate reactivity ratio predictions by AP model. Accordingly, in this study, exclusively data-driven, Q-e parameter-based new models have been developed for the reactivity ratio prediction in free radical copolymerization. In the model development, a novel artificial intelligence formalism known as {\textquoteleft}{\textquoteleft}genetic programming (GP){\textquoteright}{\textquoteright} that performs symbolic regression has been employed. The GP-based models possess a different functional form than AP model. Further, parameters of GP-based models were fine-tuned using Levenberg-Marquardt (LM) nonlinear regression method. A comparison of AP, GP and GP-LM as well as artificial neural network (ANN)-based models indicates that GP and GP-LM models exhibit superior reactivity ratio prediction accuracy and generalization performance (with correlation coefficient magnitudes close to or greater than 0.9) when compared with AP and ANN models. The GPbased reactivity ratio prediction models developed here due to their higher accuracy and generalization capability have the potential of replacing the widely used AP models.

}, keywords = {Alfrey-Price scheme, free radical copolymerization, genetic programming, reactivity ratio, symbolic regression}, issn = {2194-5748}, doi = {10.1515/ijcre-2014-0039}, author = {Shrinivas, K. and Kulkarni, Rahul P. and Shaikh, Saif and Ghorpade, Ravindra V. and Vyas, Renu and Tambe, Sanjeev S. and Ponrathnam, S. and Kulkarni, Bhaskar D.} } @article { ISI:000378935400002, title = {Pretreatment and enzymatic process modification strategies to improve efficiency of sugar production from sugarcane bagasse}, journal = {3 Biotech}, volume = {6}, year = {2016}, month = {JUN}, pages = {Article Number: 126}, publisher = {SPRINGER HEIDELBERG}, address = {TIERGARTENSTRASSE 17, D-69121 HEIDELBERG, GERMANY}, abstract = {

Pretreatment and enzymatic hydrolysis play a critical role in the economic production of sugars and fuels from lignocellulosic biomass. In this study, we evaluated diverse pilot-scale pretreatments and different post-pretreatment strategies for the production of fermentable sugars from sugarcane bagasse. For the pretreatment of bagasse at pilot-scale level, steam explosion without catalyst and combination of sulfuric and oxalic acids at low and high loadings were used. Subsequently, to enhance the efficiency of enzymatic hydrolysis of the pretreated bagasse, three different post-pretreatment process schemes were investigated. In the first scheme (Scheme 1), enzymatic hydrolysis was conducted on the whole pretreated slurry, without treatments such as washing or solid-liquid separation. In the second scheme (Scheme 2), the pretreated slurry was first pressure filtered to yield a solid and liquid phase. Following filtration, the separated liquid phase was remixed with the solid wet cake to generate slurry, which was then subsequently used for enzymatic hydrolysis. In the third scheme (Scheme 3), the pretreated slurry was washed with more water and filtered to obtain a solid and liquid phase, in which only the former was subjected to enzymatic hydrolysis. A 10 \% higher enzymatic conversion was obtained in Scheme 2 than Scheme 1, while Scheme 3 resulted in only a 5-7 \% increase due to additional washing unit operation and solid-liquid separation. Dynamic light scattering experiments conducted on post-pretreated bagasse indicate decrease of particle size due to solid-liquid separation involving pressure filtration provided increased the yield of C6 sugars. It is anticipated that different process modification methods used in this study before the enzymatic hydrolysis step can make the overall cellulosic ethanol process effective and possibly cost effective.

}, keywords = {Dilute acid treatment, High-solid enzymatic hydrolysis, Pilot-scale pretreatment, Pressure filtration, Solid-liquid separation}, issn = {2190-5738}, doi = {10.1007/s13205-016-0446-2}, author = {Pal, Siddhartha and Joy, Shereena and Trimukhe, Kalpana D. and Kumbhar, Pramod S. and Varma, Anjani J. and Padmanabhan, Sasisanker} } @article {43038, title = {Product distribution in hydrogenation of styrene oxide over Pd/chitosan catalyst}, journal = {Research on Chemical Intermediates}, volume = {42}, year = {2016}, month = {OCT}, pages = {7581-7595}, abstract = {

Palladium-decorated chitosan catalyst was synthesized by an impregnation method by varying the Pd loading in the range of 1-6 \%, and was evaluated for the regioselective hydrogenation of styrene oxide. In order to correlate the chemical and textural properties with the catalytic activity, all the prepared catalysts were characterized by techniques such as Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron spectroscopy, thermo-gravimetric analysis, temperature-programmed desorption of NH3, and CO2 and N-2 physisorption. The synthesized catalysts were utilized for the efficient and regioselective ring opening of styrene oxide by hydrogenation under different conditions. The complete conversion of styrene oxide with 65 \% selectivity for 2-phenyl ethanol and 33 \% for 1-phenyl ethanol were obtained using 4 \% Pd/CS catalyst at 70 degrees C temperature and 3 MPa pressure. The mechanism for the regio selective ring opening of styrene oxide to 1- and 2-phenyl ethanol was also proposed on the basis of properties of the catalyst support, catalytic activity and selectivity. These results indicated that the catalytic activity and selectivity of the catalysts were affected by the nature of support. Further, the basic properties of the support play an important role in the selectivity of the styrene oxide hydrogenation reaction.

}, doi = {10.1007/s11164-016-2554-3}, author = {Viswanadhan, Maya and Potdar, Aparna and Divakaran, Anumon V. and Badiger, Manohar V. and Rode, Chandrashekhar} } @article { ISI:000369508800059, title = {Promotional effect of Fe on the performance of supported Cu catalyst for ambient pressure hydrogenation of furfural}, journal = {RSC Advances}, volume = {6}, number = {5}, year = {2016}, month = {DEC}, pages = {3888-3898}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

A noble-metal free FeCu based bimetallic catalyst system prepared by facile co-impregnation method was found to be highly admirable for vapour phase selective hydrogenation of furfural to furfuryl alcohol at ambient pressure. Monometallic Cu/gamma-Al2O3, Fe/gamma-Al2O3 and bimetallic FeCu/gamma-Al2O3 catalysts with different Fe loadings were prepared. Structural and morphological features of the catalysts were thoroughly investigated by several physico-chemical characterization techniques. The influence of various reaction parameters, such as Fe loading, reaction temperature and flow of reactants was examined with respect to furfural conversion and furfuryl alcohol yield. The results clearly showed that an optimum amount of Fe is necessary to enhance the catalytic activity of monometallic Cu/gamma-Al2O3 for the selective hydrogenation of furfural. The catalyst FC-10 with 10 wt\% Fe exhibited excellent activity which led to high furfural conversion (\>93\%) and furfuryl alcohol selectivity (\>98\%) under mild reaction conditions. The higher activity of bimetallic FeCu/gamma-Al2O3 compared to monometallic Cu/gamma-Al2O3 is ascribed to the formation of FeCu bimetallic particles and the existence of oxygen vacancies in the Fe oxide system. The superior activity after Fe loading on the Cu-based catalyst was attributed to the synergy between Cu and Fe. A plausible mechanism is proposed to explain the promoting effect of Fe, which involves synergism between Fe sites with strong oxophilic nature and Cu sites with a high ability for hydrogen activation. Based on the activity results, prolonged catalytic activity and spent catalyst analysis, the developed FeCu/gamma-Al2O3 catalyst is inexpensive, eco-benign and robust, which makes it a promising candidate for the efficient conversion of biomass-derived substrates to fine chemicals and drop-in biofuels.

}, issn = {2046-2069}, doi = {10.1039/c5ra24742j}, author = {Manikandan, Marimuthu and Venugopal, Ashok Kumar and Nagpure, Atul S. and Chilukuri, Satyanarayana V. and Raja, Thirumalaiswamy} } @article {43452, title = {Proton-coupled electron transfer in a hydrogen-bonded charge transfer complex}, journal = {Journal of Physical Chemistry B}, volume = {120}, year = {2016}, month = {OCT}, pages = {10780-10785}, abstract = {A proton-coupled electron transfer (PCET) reaction in a hydrogen bonded charge-transfer (CT) complex of 4-([2,2{\textquoteright}-bipyridin]-4-yl)phenol (bpy-phenol) with a F- ion has been investigated by ultrafast time-resolved transient absorption spectroscopy. The phenolic receptor molecule, bpy-phenol, binds to the F- ion through a hydrogen bond and senses the F- ion-via the Stokes-shifted CT band. Upon photoexcitation, CT from the phenol residue to the bpy residue promotes proton transfer from the phenol radical cation (ArOH center dot+) to the fluoride ion at ultrafast time scales of <150 fs (instrument response function limited) and 3 ps, separately. The fast and slow proton-transfer times are linked to two different types of hydrogen-bonding networks between the phenol residue and fluoride ion. Crystalline water in the fluoride salt hydrates mediates the proton-transfer reaction. This work demonstrates the participation of a hydrogen-bonded water bridge within a PCET reaction in a water restricted environment.}, doi = {10.1021/acs.jpcb.6b06032}, author = {Verma, Sandeep and Aute, Sunil and Das, Amitava and Ghosh, Hirendra N.} } @article {45657, title = {Pyramiding PvPGIP2 and TAXI-III but not PvPGIP2 and PMEI enhances resistance against fusarium graminearum}, journal = {Molecular Plant-Microbe Interactions}, volume = {29}, year = {2016}, month = {AUG}, pages = {629-639}, type = {Article}, abstract = {

Plant protein inhibitors counteract the activity of cell wall degrading enzymes (CWDEs) secreted by pathogens to breach the plant cell-wall barrier. Transgenic plants expressing a single protein inhibitor restrict pathogen infections. However, since pathogens secrete a number of CWDEs at the onset of infection, we combined more inhibitors in a single wheat genotype to reinforce further the cell-wall barrier. We combined polygalacturonase (PG) inhibiting protein (PGIP) and pectin methyl esterase inhibitor (PMEI), both controlling the activity of PG, one of the first CWDEs secreted during infection. We also pyramided PGIP and TAXI-M, a xylanase inhibitor that controls the activity of xylanases, key factors for the degradation of xylan, a main component of cereal cell wall. We demonstrated that the pyramiding of PGIP and PMEI did not contribute to any further improvement of disease resistance. However, the presence of both pectinase inhibitors ensured a broader spectrum of disease resistance. Conversely, the PGIP and TAXI-HI combination contributed to further improvement of Fusarium head blight (FHB) resistance, probably because these inhibitors target the activity of different types of CWDEs, i.e., PGs and xylanases. Worth mentioning, the reduction of FHB symptoms is accompanied by a reduction of deoxynivalenol accumulation with a foreseen great benefit to human and animal health.

}, issn = {0894-0282}, doi = {10.1094/MPMI-05-16-0089-R}, author = {Tundo, Silvio and Kalunke, Raviraj and Janni, Michela and Volpi, Chiara and Lionetti, Vincenzo and Bellincampi, Daniela and Favaron, Francesco and D{\textquoteright}Ovidio, Renato} } @article { ISI:000371560100018, title = {Rapid methane hydrate formation to develop a cost effective large scale energy storage system}, journal = {Chemical Engineering Journal}, volume = {290}, year = {2016}, month = {APR}, pages = {161-173}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

Natural gas (NG) is the cleanest burning fossil fuel and its usage can significantly reduce CO2 emissions from power plants. With its widespread use, there is an ever increasing need to develop technologies to store NG on a large scale. NG storage via clathrate hydrates is the best option for a large scale storage system because of its non-explosive nature, mild storage conditions, high volumetric capacity and being an environmentally benign process. In this work, we demonstrate a new method to achieve rapid methane hydrate formation in an unstirred tank reactor configuration (UTR) at moderate temperature and pressure conditions employing tetrahydrofuran (THF) as a promoter. For the first time, THF is reported to act both as a thermodynamic and an excellent kinetic promoter for methane hydrate formation. We demonstrate a multi-scale experimental validation of our method to a volumetric sample scale-up factor of 120 and internal reactor diameter scale-up factor of 10. Further, new insights on the dissociation behavior of the hydrates are reported. There is a competitive edge for storing NG via clathrate hydrates compared to compressed natural gas storage both in terms of cost and safety. (C) 2016 Elsevier B.V. All rights reserved.

}, keywords = {Energy storage, Enhanced kinetics, Gas hydrates, Natural gas storage, Tetrahydrofuran, Unstirred tank reactor}, issn = {1385-8947}, doi = {10.1016/j.cej.2016.01.026}, author = {Veluswamy, Hari Prakash and Wong, Alison Jia Hui and Babu, Ponnivalavan and Kumar, Rajnish and Kulprathipanja, Santi and Rangsunvigit, Pramoch and Linga, Praveen} } @article { ISI:000375837100034, title = {Reclassification of bacillus isronensis shivaji et al. 2009 as solibacillus isronensis comb. nov and emended description of genus solibacillus krishnamurthi et al. 2009}, journal = {International Journal of Systematic and Evolutionary Microbiology}, volume = {66}, number = {5}, year = {2016}, month = {MAY}, pages = {2113-2120}, publisher = {SOC GENERAL MICROBIOLOGY}, address = {MARLBOROUGH HOUSE, BASINGSTOKE RD, SPENCERS WOODS, READING RG7 1AG, BERKS, ENGLAND}, abstract = {

An investigation into the taxonomic position of Bacillus isronensis MTCC 7902(T) revealed that the strain shares a common phylogenetic lineage with Solibacillus silvestris MTCC 10789(T). It displays considerable overlap in phenotypic properties with the genus Solibacillus, including endospore shape and position, oxidase and catalase activities, presence of iso-C-15 : 0, C-16 : (1)omega 7c alcohol and iso-C-17 : 1 omega 7c as major cellular fatty acids, A4 alpha-type cell-wall peptidoglycan, polar lipids and menaquinone pattern. These features reinforce the findings of molecular phylogenetic analyses based on 16S rRNA gene, gyrB gene and 16S-23S internal transcribed spacer (ITS) region sequences and, in line with the recommendations of Kampfer et al. [Int J Syst Evol Microbiol 56 (2006), 781-786], provide justification for the transfer of Bacillus isronensis from the genus Bacillus to Solibacillus as Solibacillus isronensis comb. nov. The type strain is B3W22(T) (=MTCC 7902(T) =DSM 21046(T) =JCM 13838(T)). An emended description of the genus Solibacillus is also provided.

}, issn = {1466-5026}, doi = {10.1099/ijsem.0.000982}, author = {Mual, Poonam and Singh, Nitin Kumar and Verma, Ashish and Schumann, Peter and Krishnamurthi, Srinivasan and Dastager, Syed Gulam and Mayilraj, Shanmugam} } @article {45632, title = {Reduced graphene oxide modified electrodes for sensitive sensing of gliadin in food samples}, journal = {ACS Sensors}, volume = {1}, year = {2016}, month = {DEC}, pages = {1462-1470}, type = {Article}, abstract = {

Incidences of food allergies are on the rise, which can greatly affect the well-being of children as well as adults. Intolerance to gluten, a protein composite of gliadin and glutenin, present in wheat, barley, and rye and several cereals, can be the causative agent of celiac disease (CD) and other allergic reactions. A gluten-free diet has become essential for people affected by CD, and consequently, the amount of gluten in food products needs to be strictly controlled. In this paper, we report an electrochemical label-free immunosensor for ultrasensitive and specific detection of gliadin. The sensor takes advantage of the specific properties of porous reduced graphene oxide (prGO) covalently functionalized with anti-gliadin antibodies using 1-pyrenecarboxylic acid as linker molecule. Using differential pulse voltammetry (DPV) and [Fe(CN)6](3-/4-) as a redox probe, a decrease of current is linked to the presence of gliadin. The sensor achieved a detection limit of 1.2 ng mL(-1) over a 1.2-34 ng mL(-1) linear range with high selectivity. The advantages offered by this sensor are the possibility to regenerate the surface of the immunosensor, its rapid and ease of production, as well as applicability for the screening of gliadin concentrations in real food samples, as shown here.

}, keywords = {anti-gliadin antibody, food samples, gliadin, Immunosensor, Porous reduced graphene oxide}, issn = {2379-3694}, doi = {10.1021/acssensors.6b00608}, author = {Chekin, Fereshteh and Singh, Santosh K. and Vasilescu, Alina and Dhavale, Vishal M. and Kurungot, Sreekumar and Boukherroub, Rabah and Szunerits, Sabine} } @article { ISI:000378392200016, title = {Reductive nitrosylation of nickel(II) complex by nitric oxide followed by nitrous oxide release}, journal = {Dalton Transactions}, volume = {45}, number = {25}, year = {2016}, month = {MAY}, pages = {10200-10208}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Ni(II) complex of ligand L (L = bis(2-ethyl-4-methylimidazol-5-yl)methane) in methanol solution reacts with an equivalent amount of NO resulting in a corresponding Ni(I) complex. Adding further NO equivalent affords a Ni(I)-nitrosyl intermediate with the {NiNO}(10) configuration. This nitrosyl intermediate upon subsequent reaction with additional NO results in the release of N2O and formation of a Ni(II)-nitrito complex. Crystallographic characterization of the nitrito complex revealed a symmetric eta(2)-O,O-nitrito bonding to the metal ion. This study demonstrates the reductive nitrosylation of a Ni(II) center followed by N2O release in the presence of excess NO.

}, issn = {1477-9226}, doi = {10.1039/c6dt00826g}, author = {Ghosh, Somnath and Deka, Hemanta and Dangat, Yuvraj B. and Saha, Soumen and Gogoi, Kuldeep and Vanka, Kumar and Mondal, Biplab} } @article { ISI:000377497000004, title = {Relativistic coupled-cluster study of RaF as a candidate for the parity- and time-reversal-violating interaction}, journal = {Physical Review A}, volume = {93}, number = {6}, year = {2016}, month = {JUN}, pages = {062506}, publisher = {AMER PHYSICAL SOC}, address = {ONE PHYSICS ELLIPSE, COLLEGE PK, MD 20740-3844 USA}, abstract = {

We have employed both the Z-vector method and the expectation-value approach in the relativistic coupled-cluster framework to calculate the scalar-pseudoscalar (S-PS) P, T-odd interaction constant W-s and the effective electric field E-eff experienced by the unpaired electron in the ground electronic state of RaF. Further, the magnetic hyperfine structure constants of Ra-223 in RaF and Ra-223(+) are also calculated and compared with the experimental values wherever available to judge the extent of the accuracy obtained with the employed methods. The outcome of our study reveals that the Z-vector method is superior to the expectation-value approach in terms of accuracy obtained for the calculation of ground-state property. The Z-vector calculation shows that RaF has a high Eeff (52.5 GV/cm) and W-s (141.2 kHz), which makes it a potential candidate for the electric dipole moment of the electron (eEDM) experiment. An estimation of uncertainty associated with our final results is made, and it is found that it lies below 10\%.

}, issn = {2469-9926}, doi = {10.1103/PhysRevA.93.062506}, author = {Sasmal, Sudip and Pathak, Himadri and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article {42619, title = {Relativistic equation-of-motion coupled-cluster method for the electron attachment problem}, journal = {Computational and Theoretical Chemistry}, volume = {1076}, year = {2016}, month = {JAN}, pages = {94-100}, abstract = {

The article considers the successful implementation of relativistic equation-of-motion coupled cluster method for the electron attachment problem (EA-EOMCC) at the level of single- and double- excitation approximation. The implemented relativistic EA-EOMCC method is employed to calculate ionization potential values of alkali metal atoms (Li, Na, K, Rb, Cs, Fr) and the vertical electron affinity values of LiX (X = H, F, Cl, Br), NaY (Y = H, F, Cl) starting from their closed-shell configuration. Both four component and exact two-component calculations are done for all the opted systems. Further, we have shown the effect of spin-orbit interaction considering the atomic systems. The results of our atomic calculations are compared with the values from the NIST database and the results are found to be very accurate (\<1\%). (C) 2015 Elsevier B.V. All rights reserved.

}, doi = {10.1016/j.comptc.2015.12.015}, author = {Pathak, Himadri and Sasmal, Sudip and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article {45870, title = {Relativistic equation-of-motion coupled-cluster method using open-shell reference wavefunction: application to ionization potential}, journal = {Journal of Chemical Physics}, volume = {145}, year = {2016}, month = {AUG}, type = {Article}, chapter = {074110}, abstract = {The open-shell reference relativistic equation-of-motion coupled-cluster method within its four-component description is successfully implemented with the consideration of single- and double- excitation approximations using the Dirac-Coulomb Hamiltonian. At the first attempt, the implemented method is employed to calculate ionization potential value of heavy atomic (Ag, Cs, Au, Fr, and Lr) and molecular (HgH and PbF) systems, where the effect of relativity does really matter to obtain highly accurate results. Not only the relativistic effect but also the effect of electron correlation is crucial in these heavy atomic and molecular systems. To justify the fact, we have taken two further approximations in the four-component relativistic equation-of-motion framework to quantify how the effect of electron correlation plays a role in the calculated values at different levels of theory. All these calculated results are compared with the available experimental data as well as with other theoretically calculated values to judge the extent of accuracy obtained in our calculations. }, doi = {10.1063/1.4960954}, author = {Pathak, H. and Sasmal, S. and Nayak, M. K. and Vaval, N. and Pal, S.} } @article {42900, title = {Repurposing of a drug scaffold: identification of novel sila analogues of rimonabant as potent antitubercular agents}, journal = {European Journal of Medicinal Chemistry}, volume = {122}, year = {2016}, month = {OCT}, pages = {723-730}, abstract = {

The structural similarity between an MmpL3 inhibitor BM212, and a cannabinoid receptor modulator rimonabant, prompted us to investigate the anti-tubercular activity of rimonabant and its analogues. Further optimization, particularly through incorporation of silicon into the scaffold, resulted in new compounds with significant improvement in anti-tubercular activity against Mycobacterium tuberculosis (H37Rv). The sila analogue 18a was found to be the most potent antimycobacterial compound (MIC, 31 ng/mL) from this series with an excellent selectivity index. (C) 2016 Elsevier Masson SAS. All rights reserved.

}, doi = {10.1016/j.ejmech.2016.07.009}, author = {Ramesh, Remya and Shingare, Rahul D. and Kumar, Vinod and Anand, Amitesh and Swetha, B. and Veeraraghavan, Sridhar and Viswanadha, Srikant and Ummanni, Ramesh and Gokhale, Rajesh S. and Reddy, D. Srinivasa} } @article { ISI:000374876700814, title = {Repurposing of old drugs: identification of novel sila analogues of rimonabant as potent antitubercular agents}, journal = {International Journal of Infectious Diseases}, volume = {45}, number = {1}, year = {2016}, month = {APR}, pages = {407-408}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, issn = {1201-9712}, doi = {10.1016/j.ijid.2016.02.870}, author = {Ramesh, R. and Shingare, R. and Anand, Amitesh and Veeraraghavan, S. and Viswanadha, S. and Ummanni, R. and Gokhale, R. and Reddy, D. S.} } @article { ISI:000374349600022, title = {Residue dependent hydrogen-bonding preferences in orthanilic acid-based short peptide beta-turn motifs}, journal = {RSC Advances}, volume = {6}, number = {42}, year = {2016}, month = {MAR}, pages = {35328-35331}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

This communication describes the competition between native beta-turn (C10) and 2-aminobenzenesulfonic acid (SAnt)( orthanilic acid)-based pseudo beta-turn (C11) in their hybrid peptides. Solid-state crystal structure and solution-state NMR studies revealed that C10 and C11 can be simultaneously observed under appropriate conditions. The variable temperature NMR coefficient data suggest that the isolated C11/C14 hydrogen bond is weaker in comparison with the consecutive C10 and C11 turns.

}, issn = {2046-2069}, doi = {10.1039/c6ra05684a}, author = {Jedhe, Ganesh S. and Vijayadas, Kuruppanthara N. and Kotmale, Amol S. and Sangtani, Ekta and Shinde, Dinesh R. and Gonnade, Rajesh G. and Rajamohanan, Pattuparambil R. and Sanjayan, Gangadhar J.} } @article {43592, title = {Role of aliasing and interacting factors in the enhanced production of dehalogenase from Yarrowia lipolytica for degradation of brominated compounds}, journal = {Journal of Industrial and Engineering Chemistry}, volume = {41}, year = {2016}, month = {SEP}, pages = {114-121}, abstract = {Use of persistent organobromines for industrial applications has led to their accumulation in environment. Yarrowia lipolytica NCIM 3589, a tropical marine yeast, degrades and detoxifies bromocompounds by an initial hydrolytic step. By optimizing culture conditions with 1-bromodecane as reference compound, the dehalogenase involved was remarkably enhanced 13-fold (384.13 U/ml) by a hybrid statistical Plackett-Burman and Box-Behnken design of experiments. Studies bring out in a novel way the role of aliasing and other masked interactions in growth media factors. Importantly, the enzyme acted on C3-C16 bromoalkanes and bromoaromatics, thereby generalizing the {\textquoteright}green chemistry{\textquoteright} applicability of optimized media formulation for biotechnological applications. (C) 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.}, doi = {10.1016/j.jiec.2016.07.015}, author = {Vatsal, Aakanksha and Potdar, Chirag and Smita S. Zinjarde and Kumar, V. Ravi and Kulkarni, Bhasker D. and RaviKumar, Ameeta} } @article { ISI:000374626200020, title = {Role of surface synergistic effect on the performance of Ni-based hydrotalcite catalyst for highly efficient hydrogenation of furfural}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {417}, year = {2016}, month = {JUN}, pages = {153-162}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The selective vapor phase hydrogenation of furfural at ambient pressure has been investigated using a facile and robust hydrotalcite derived Ni containing mixed oxide catalyst. The systematic characterization results conferred that the difficulty in the reduction of Ni species due to the strong interaction between Ni and support, which facilitated from the homogeneous distribution of hydrotalcite structure. It was also found that the structure and catalytic performance of the catalysts were greatly influenced by Ni loading. Through fine-tuned surface elemental sites and reaction conditions, furfural conversion of 98\% with 95\% of furfuryl alcohol selectivity was achieved over a MAN-2 catalyst containing two molar ratio of Ni. The results have demonstrated that the incorporation of Mg significantly enhances the Ni-support interaction, Ni dispersion and catalytic performance. The high efficiency of the Ni-based hydrotalcite derived catalyst was mainly attributed to the surface synergistic interaction between the catalytically active metallic Ni sites and the strong basic sites, which furnished an eco-benign and sustainable catalyst for the selective hydrogenation of furfural. Furthermore, the spent catalyst analysis substantiated that no significant difference in the catalyst phase was observed even after 48 h of reaction stream. (C) 2016 Elsevier B.V. All rights reserved.

}, keywords = {alcohol-hydrotalcites-selective, Biomass-frurfural-furfuryl, Hydrogenation}, issn = {1381-1169}, doi = {10.1016/j.molcata.2016.03.019}, author = {Manikandan, Marimuthu and Venugopal, Ashok Kumar and Prabu, Kandasamy and Jha, Ratnesh Kumar and Thirumalaiswamy, Raja} } @article {42621, title = {Search for parity and time reversal violating effects in HgH: relativistic coupled-cluster study}, journal = {Journal of Chemical Physics}, volume = {144}, year = {2016}, month = {MAR}, pages = {Article No. 124307}, abstract = {

The high effective electric field (E-eff) experienced by the unpaired electron in an atom or a molecule is one of the key ingredients in the success of electron electric dipole moment (eEDM) experiment and its precise calculation requires a very accurate theory. We, therefore, employed the Z-vector method in the relativistic coupled-cluster framework and found that HgH has a very large E-eff value (123.2 GV/cm) which makes it a potential candidate for the next generation eEDM experiment. Our study also reveals that it has a large scalar-pseudoscalar (S-PS) P, T-violating interaction constant, W-s = 284.2 kHz. To judge the accuracy of the obtained results, we have calculated parallel and perpendicular magnetic hyperfine structure (HFS) constants and compared with the available experimental values. The results of our calculation are found to be in nice agreement with the experimental values. Therefore, by looking at the HFS results, we can say that both E-eff and W-s values are also very accurate. Further, We have derived the relationship between these quantities and the ratio which will help to get model independent value of eEDM and S-PS interaction constant. (C) 2016 AIP Publishing LLC.

}, doi = {10.1063/1.4944673}, author = {Sasmal, Sudip and Pathak, Himadri and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article { ISI:000374811300057, title = {Shape and size engineered cellulosic nanomaterials as broad spectrum anti-microbial compounds}, journal = {International Journal of Biological Macromolecules}, volume = {87}, year = {2016}, month = {JUN}, pages = {460-465}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Oxidized celluloses have been used for decades as antimicrobial wound gauzes and surgical cotton. We now report the successful synthesis of a next generation narrow size range (25-35 nm) spherical shaped nanoparticles of 2,3,6-tricarboxycellulose based on cellulose I structural features, for applications as new antimicrobial materials. This study adds to our previous study of 6-carboxycellulose. A wide range of bacteria such as Escherichia coli, Staphloccocus aureus, Bacillus subtilis and Mycobacterium tuberculosis (non-pathogenic as well as pathogenic strains) were affected by these polymers in in vitro studies. Activity against Mycobacteria were noted at high concentrations (MIC99 values 250-1000 mu g/ml, as compared to anti-TB drug Isoniazid 0.3 mu g/ml). However, the broad spectrum activity of oxidized celluloses and their nanoparticles against a wide range of bacteria, including Mycobacteria, show that these materials are promising new biocompatible and biodegradable drug delivery vehicles wherein they can play the dual role of being a drug encapsulant as well as a broad spectrum anti-microbial and anti-TB drug. (C) 2016 Published by Elsevier B.V.

}, keywords = {Anti-microbial, cellulose, Spherical nanoparticles, Tricarboxycellulose}, issn = {0141-8130}, doi = {10.1016/j.ijbiomac.2016.02.024}, author = {Sharma, Priyanka R. and Kamble, Sunil and Sarkar, Dhiman and Anand, Amitesh and Varma, Anjanikumar} } @article { ISI:000372425600066, title = {Simple, phosphine free, reusable Pd(II)-2,2 {\textquoteleft}-dihydroxybenzophenone-SBA-15 catalyst for arylation and hydrogenation reactions of alkenes}, journal = {New Journal of Chemistry}, volume = {40}, number = {3}, year = {2016}, month = {JAN}, pages = {2423-2432}, publisher = {ROYAL SOC CHEMISTRY}, type = {Article}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

An efficient, simple, phosphine and co-catalyst free C-C coupling reaction heterogeneous catalyst via a post grafting method is developed and reported. A covalently anchored phosphine free Pd(II) based 2,2{\textquoteright}-dihydroxybenzophenone (DHBP) complex over organofunctionalized SBA-15 has been synthesized by the reaction between aminofunctionalized SBA-15 (NH(2)SBA-15) and a 2,2{\textquoteright}-dihydroxybenzophenone (DHBP) ligand, and further complexation with Pd(II)Cl-2 to get Pd(II)-DHBP@ SBA-15. The synthesized catalysts were characterized by elemental analysis, XRD, N-2 sorption analyses, TG, DTA, FT-IR, solid state C-13 and Si-29 NMR spectra, XPS, UV-Visible, SEM, EDAX and TEM. The synthesized catalysts were screened in arylation (Heck reactions) and hydrogenation reactions of alkenes, and the results show that Pd(II)-DHBP@ SBA-15 exhibits high conversion and selectivity towards arylation and hydrogenation reactions of alkenes with high stability. The anchored solid catalysts can be recycled effectively and reused several times without major loss in activity.

}, issn = {1144-0546}, doi = {10.1039/c5nj02686e}, author = {Lazar, Anish and Vinod, Chathakudath P. and Singh, Anand Pal} } @article { ISI:000369211700025, title = {Small molecule activation by constrained phosphorus compounds: insights from theory}, journal = {Inorganic Chemistry}, volume = {55}, number = {2}, year = {2016}, month = {JAN}, pages = {558-565}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

An exciting new development in main group chemistry has been the use of a constrained, flat, phosphorus-based complex to mediate in reactions such as the dehydrogenation of ammonia borane (AB), and the activation of the NH bond in primary amines. Its importance is based on the fact that it shows that main group compounds, when properly designed, can be as effective as transition metal complexes for doing significant chemical transformations. What the current computational study, employing density functional theory (DFT), reveals is that a common, general mechanism exists that accounts for the behavior of the flat phosphorus compound in the different reactions that have been experimentally reported to date. This mechanism, which involves the mediation by a base as a proton transfer agent, is simpler and energetically more favorable than the previous mechanisms that have been proposed for the same reactions in the literature. It is likely that the knowledge gained from the current work about the chemical behavior of this phosphorus compound can be utilized to design new constrained phosphorus-based compounds.

}, issn = {0020-1669}, doi = {10.1021/acs.inorgchem.5b01074}, author = {Pal, Amrita and Vanka, Kumar} } @article {45646, title = {Synthesis and characterization of FeTiO3 ceramics}, journal = {Arabian Journal of Chemistry}, volume = {9}, year = {2016}, month = {SEP}, pages = {S429-S432}, type = {Article}, abstract = {

Nanocrystalline FeTiO3 ceramics powders were prepared by the sol-gel process combined with a surfactant-assisted template method. The resulting powders were calcined at different temperatures ranging from 150 degrees C to 600 degrees C for 2 h in an air. The results revealed that a pure hexagonal phase of FeTiO3 could be obtained at low temperature, 600 degrees C. The phase evolution of FeTiO3 was investigated by X-ray diffraction patterns (XRD), Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). Particle size and morphology was studied by transmission electron microscopy (TEM). (C) 2011 Production and hosting by Elsevier B.V. on behalf of King Saud University.

}, keywords = {Electron microscopy, hexagonal phase, Nanoparticles, sol-gel process, Ti-O bond}, issn = {1878-5352}, doi = {10.1016/j.arabjc.2011.05.012}, author = {Gambhire, Anil B. and Lande, Machhindra K. and Rathod, Sandip B. and Arbad, Balasaheb R. and Vidhate, Kaluram N. and Gholap, Ramakrishna S. and Patil, Kashinath R.} } @article {45828, title = {Synthesis and characterization of novel polymer-hybrid silver nanoparticles and its biomedical study}, journal = {Materials Today: Proceedings}, volume = {3}, year = {2016}, month = {JUN}, pages = {1949-1957}, type = {Article}, abstract = {

Hybrid polymer metal nanoparticles have advantages over conventional metal nanoparticles with respect to their stability, chemical resistance, antibacterial activity and drug delivery properties. In the current work, we have synthesized novel stimuli-responsive polymer hybrid silver nanoparticles using green synthesis method, where the plant extract is used as a reducing agent in the synthesis. Encapsulating metal nanoparticles with stimuli-responsive soft-polymeric system is novel and provides additional versatility whose functions and properties can be tailored by controlling any of the stimuli such as pH, temperature, ionic strength with respect to their antibacterial activity and physiological condition. Moreover, green synthesis methods have advantages over conventional methods involving chemical reducing agents that are often associated with environmental toxicity because of their enhanced antibacterial and other biological effects. The synthesized hybrid particles were characterized using Dynamic light scattering, UV-Visible spectroscopy and Small angle x-ray scattering. Further, we have investigated the antibacterial and cytotoxicity effect of these hybrid particles against different bacterial cells ( Salmonella) and mammalian cell lines (HCT116) respectively. These results are discussed in the light of previous studied work and these results suggest that our synthesized polymer hybrid nanoparticles are more antibacterial and less cytotoxic than the usual silver nanoparticles. (C) 2015Elsevier Ltd.All rights reserved.

}, keywords = {Antibacterial effect, Cytotoxicity, Polymeric hybrid particless, silver nanoparticles}, doi = {10.1016/j.matpr.2016.04.096}, author = {Verma, Suresh Kumar and Jha, Ealisha and Kiran, K. J. and Bhat, Suresh and Suar, Mrutyunjay and Mohanty, P. S.} } @article { ISI:000370693900022, title = {Synthesis and evaluation of thieno[2,3-d]pyrimidin-4(3H)-ones as potential antitubercular agents (vol 6, pg 2209, 2015)}, journal = {Medchemcomm}, volume = {7}, number = {2}, year = {2016}, month = {DEC}, pages = {379}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, issn = {2040-2503}, doi = {10.1039/c5md90062j}, author = {Borate, Hanumant B. and Annadate, Ritesh A. and Vagh, Sandip S. and Pisal, Mahesh M. and Deokate, Sagar B. and Arkile, Manisha A. and Jadhav, Nandadeep J. and Nawale, Laxman U. and Sarkar, Dhiman} } @article { ISI:000373492800012, title = {Synthesis and properties of poly(arylene ether)s based on 3-pentadecyl 4,4{\textquoteright}-biphenol}, journal = {Polymer International}, volume = {65}, number = {5}, year = {2016}, month = {MAY}, pages = {567-576}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

A new biphenol, 3-pentadecyl 4,4-biphenol, was synthesized starting from 3-pentadecylphenol and was polycondensed with 4,4-difluorobenzophenone, 1,3-bis(4-fluorobenzoyl)benzene and bis(4-fluorophenyl)sulfone to obtain poly(arylene ether)s with biphenylene linkages in the backbone and pendent pentadecyl chains. Inherent viscosities and number-average molecular weights (M-n) of the poly(arylene ether)s were in the range 0.50 - 0.81 dL g(-1) and 2.2 x 10(4) - 8.3 x 10(4), respectively. Detailed NMR spectroscopic studies of the poly(arylene ether)s indicated the presence of constitutional isomerism which existed because of the non-symmetrical structure of 3-pentadecyl 4,4-biphenol. The poly(arylene ether)s readily dissolved in common organic solvents such as dichloromethane, chloroform and tetrahydrofuran and could be cast into tough, transparent and flexible films from their chloroform solutions. The poly(arylene ether)s exhibited T-g values in the range 35-60 degrees C which are lower than that of reference poly(arylene ether)s without pentadecyl chains. The 10\% decomposition temperatures (T-10) of the poly(arylene ether)s were in the range 410-455 degrees C indicating their good thermal stability. A gas permeation study of poly(ether sulfone) containing pendent pentadecyl chains revealed a moderate increase in permeability for helium, hydrogen and oxygen. However, there was a large increase in permeability for carbon dioxide which could be attributed to the internal plasticization effect of pendent pentadecyl chains. (c) 2016 Society of Chemical Industry

}, keywords = {cashew nut shell liquid (CNSL), gas permeation study, pentadecyl, poly(arylene ether)s, thermal stability}, issn = {0959-8103}, doi = {10.1002/pi.5095}, author = {Tawade, Bhausaheb V. and Shaligram, Sayali V. and Valsange, Nitin G. and Kharul, Ulhas K. and Wadgaonkar, Prakash P.} } @article {45830, title = {Synthesis of Au@Ni bimetallic core shell nanoparticle and nanochains in soyabean oil and their catalytic hydrogenation reactions}, journal = {ChemistrySelect}, volume = {1}, year = {2016}, month = {FEB}, pages = {140-146}, type = {Article}, abstract = {

Synthesis of Au@Ni bimetallic core shell nanostructures using commercially available soya bean oil as the solvent through a sequential reduction strategy is reported. The energy efficiency and economic viability comes from the much milder temperatures and replacement of expensive and environmentally hazardous solvents like long chain organic amines and acids previously reported for synthesis. Thus, core shell nanoparticles having size regime of 10-15 nm with an excellent control over the nickel shell thickness (2 nm) over the gold core (8-10 nm) and Au@Ni nanochains is achieved. The synthesized materials are demonstrated to synergistically catalyze hydrogenation of nitro and C-C multiple bonds with much better efficiency as compared to individual nanoparticle counterparts.

}, keywords = {Bimetallic nanoparticles, Gold catalysis, hydrogenation reactions, synergistic effects}, issn = {2365-6549}, doi = {10.1002/slct.201500006}, author = {Bharathan, Vysakh A. and Yadukiran, V. and Lazar, Anish and Singh, Anand. P. and Vinod, Chathakudath P.} } @article {42572, title = {Synthesis of (-)-phaitanthrin D and (+)-dihydropyrroloindoloquinazolinone}, journal = {Synthesis-Stuttgart}, volume = {48}, year = {2016}, month = {SEP}, pages = {2896-2903}, abstract = {

The synthesis of (-)-phaitanthrin D and (+)-dihydropyrroloindoloquinazolinone are reported starting from the corresponding especially designed enantiomerically pure pivotal anthranilamide based building blocks using HMDS/ZnCl2 and NaHMDS.

}, doi = {10.1055/s-0035-1562098}, author = {Vaidya, Sagar D. and N. P. Argade} } @book {43012, title = {Taxonomy of mycotoxigenic fungi}, year = {2016}, publisher = {Scientific Publisher}, organization = {Scientific Publisher}, abstract = {

Mycotoxins, toxic metabolites of molds elaborated during their colonization of foods and feeds, pose a threat to human and animal life. Molds are the diverse group of fungi, which grow in compatatively dry and warm environments, produce copious amount of spores and promote the elaboration of these mycotoxins. Mycotoxigenic fungi, which are unique their sporulating apparatus and exhibit wide variation in their morphology, poses a challenge in their identification. There are numerous examples of their misidentification leading to wrong conclusions. Precise information on taxonomy of these fungi is lacking. Therefore, this book fulfills the need of providing comprehensive information and keys helpful for the accurate identification of these moulds. The book also provides comprehensive account of morphology, mycotoxins produced and factors leading to the elaboration of mycotoxins. Information on their molecular detection, anamorphic and teleomorphic relationships is also included.

}, author = {Vankudoth, Koteswara Rao and Sivadevuni, Girisham and Reddy S. M.} } @article { ISI:000380241600003, title = {Ultrasound- and molecular sieves-assisted synthesis, molecular docking and antifungal evaluation of 5-(4-(benzyloxy)-substituted phenyl)-3-((phenylamino)methyl)-1,3,4-oxadiazole-2(3H)-thiones}, journal = {Molecules}, volume = {21}, number = {5}, year = {2016}, month = {MAY}, pages = {484}, publisher = {MDPI AG}, address = {ST ALBAN-ANLAGE 66, CH-4052 BASEL, SWITZERLAND}, abstract = {

A novel series of 5-(4-(benzyloxy) substituted phenyl)-3-((phenyl amino) methyl)-1,3,4-oxadiazole-2(3H)-thione Mannich bases 6a-o were synthesized in good yield from the key compound 5-(4-(benzyloxy) phenyl)-1,3,4-oxadiazole-2(3H)-thione by aminomethylation with paraformaldehyde and substituted amines using molecular sieves and sonication as green chemistry tools. The antifungal activity of the new products was evaluated against seven human pathogenic fungal strains, namely, Candida albicans ATCC 24433, Candida albicans ATCC 10231, Candida glabrata NCYC 388, Cryptococcus neoformans ATCC 34664, Cryptococcus neoformans PRL 518, Aspergillus fumigatus NCIM 902 and Aspergillus niger ATCC 10578. The synthesized compounds 6d, 6f, 6g, 6h and 6j exhibited promising antifungal activity against the tested fungal pathogens. In molecular docking studies, derivatives 6c, 6f and 6i showed good binding at the active site of C. albicans cytochrome P450 enzyme lanosterol 14 alpha-demethylase. The in vitro antifungal activity results and docking studies indicated that the synthesized compounds have potential antifungal activity and can be further optimized as privileged scaffolds to design and develop potent antifungal drugs.

}, keywords = {1, 3, 4-oxadiazoles, Antifungal activity, Mannich reaction, Molecular docking, Molecular sieves, Ultrasound}, issn = {1420-3049}, doi = {10.3390/molecules21050484}, author = {Nimbalkar, Urja D. and Tupe, Santosh G. and Seijas Vazquez, Julio A. and Khan, Firoz A. Kalam and Sangshetti, Jaiprakash N. and Nikalje, Anna Pratima G.} } @article { ISI:000371953000024, title = {Unraveling origins of the heterogeneous curvature dependence of polypeptide interactions with carbon nanostructures}, journal = {Physical Chemistry Chemical Physics}, volume = {18}, number = {8}, year = {2016}, month = {FEB}, pages = {5910-5924}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Emerging nanotechnology has rapidly broadened interfacial prospects of biological molecules with carbon nanomaterials (CNs). A prerequisite for effectively harnessing such hybrid materials is a multifaceted understanding of their complex interfacial interactions as functions of the physico-chemical characteristics and the surface topography of the individual components. In this article, we address the origins of the curvature dependence of polypeptide adsorption on CN surfaces (CNSs), a phenomenon bearing an acute influence upon the behavior and activity of CN-protein conjugates. Our benchmark molecular dynamics (MD) simulations with the amphiphilic full-length amyloid beta (A beta) peptide demonstrate that protein adsorption is strongest on the concave (inner) CN-surface, weakest on the convex (outer) surface, and intermediary on the planar surface, in agreement with recent experimental reports. The curvature effects, however, are found to manifest non-uniformly between the amino acid subtypes. To understand the underlying interplay of the chemical nature of the amino acids and surface topography of the CNs, we performed high-level quantum chemical (QM) calculations with amino acid analogs (MA) representing their five prominent classes, and convex, concave and planar CN fragments. Molecular electrostatic potential maps reveal pronounced curvature dependence in the mixing of electron densities, and a resulting variance in the stabilization of the non-covalentty bound molecular complexes. Interestingly, our study revealed that the interaction trends of the high-level QM calculations were captured well by the empirical force field. The findings in this study have important bearing upon the design of carbon based bio-nanomaterials, and additionally, provide valuable insights into the accuracy of various computational techniques for probing non-bonded interfacial interactions.

}, issn = {1463-9076}, doi = {10.1039/c5cp04675k}, author = {Jana, Asis K. and Tiwari, Mrityunjay K. and Vanka, Kumar and Sengupta, Neelanjana} } @article { ISI:000380045400014, title = {Unravelling the mechanism of electrochemical degradation of PANI in supercapacitors: achieving a feasible solution}, journal = {Chemelectrochem}, volume = {3}, number = {6}, year = {2016}, month = {JUN}, pages = {933-942}, publisher = {WILEY-V C H VERLAG GMBH}, address = {POSTFACH 101161, 69451 WEINHEIM, GERMANY}, abstract = {

Herein, we have investigated the mode of electrochemical degradation of polyaniline (PANI) when it was utilized as electrodes for supercapacitors. The PANI-based electrodes in supercapacitor devices were biased at a constant potential of 0.80 V, and the performance characteristics and property changes were carefully investigated as a function of the difference in the polarity of the electrodes. Subsequent to this, the analysis of the individual electrodes [positive (POS-PANI) and negative (NEG-PANI)] shows that the degradation mainly occurs at POS-PANI in comparison to NEG-PANI. Moreover, NEG-PANI retains a maximum capacitance of 510 Fg(-1), with a low charge-transfer resistance (R-CT) of 1.84 Omega and similar redox behavior in comparison to the fresh PANI (f-PANI). In contrast to this case, POS-PANI shows significant loss in capacitance (250 Fg(-1)) and increase in R-CT (3.5 Omega) with a disappearance of the characteristic redox behavior normally displayed by PANI. Furthermore, the drastic drop in the electrical conductivity for POS-PANI (1.2 Scm(-1)) compared to f-PANI (3.4 Scm(-1) and NEG-PANI (2.4 Scm(-1)) shows that the degradation of PANI occurs mainly at the anode (POS-PANI) and, thus, contributes to reduce the net performance of the cell. Hence, to ensure this potential-induced degradation of PANI in supercapacitors and also to promote the system stability, we made an asymmetric supercapacitor (ASC) by keeping PANI as a negative electrode and using carbon as a positive electrode. The derived system is found to display stable capacitance behavior before and after the potential application, in contrast to the ASC fabricated by using conventional method, that is, by keeping PANI as the positive electrode and carbon as the negative electrode. Furthermore, the durability analysis of the prototype solid-state ASC shows an enhanced durability of 27000 cycles with excellent columbic efficiency. The findings of the present study will be helpful in the development of highly stable supercapacitors and other similar energy systems when a material like PANI should be utilized for the electrode applications.

}, keywords = {asymmetric supercapacitors, cycle stability, electrochemical degradation, polarization, redox chemistry}, issn = {2196-0216}, doi = {10.1002/celc.201500502}, author = {Sekar, Pandiaraj and Anothumakkool, Bihag and Vijayakumar, Vidyanand and Lohgaonkar, Apurva and Kurungot, Sreekumar} } @article {45651, title = {Urinary proteome alterations in HER2 enriched breast cancer revealed by multipronged quantitative proteomics}, journal = {Proteomics}, volume = {16}, year = {2016}, month = {SEP}, pages = {2403-2418}, type = {Article}, abstract = {

Globally, breast cancer is the second most common cancer among women. Although biomarker discoveries through various proteomic approaches of tissue and serum samples have been studied in breast cancer, urinary proteome alterations in breast cancer are least studied. Urine being a noninvasive biofluid and a significant source of proteins, it has the potential in early diagnosis of breast cancer. This study used complementary quantitative gel-based and gel-free proteomic approaches to find a panel of urinary protein markers that could discriminate HER2 enriched (HE) subtype breast cancer from the healthy controls. A total of 183 differentially expressed proteins were identified using three complementary approaches, namely 2D-DIGE, iTRAQ, and sequential window acquisition of all theoretical mass spectra. The differentially expressed proteins were subjected to various bioinformatics analyses for deciphering the biological context of these proteins using protein analysis through evolutionary relationships, database for annotation, visualization and integrated discovery, and STRING. Multivariate statistical analysis was undertaken to identify the set of most significant proteins, which could discriminate HE breast cancer from healthy controls. Immunoblotting and MRM-based validation in a separate cohort testified a panel of 21 proteins such as zinc-alpha2-glycoprotein, A2GL, retinol-binding protein 4, annexin A1, SAP3, SRC8, gelsolin, kininogen 1, CO9, clusterin, ceruloplasmin, and alpha 1-antitrypsin could be a panel of candidate markers that could discriminate HE breast cancer from healthy controls.

}, keywords = {2D-DIGE, Biomedicine, Breast cancer, HER2 enriched, SWATH, Urinary biomarkers}, issn = {1615-9853}, doi = {10.1002/pmic.201600015}, author = {Gajbhiye, Akshada and Dabhi, Raju and Taunk, Khushman and Vannuruswamy, Garikapati and RoyChoudhury, Sourav and Adhav, Ragini and Seal, Shubhendu and Mane, Anupama and Bayatigeri, Santhakumari and Santra, Manas K. and Chaudhury, Koel and Rapole, Srikanth} } @conference { ISI:000382147300037, title = {Use genetic programming for selecting predictor variables and modeling in process identification}, booktitle = {2016 Indian Control Conference (ICC)}, year = {2016}, note = {2nd Indian Control Conference (ICC), Indian Inst Technol, Hyderabad, INDIA, JAN 04-06, 2016}, month = {JAN}, pages = {230-237}, publisher = {IEEE Control Syst Soc; Honeywell; Mathworks; ABB R \& D Div; GE; Mahindra Ecole Centrale}, organization = {IEEE Control Syst Soc; Honeywell; Mathworks; ABB R \& D Div; GE; Mahindra Ecole Centrale}, address = {345 E 47th ST, New York, NY 10017 USA}, abstract = {

Availability of an accurate and robust dynamic model is essential for implementing the model dependent process control. When first principles based modeling becomes difficult, tedious and/or costly, a dynamic model in the black-box form is obtained (process identification) by using the measured input-output process data. Such a dynamic model frequently contains a number of time delayed inputs and outputs as predictor variables. The determination of the specific predictor variables is usually done via a trial and error approach that requires an extensive computational effort. The computational intelligence (CI) based data-driven modeling technique, namely, genetic programming (GP) can search and optimize both the structure and parameters of a linear/nonlinear dynamic process model. It is also capable of choosing those predictor variables that significantly influence the model output. Thus usage of GP for process identification helps in avoiding the extensive time and efforts involved in the selection of the time delayed input-output variables. This advantageous GP feature has been illustrated in this study by conducting process identification of two chemical engineering systems. The results of the GP-based identification when compared with those obtained using the transfer function based identification clearly indicates the outperformance by the former method.

}, keywords = {dynamic model, genetic programming, predictor variable, process identification, Sensitivity analysis}, isbn = {978-1-4673-7993-9}, author = {Verma, Devendra and Goel, Purva and Patil-Shinde, Veena and Tambe, Sanjeev S.} } @article {43932, title = {Abundance matters: role of albumin in diabetes, a proteomics perspective}, journal = {Expert Review of Proteomics}, volume = {14}, year = {2017}, month = {JUL}, type = {Article}, abstract = {Introduction: Human serum albumin (HSA) is a multifaceted protein with vital physiological functions. It is the most abundant plasma protein with inherent capability to bind to diverse ligands, and thus susceptible to various post-translational modifications (PTMs) which alter its structure and functions. One such PTM is glycation, a non-enzymatic reaction between reducing sugar and protein leading to formation of heterogeneous advanced glycation end products (AGEs). Glycated albumin (GA) concentration increases significantly in diabetes and is implicated in development of secondary complications. Areas covered: In this review, we discuss in depth formation of GA and its consequences, approaches used for characterization and quantification of GA, milestones in GA proteomics, clinical relevance of GA as a biomarker, significance of maintaining abundant levels of albumin and future perspectives. Expert commentary: Elevated GA levels are associated with development of insulin resistance as well as secondary complications, in healthy and diabetic individuals respectively. Mass spectrometry (MS) based approaches aid in precise characterization and quantification of GA including early and advanced glycated peptides, which can be useful in prediction of the disease status. Thus GA has evolved to be one of the best candidates in the pursuit of diagnostic markers for prediction of prediabetes and diabetic complications.}, doi = {10.1080/14789450.2017.1352473}, author = {Bhat, Shweta and Jagadeeshaprasad, Mashanipalya G. and Venkatasubramani, Vinashya and Kulkarni, Mahesh J.} } @article {45684, title = {All-solid-state-supercapacitor possessing a non-aqueous gel polymer electrolyte prepared using a UV-assisted in situ polymerization strategy}, journal = {Journal of Materials Chemistry A}, volume = {5}, year = {2017}, month = {MAY}, pages = { 8461-8476}, type = {Article}, abstract = {

In this work, we report the synthesis of a high ionic conducting and mechanically stable non-aqueous gel polymer electrolyte (GPE) in which a liquid electrolyte (LiClO4/propylene carbonate) is entrapped in a poly(2-hydroxy-3-phenoxy propyl acrylate) matrix by a UV assisted in situ polymerisation strategy. Unlike conventional dry and quasi-solid non-aqueous GPEs, our system (H-P-L-3M-80\%) shows an excellent ionic conductivity of 4.7 x 10(-3) S cm(-1), a value which is comparable to those of non-aqueous liquid electrolytes. The high mechanical stability of GPE arises due to the covalent cross-links present in the polymer matrix as well as the reversible non-covalent cross-links between the solvent and the polymer matrix through the Li+ cations. Subsequently, the GPE has been prepared in situ on the inner and the outer surface of the electrode material to fabricate a 2.0 V supercapacitor device with a high mass loading (3.8 mg cm(-2)) of the active material (YP-80F, a high surface area porous carbon). The device shows an equivalent series resistance (ESR) as low as 2.2 Omega, which is close to that of the device fabricated from the corresponding liquid electrolyte and is far better than those of the devices evolved from conventional GPEs and dry polymer electrolytes. The mass specific capacitance of 113 F g(-1) obtained at a current density of 2 mA cm(-2) shows 81\% retention even at a high current density of 20 mA cm(-2). The scalability of the strategy is demonstrated by fabricating a large area (area = 16 cm(2), loading = 4.0 mg cm(-2)) all-solid-state flexible-supercapacitor (H-P-L-3M-S-4.0) device which can be operated at a potential window of 2.5 V. The device was found to show a mass specific capacitance of 111 F g(-1) at a current density of 1 mA cm(-2) (0.25 A g(-1)), all the while, retaining a very low ESR of 2.2 Omega. The potential of the strategy to mimic the liquid-like electrode-electrolyte interface, augmented with the ability to tune further, opens up new horizons for energy storage devices.

}, doi = {10.1039/c7ta01514c}, author = {Vijayakumar, V. and Anothumakkool, B. and Torris, A. T. A. and Nair, S. B. and Badiger, M. V. and Kurungot, S.} } @article {45702, title = {Aromatic polyesters containing pendent 4-(phenylsulfonyl)phenyl groups: synthesis and characterization}, journal = {Journal of Polymer Research}, volume = {24}, year = {2017}, month = {MAR }, pages = {57}, type = {Article}, abstract = {

A new bisphenol, 1,1-bis-[(4-hydroxyphenyl)-1-(4-phenylsulfonyl) phenyl)] ethane (DPSBP) was synthesized starting from diphenylsulfide and was characterized by spectroscopic methods. DPSBP was polycondensed with isophthalic acid chloride (IPC), terephthalic acid chloride (TPC) and a mixture of IPC and TPC (50: 50 mol\%) by phase-transfer catalysed interfacial polymerization method to obtain aromatic polyesters containing pendent 4-(phenylsulfonyl)phenyl groups. A series of copolyesters was also obtained by polycondensation of varying molar proportions of DPSBP and bisphenol-A (BPA) with TPC. (Co) polyesters exhibited inherent viscosities in the range 0.56-1.57 dLg(-1) and number average molecular weights (Mn) were in the range 28,650-80,230 g/mol. Polyesters dissolved readily in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and aprotic polar solvents such as N-methylpyrrolidone, and N, N-dimethylacetamide. Tough, transparent and flexible films of polyesters could be cast from their chloroform solutions. X-Ray diffraction studies indicated amorphous nature of aromatic polyesters. Polyesters showed T-g values in the range 223-257 degrees C while T-10 values were in the range of 469-484 degrees C indicating their excellent thermal stability.

}, keywords = {Aromatic polyesters, Bulky pendent group, solubility, thermal stability}, issn = {1022-9760}, doi = {10.1007/s10965-017-1217-4}, author = {Bapat, Snehalata P. and Jadhav, Sushilkumar A. and Valsange, Nitin G. and Tawade, Bhausaheb V. and Honkhambe, Pandurang N. and Chavan, Nayaku N. and Wadgaonkar, Prakash P.} } @article {43949, title = {Assessing therapeutic potential of molecules: molecular property diagnostic suite for tuberculosis}, journal = {Journal of Chemical Sciences}, volume = {129}, year = {2017}, month = {MAY}, pages = {515-531}, type = {Article}, abstract = {

Abstract: Molecular Property Diagnostic Suite (MPDS TB) is a web tool (http://mpds.osdd.net) designed to assist the in silico drug discovery attempts towards Mycobacterium tuberculosis (Mtb). MPDS TB tool has nine modules which are classified into data library (1{\textendash}3), data processing (4{\textendash}5) and data analysis (6{\textendash}9). Module 1 is a repository of literature and related information available on the Mtb. Module 2 deals with the protein target analysis of the chosen disease area. Module 3 is the compound library consisting of 110.31 million unique molecules generated from public domain databases and custom designed search tools. Module 4 contains tools for chemical file format conversions and 2D to 3D coordinate conversions. Module 5 helps in calculating the molecular descriptors. Module 6 specifically handles QSAR model development tools using descriptors generated in the Module 5. Module 7 integrates the AutoDock Vina algorithm for docking, while module 8 provides screening filters. Module 9 provides the necessary visualization tools for both small and large molecules. The workflow-based open source web portal, MPDS TB 1.0.1 can be a potential enabler for scientists engaged in drug discovery in general and in anti-TB research in particular. Graphical Abstract: SYNOPSIS: A web-based MPDS TB Galaxy tool is developed for assessing therapeutic potential of molecules. MPDS TB is categorized into Data Library, Data Processing and Data Analysis. It can be a potential enabler for scientists engaged in drug discovery in general and in anti-TB research in particular. [Figure not available: see fulltext.] {\textcopyright} 2017, Indian Academy of Sciences.

}, keywords = {chemical analysis, Chemoinformatics, computational chemistry, Diagnosis, Drug discovery portal, Information analysis, Libraries, Molecular graphics, Molecules, Neglected diseases, Open science, Portals, tuberculosis, Web-based technology, Websites}, issn = {0974-3626}, doi = {10.1007/s12039-017-1268-4}, author = {Gaur, A. S. and Bhardwaj, A. and Sharma, A. and John, L. and Vivek, M. R. and Tripathi, N. and Bharatam, P. V. and Kumar, R. and Janardhan, S. and Mori, A. and Banerji, A. and Lynn, A. M. and Hemrom, A. J. and Passi, A. and Singh, A. and Kumar, A. and Muvva, C. and Madhuri, C. and Choudhury, C. and Kumar, D. A. and Pandit, D. and Bharti, D. R. and Kumar, D. and Singam, E. A. and Raghava, G. P. and Sailaja, H. and Jangra, H. and Raithatha, K. and Tanneeru, K. and Chaudhary, K. and Karthikeyan, M. and Prasanthi, M. and Kumar, N. and Yedukondalu, N. and Rajput, N. K. and Saranya, P. S. and Narang, P. and Dutta, Prantu and Krishnan, R.} } @article {45660, title = {Auger decay rates of core hole states using equation of motion coupled cluster method}, journal = {Chemical Physics}, volume = {482 }, year = {2017}, month = {JAN}, pages = {160-164}, type = {Article}, abstract = {The recent development of Linac coherent light source high intense X-ray laser makes it possible to create double core ionization in the molecule. The generation of double core hole state and its decay is identified by Auger spectroscopy. The decay of this double core hole (DCH) states can be used as a powerful spectroscopic tool in chemical analysis. In the present work, we have implemented a promising approach, known as CAP-EOMCC method, which is a combination of complex absorbing potential (CAP) and equation -of-motion coupled cluster (EOMCC) approach to calculate the lifetime of single and double core hole states. We have applied this method to calculate the lifetime of the single core hole (K-LL) and double core hole (KK-KLL) states of CH4, NH3 and HF molecules. The predicted lifetime is found to be extremely short. (C) 2016 Elsevier B.V. All rights reserved.}, doi = {10.1016/j.chemphys.2016.09.038}, author = {Ghosh, Aryya and Vaval, Nayana and Pal, Sourav} } @conference {45756, title = {Biomedical literature mining for protein-protein interactions analysis using electronic mailing system}, booktitle = {253rd National Meeting of the American-Chemical-Society (ACS) on Advanced Materials, Technologies, Systems, and Processes}, year = {2017}, month = {APR }, publisher = {Amer chemical soc, 1155 16TH ST, NW, Washington, DC 20036 USA}, organization = {Amer chemical soc, 1155 16TH ST, NW, Washington, DC 20036 USA}, address = { San Francisco, CA}, author = {Karthikeyan, Muthukumarasamy and Vyas, Renu} } @inbook {45774, title = {Biotechnological interventions to modulate terpenoid indole alkaloid pathway in catharanthus roseus using in vitro tools and approaches}, booktitle = {Catharanthus Roseus: Current Research and Future Prospects}, year = {2017}, pages = {247-275}, publisher = {Springer International Publishing}, organization = {Springer International Publishing}, chapter = {18}, address = { Switzerland}, abstract = {

Catharanthus roseus plant is valued for harboring more than 130 bioactive terpenoid indole alkaloids (TIAs) including the two of its leaf derived bisindole alkaloids-vinblastine and vincristine which are indispensible constituents of antineoplastic drugs used in metastatic malignancy associated with acute lymphoblastic leukaemia{\textquoteright}s and Hodgkin{\textquoteright}s/Non-Hodgkin{\textquoteright}s lymphomas. The extremely low in planta occurrence of TIAs in C. roseus plants resulting in high commercial demand and exorbitant price have brought this herb in focus of an intense scientific scrutiny in last 30 years. Research efforts have so far advanced in two major directions: towards understanding the enzymology and genetic regulation of the concerned metabolic pathway(s) leading to TIAs biosynthesis in plant and, secondly, exploring the possibility of developing cell/tissue culture based platforms for in vitro TIAs production to meet the industry{\textquoteright}s demand. Designing plants, free from such metabolic constraints, can be a possible approach to enhance the production of plant based medicines. This subject of plant metabolic engineering is gaining lot of attention these days. Pathway manipulation using the modern tools of genetic engineering to over-express a limiting enzyme or to suppress the expression of an enzyme using a shared substrate of a branched pathway are attractive options of metabolic engineering for diverting the metabolic flux towards the synthesis of a desired end product. Knowledge, thus gained, indicates that TIAs biogenetic route is characterized by extensive metabolic cross-talk and shuttling of at least 35 intermediates synthesized via 30 enzymatic reactions occurring in four different types of tissues (epidermis, internal phloem parenchyma, idioblasts and leticifers) and five different sub-cellular compartments (cytosol, vacuole, thyllakoid membrane, nucleus and endoplasmic reticulum). The complexity is further compounded by extremely high level of recalcitrancy of C. roseus plant for regeneration and Agrobacterium- mediated genetic transformation for pathway engineering. As a consequence, all genetic modulation efforts so far made in C. roseus are confined to cell suspension and transformed hairy root cultures that lack the required level of cyto- and tissue- differentiation essential for the expression of entire TIAs pathway genes and enzymes. A perusal of published work in C. roseus clearly suggests that inspite of several pathway manipulation/engineering attempts, the level of TIAs production in cell/tissue/hairy root cultures of this herb could never be enhanced to the level of expectations. The enzymatic, developmental and environmental rigidity/complexi- ties associated with the biosynthetic pathway of these alkaloids have often been cited as possible reasons for these disappointing outcomes Therefore, three major areas of investigation are in focused attention of Catharanthus researchers{\textquoteright} the world over are: (1) how to select or design the starting cells or tissue(s) to realize the full potential of applying metabolic engineering tools for up-regulating the TIAs pathway in them; (2) how to overcome the strong recalcitrancy of Catharanthus plant tissues for de novo organogenesis and in vitro plant regeneration for whole plant-level expression of a transgene coding either for a limiting pathway enzyme or a transcription factor that can control the global expression of several pathway genes and, (3) how to overcome the inability of non-differentiated cell cultures to execute those pathway steps that are expressed only in specialized tissues/cells of C. roseus plants. Various biotechnological approaches and generation of novel tissue types have been discussed in the present chapter for the modulation and increased TIAs flux in C. Roseus.

}, isbn = {978-331951619-6}, doi = {10.1007/978-3-319-51620-2_10}, author = {Verma, P. and Khan, S. A. and Parasharami, V. and Mathur, A. K.} } @article {43921, title = {Carbonylation of glycerol with urea to glycerol carbonate over supported Zn catalysts}, journal = {Applied Petrochemical Research}, volume = {7}, year = {2017}, month = {APR}, chapter = {41-53}, abstract = {

Glycerol carbonylation with urea is a very feasible option to produce glycerol carbonate with a net result of CO2 fixation through urea synthesis. The prerequisite of an efficient catalyst for this reaction is to possess both acid and basic sites together. Several acidic supports were screened for ZnO catalyst in this work and Zn/MCM-41 was found to exhibit the best activity and almost complete selectivity to glycerol carbonate (GC). Although, non-catalytic glycerol carbonylation resulted in GC formation but glycerol conversion achieved was twice with Zn/MCM-41 as a catalyst. Further to that increase in Zn loading from 2 to 5\% resulted in increase in glycerol conversion from 63 to 82\%. The prepared catalysts were characterized by XRD, NH3 and CO2-TPD and effects of reaction parameters such as catalyst loading, glycerol to urea mole ratio and temperature on glycerol conversion and GC selectivity in batch mode of operation were also studied. Time on stream activity of 5\% Zn/MCM-41 catalyst for continuous carbonylation of glycerol was also studied for ~100 h with an average conversion of ~55\% and complete selectivity to GC. This indicated five times lower productivity of GC per h due to lower residence time than that in a batch operation as compared to that of a continuous operation. Activation energy estimated from the Arrhenius plot was found to be 39.82 kJ mol-1 suggesting that the reaction is kinetically controlled. A reaction pathway mediated by acid and basic sites of the Zn/MCM-41 catalyst is also proposed.

}, keywords = {Acid{\textendash}base ratio, Continuous process, Glycerol carbonate, Glycerol-urea carbonylation, reaction pathway, Supported Zn, Zn loading}, issn = {2190-5533}, doi = {10.1007/s13203-017-0177-2}, author = {Kondawar, S. E. and Mane, R. B. and Vasishta, A. and More, S. B. and Dhengale, S. D. and Rode, C. V.} } @article {45738, title = {Convenient route for Au@Ti-SiO2 nanocatalyst synthesis and its application for room temperature CO oxidation}, journal = {Journal of Physical Chemistry C}, volume = {121}, year = {2017}, month = {MAR }, pages = {4946-4957}, type = {Article}, abstract = {

Small gold nanoparticles.of size less than 5 nm encapsulated inside titanium modified silica shell have been reported. Here, a modified sol-gel method, which is a one-step process, produces Au@Ti-SiO2 nanocatalyst with a good control of titanium loading. With a titanium loading of 0.9 and 2.2 wt \% in silica, unprecedented low temperature activity (full conversion) is observed for this catalyst for CO oxidation reaction compared to Au@SiO2 catalyst. A combination of optimum sized gold nanoparticles with a large amount of oxygen vacancies created due to Ti incorporation in silica matrix is considered to be the reason for this enhanced catalytic activity. The size of.gold nanoparticles is maintained even after high temperature pretreatments, which show the benefit of encapsulation. The effect of the various pretreatments on the catalytic activity has also been reported.

}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.6b10202}, author = {Soni, Yogita and Kumar, Anumol Erumpukuthical Ashok and Nayak, Chandrani and Deepak, Francis Leonard and Vinod, C. P.} } @article {45768, title = {Crystallisation-enhanced bulk hole mobility in phenothiazine-based organic semiconductors}, journal = {Scientific Reports}, volume = {7}, year = {2017}, month = {APR }, pages = {46268}, type = {Article}, abstract = {

A series of three novel donor-acceptor systems based on C(3)-malononitrile-substituted phenothiazines was synthesised in good overall yields and their thermal, spectroscopic, and electrochemical properties were characterised. The compounds were prepared through a sequence of Ullmann-coupling, Vilsmeier-Haack formylation and Knoevenagel-condensation, followed by Suzuki-coupling reactions for introduction of aryl substitutents at C(7) position of the phenothiazine. The introduction of a donor unit at the C(7) position exhibited a weak impact on the optical and electrochemical characteristics of the compounds and led to amorphous films with bulk hole mobilities in the typical range reported for phenothiazines, despite the higher charge delocalisation as attested by computational studies. In contrast, highly ordered films were formed when using the C(7)-unsubstituted 3-malononitrile phenothiazine, exhibiting an outstanding mobility of 1 x 10(-3) cm(2) V-1 s(-1), the highest reported for this class of compounds. Computational conformational analysis of the new phenothizanes suggested that free rotation of the substitutents at the C(7) position suppresses the ordering of the system, thereby hampering suitable packing of the new materials needed for high charge carrier mobility.

}, issn = {2045-2322}, doi = {10.1038/srep46268}, author = {Shinde, D. B. and Salunke, Jagadish K. and Candeias, Nuno R. and Tinti, Francesca and Gazzano, Massimo and Wadgaonkar, P. P. and Priimagi, Arri and Camaioni, Nadia and Vivo, Paola} } @article {43728, title = {DBU-mediated diastereoselective aldol-type cyanomethylation of isatins}, journal = {Journal of Organic Chemistry}, volume = {82}, year = {2017}, month = {APR}, pages = {4489-4496}, type = {Article}, abstract = {An efficient, metal-free approach to 3-substituted 3-hydroxybxindole by DBU-mediated highly diastereoselective addition of aryl acetonitrile to N-protected isatin under mild conditions has been developed. The reaction proceeds smoothly to produce respective cyanomethylated adducts in good yield and excellent diastereoselectivity. Further transformation of the cyanide group allowed the synthesis of an advance intermediate of corresponding (+/-) CPC analogue. The mechanistic insight :toward the aldol-type cyanomethylation, of N-tritylisatin with benzyl cyanide was obtained by DFT calculations.}, doi = {10.1021/acs.joc.7b00512}, author = {Rao, V. U. Bhaskara and Kumar, Krishna and Das, Tamal and Vanka, Kumar} } @article {45716, title = {Defect induced modification of structural, topographical and magnetic properties of zinc ferrite thin films by swift heavy ion irradiation}, journal = {Nuclear Instruments \& Methods In Physics Research Section B-Beam Interactions With Materials And Atoms}, volume = {396}, year = {2017}, month = {APR }, pages = {68-74}, type = {Article}, abstract = {

Swift heavy ion irradiation provides unique ways to modify physical and chemical properties of materials. In ferrites, the magnetic properties can change significantly as a result of swift heavy ion irradiation. Zinc ferrite is an antiferromagnet with a Neel temperature of 10 K and exhibits anomalous magnetic properties in the nano regime. Ion irradiation can cause amorphisation of zinc ferrite thin films; thus the role of crystallinity on magnetic properties can be examined. The influence of surface topography in these thin films can also be studied. Zinc ferrite thin films, of thickness 320 nm, prepared by RF sputtering were irradiated with 100 MeV Ag ions. Structural characterization showed amorphisation and subsequent reduction in particle size. The change in magnetic properties due to irradiation was correlated with structural and topographical effects of ion irradiation. A rough estimation of ion track radius is done from the magnetic studies. (C) 2017 Elsevier B.V. All rights reserved.

}, keywords = {Spin glass, Swift heavy ion, Zinc Ferrite}, issn = {0168-583X}, doi = {10.1016/j.nimb.2017.01.046}, author = {Raghavan, Lisha and Joy, P. A. and Vijaykumar, B. Varma and Ramanujan, R. V. and Anantharaman, M. R.} } @article {44089, title = {Differential rubisco content and photosynthetic efficiency of rol gene integrated Vinca minor transgenic plant: correlating factors associated with morpho-anatomical changes, gene expression and alkaloid productivity}, journal = {Journal of Plant Physiology}, volume = {219}, year = {2017}, month = {DEC}, pages = {12-21}, type = {Article}, abstract = {Transgenic plants obtained from a hairy root line (PVG) of Vinca minor were characterized in relation to terpenoid indole alkaloids (TIAs) pathway gene expression and vincamine production. The hairy roots formed callus with green nodular protuberances when transferred onto agar-gelled MS medium containing 3.0 mg/l zeatin. These meristematic zones developed into shoot buds on medium with 1.0 mg/l 2, 4-dichlorophenoxyacetic acid and 40 mg/l ascorbic acid. These shoot buds subsequently formed rooted plants when shifted onto a hormone-free MS medium with 6\% sucrose. Transgenic nature of the plants was confirmed by the presence of rol genes of the Ri plasmid in them. The transgenic plants (TP) had elongated internodes and a highly proliferating root system. During glass house cultivation TP consistently exhibited slower growth rate, low chlorophyll content (1.02 +/- 0.08 mg/gm fr. wt.), reduced carbon exchange rate (2.67 +/- 0.16 mu mol m(-2) s(-1)), less transpiration rate (2.30 +/- 0.20 mmol m(-2) s(-1)) and poor stomatal conductance (2.21 +/- 0.04 mmol m-2 s(-1)) when compared with non-transgenic population. The activity of rubisco enzyme in the leaves of TP was nearly two folds less in comparison to non-transgenic controls (1.80 milliunits ml(-1) mg protein-1 against 3.61 milliunits ml(-1) mg protein-1, respectively). Anatomically, the TP had a distinct tetarch arrangement of vascular bundles in their stem and roots against a typical ployarched pattern in the non-transgenic plants. Significantly, the transgenic plants accumulated 35\% higher amount of total TIAs (3.10 +/- 0.21\% dry wt.) along with a 0.03\% dry wt. content of its vasodilatory and nootropic alkaloid vincamine in their leaves. Higher productivity of alkaloids in TP was corroborated with more than four (RQ = 4.60 +/- 0.30) and five (RQ = 5.20 +/- 0.70) times over-expression of TIAs pathway genes tryptophan decarboxylase (TDC) and strictosidine synthase (STR) that are responsible for pushing the metabolic flux towards TIAs synthesis in this medicinal herb.}, doi = {10.1016/j.jplph.2017.09.004}, author = {Verma, Priyanka and Khan, Shamshad Ahmad and Masood, Nusrat and Manika, N. and Sharma, Abhishek and Verma, Neha and Luqman, Suaib and Mathur, Ajay K.} } @article {44167, title = {Diverse reactivity trends of Ni surfaces in Au@Ni core-shell nanoparticles probed by near ambient pressure (NAP) XPS}, journal = {Catalysis Science \& Technology}, volume = {7}, year = {2017}, month = {OCT }, pages = {4489-4498}, type = {Article}, abstract = {A mild temperature sequential reduction method in aqueous medium is reported for the synthesis of Au@Ni nanoparticles with a core-shell morphology. The nickel shell thickness with a gold core in the nanostructure can be tuned from 2 nm up to about 10 nm. Near ambient pressure XPS (NAPXPS) studies under oxygen atmosphere show that Au-80@Ni-20 with an extremely thin nickel shell (similar to 2 nm) follows a distinctly different decomposition pathway of metastable Ni(OOH) species compared to those with larger shell thickness which behave more like individual nickel surfaces. Thus, Ni(OOH) on Au-80@Ni-20 decomposes to metallic Ni at 100 degrees C and is found to resist oxidation at 0.1 mbar oxygen at this temperature. Those with a larger nickel shell thickness behave more like monometallic Ni in terms of their decomposition and oxidation properties. The Au@Ni system with an ultra thin metallic nickel overlayer (2 nm) shows high catalytic activity and selectivity for phenylacetylene hydrogenation under mild conditions which outweighs their monometallic counterparts and those with higher nickel shell thickness.}, issn = {2044-4753}, doi = {10.1039/c7cy01070b}, author = {Bharathan, Vysakh A. and Jain, Ruchi and Gopinath, Chinnakonda S. and Vinod, C. P.} } @article {43816, title = {Domibacillus mangrovi sp nov and domibacillus epiphyticus sp nov., isolated from marine habitats of the central west coast of India}, journal = {International Journal of Systematic and Evolutionary Microbiology}, volume = {67}, year = {2017}, month = {AUG}, pages = {3063-3070}, type = {Article}, abstract = {While studying culturable bacterial diversity in different marine habitats of the central west coast of India, two novel Gramstain-positive, strictly aerobic, motile, endospore-forming and rod-shaped bacterial strains designated as SAOS 44(T) and SAB 38(T) were isolated from mangrove sediment soil and the surface of a macroalga, respectively. The strains were taxonomically characterized by using a polyphasic approach and genomic methods. The phylogenetic analysis based on 16S rRNA gene sequencing placed the strains firmly in the genus Domibacillus and were most closely related to Domibacillus antri KCTC 33636(T). The predominant fatty acids were iso-C-15 : 0 and anteiso-C-15 : 0. The major polar lipids were diphosphatidylglycerol and phosphatidylglycerol in addition to an aminophosphoglycolipid. MK-6 was the only respiratory quinone. The range of values of digital DNA-DNA hybridization (19.2-24.9 \%) and the ortho-average nucleotide identity (74.1-81.4 \%) among strains SAOS 44(T), SAB 38(T) and other Domibacillus species clearly supports their status as a distinct and novel species for which the names Domibacillus mangrovi sp. nov. SAOS 44(T) (=DSM 100930(T)=KCTC 33820(T)=MTCC 12571(T)) and Domibacillus epiphyticus sp. nov. SAB 38(T) (=DSM 100929(T)= KCTC 33830(T)=MTCC 12575(T)) are proposed, respectively.}, doi = {10.1099/ijsem.0.002085}, author = {Verma, Ashish and Ojha, Anup Kumar and Dastager, Syed G. and Natarajan, Rameshkumar and Mayilraj, Shanmugam and Krishnamurthi, Srinivasan} } @article {45653, title = {Efficient synthesis of functionalized olefins by wittig reaction using amberlite resin as a mild base}, journal = {Synthetic Communications}, volume = {47 }, year = {2017}, month = {JUL}, pages = {581-589}, type = {Article}, abstract = {

A convenient procedure for the synthesis of olefins by the reaction of stabilized, semistabilized, and nonstabilized phosphorous ylides with various aldehydes or ketone using Amberlite resin as a mild base is described. Our developed method offers facile and racemization-free synthesis of ,-unsaturated amino esters and chiral allylic amine. The developed methodology offers mild reaction conditions, high efficiency, and facile isolation of the final products, a practical alternative to known procedures

}, doi = {10.1080/00397911.2016.1276191}, author = {Valkute, Tushar R. and Aratikatla, Eswar K. and Bhattacharya, Asish K.} } @article {45734, title = {Electronic control on linear versus branched alkylation of 2-/3-aroylbenzofurans with acrylates: combined DFT and synthetic studies}, journal = {Chemistry-A European Journal}, volume = {23}, year = {2017}, month = {JUN }, pages = {7570-7581}, type = {Article}, abstract = {

Investigations on the factors that govern unusual branched alkylation of 2-aroylbenzofurans with acrylates by Ru-catalyzed carbonyl-directed C-H activation has been carried out by calculating the kinetics associated with the two key steps-the coordination of the acrylate with the intermediate ruthenacycle and the subsequent migratory insertion reaction-studied with the help of DFT calculations. Eight possible orientations for each mode of alkylation have been considered for the calculations. From these calculations, it has been understood that there is a synergistic operation of the steric and electronic effects favoring the branched alkylation. Further DFT investigations on the alkylation of the isomeric 3-aroylbenzofurans indicated a preference for the linear alkylation and this has been verified experimentally. Overall, the observed/calculated complementary selectivity in the alkylation of 2-/3-aroylbenzofurans with acrylates reveals that the substrate-dependent charge distribution of the Ru-C bond in the intermediate ruthenacycle is an important determining factor and thus the current work opens up a new domain of substrate design for controlling regioselectivity.

}, keywords = {acrylates, Alkylation, aroylbenzofuran, C-H activation, Density functional calculations}, issn = {0947-6539}, doi = {10.1002/chem.201700643}, author = {Srinivas, Kolluru and Dangat, Yuvraj and Kommagalla, Yadagiri and Vanka, Kumar and Ramana, Chepuri V.} } @article {44004, title = {Electron{\textendash}nucleus scalar{\textendash}pseudoscalar interaction in PbF: Z-vector study in the relativistic coupled-cluster framework}, journal = {Molecular Physics}, year = {2017}, month = {MAY}, chapter = {1-6}, abstract = {

The scalar{\textendash}pseudoscalar interaction constant of PbF in its ground state electronic configuration is calculated using the Z-vector method in the relativistic coupled-cluster framework. The precise calculated value is very important to set upper bound limit on (Formula presented.)-odd scalar{\textendash}pseudoscalar interaction constant, ks, from the experimentally observed (Formula presented.)-odd frequency shift. Further, the ratio of the effective electric field to the scalar{\textendash}pseudoscalar interaction constant is also calculated which is required to get an independent upper bound limit of electric dipole moment of electron, de, and ks and how these (de and ks) are interrelated is also presented here. {\textcopyright} 2017 Informa UK Limited, trading as Taylor \& Francis Group

}, author = {Sasmal, S. and Talukdar, K. and Nayak, M.K. and Vaval, N. and Pal, S.} } @article {43961, title = {Examination into the taxonomic position of Bacillus thermotolerans Yang et al., 2013, proposal for its reclassification into a new genus and species Quasibacillus thermotolerans gen. nov., comb. nov. and reclassification of B. encimensis Dastager et al., }, journal = {Systematic and Applied Microbiology}, year = {2017}, month = {SEP}, type = {Article}, abstract = {Two novel Gram-staining positive, rod-shaped, moderately halotolerant, endospore forming bacterial strains 5.5LF 38TD and 5.5LF 48TD were isolated and taxonomically characterized from a landfill in Chandigarh, India. The analysis of 16S rRNA gene sequences of the strains confirmed their closest identity to Bacillus thermotolerans SgZ-8T with 99.9\% sequence similarity. A comparative phylogenetic analysis of strains 5.5LF 38TD, 5.5LF 48TD and B. thermotolerans SgZ-8(T) confirmed their separation into a novel genus with B. badius and genus Domibacillus as the closest phylogenetic relatives. The major fatty acids of the strains are iso-C15:0 and iso-C16:0 and MK-7 is the only quinone. The major polar lipids are diphosphatidylglycerol, phosphatidylglycerol and phosphatidylethanolamine. The digital DNA-DNA hybridization (DDH) and ortho average nucleotide identity (ANI) values calculated through whole genome sequences indicated that the three strains showed low relatedness with their phylogenetic neighbours. Based on evidences from phylogenomic analyses and polyphasic taxonomic characterization we propose reclassification of the species B. thermotolerans into a novel genus named Quasibacillus thermotolerans gen. nov., comb. nov with the type strain SgZ-8(T) (=CCTCC AB2012108(T)=KACC 16706(T)). Further our analyses also revealed that B. encimensis SGD-V-25(T) is a later heterotypic synonym of Bacillus badius DSM 23(T).}, doi = {10.1016/j.syapm.2017.07.010}, author = {Verma, Ashish and Pal, Yash and Khatri, Indu and Ojha, Anup Kumar and Gruber-Vodicka, Harald and Schumann, Peter and Dastager, Syed Gulam and Subramanian, Srikrishna and Mayilraj, Shanmugam and Krishnamurthi, Srinivasan} } @article {43317, title = {Exploiting directional long range secondary forces for regulating electrostatics dominated noncovalent interactions}, journal = {Chemical Science}, volume = {8}, year = {2017}, month = {JAN}, pages = {1378-1390}, abstract = {

It has been well established that long range secondary electrostatic interactions (SEIs) have a significant effect on the stability of supramolecular complexes. However, general rules for exploiting SEIs in the rational design of diverse supramolecular complexes have been difficult to obtain. In this work, we outline a quantum chemical approach for understanding the strength of electrostatic interactions. This approach is seen to provide excellent correlation between the electrostatic force and the binding energy between two partners in hydrogen-bonded complexes, as well as that between two ions in ion-pair complexes. Furthermore, we illustrate how the understanding of the binding allows for the rational design of new complexes where the association constant between the two partners can be increased or decreased, as desired, by several orders of magnitude. Hence, the current work showcases a general, simple and powerful method of understanding and exploiting long range secondary electrostatic interactions.

}, doi = {10.1039/C6SC03642B}, author = {Tiwari, Mrityunjay and Vanka, Kumar} } @article {45731, title = {Exploration of amination reactions on highly extendable active sites of Pd(II)-3-allylsalicylaldiminophenol (ASIP) complex over thiofunctionalized SBA-15}, journal = {Microporous and Mesoporous Materials}, volume = {242}, year = {2017}, month = {APR}, pages = {173-181}, type = {Article}, abstract = {

An effective and impressive heterogeneous catalyst, Pd(II)-3-allylsalicylaldiminophenol-SBA-15, dubbed as Pd(II)ASIP@SBA-15, for amination reactions of aryl halides to synthesize secondary amines (2), has been synthesized and characterized. Pd(II)ASIP@SBA-15 has been synthesized by the covalent anchoring of 3-allylsalicylaldehyde over thiofunctionalized SBA-15, then further reaction with 2-aminophenol, followed by metallation process by using Pd(11)(OAc)(2). A specifically designed cheap and easily available organic ligand, 3-allylsalicylaldiminophenol (ASIP), was synthesized from 3-allylsalicylaldehyde and 2-aminophenol. Using this, the synthesis of Pd(II)ASIP@SBA-15 was carried out whereby the ligand providing an active co-ordination or chelating sites for palladium metal. This strategy helped in exposing the Pd(11)ASIP active sites from surface to channels of SBA-15 support during the reactions. The synthesized catalyst were characterized by CHN analysis, PXRD, Nitrogen sorption analyses, TG \& DTA, FTIR, C-13 and Si-29 CPMASS NMR spectra, XPS, UV-Visible, SEM, EDAX and TEM. Pd(II)ASIP@SBA-15 catalyst was screened in heterogeneous amination reactions of aryl halides to produce N-aryl derivatives or secondary amines with high catalytic activity as revealed by turn over frequency (TOF) calculations. To explore the heterogeneous nature of catalysts, amination reactions were carried with neat Pd(II)ASIP complex and Pd(11)(OAc)(2) catalysts. The catalyst was recycled several times without much loss of activity and Sheldon hot filtration test has been performed. (C) 2017 Elsevier Inc. All rights reserved.

}, keywords = {Amination Reactions, heterogeneous catalysis, Reusable, Supported catalysis}, issn = {1387-1811}, doi = {10.1016/j.micromeso.2017.01.026}, author = {Lazar, Anish and Vinod, C. P. and Singh, A. P.} } @article {43970, title = {Fabrication, characterization and comparison of DSSC using anatase TiO 2 synthesized by various methods}, journal = {Advanced Powder Technology}, year = {2017}, month = {SEP}, type = {Article}, abstract = {In this study, anatase TiO2 nanoparticles were synthesized by three techniques, namely, sol-gel, acid-base co-catalyst and room temperature colloidal methods. The synthesized materials were characterized by X-ray diffraction, scanning electron microscopy, pore diameter, pore volume and surface area. The dye-sensitized solar cells were fabricated using the synthesized materials and characterized for incident photon to current conversion efficiency, photocurrent density to photo voltage measurement and electrochemical impedance analysis. Among the studied materials, TiO2 synthesized by sol-gel method displayed highest photon to current conversion of 76.8\% and a maximum solar cell efficiency of 7.85\% with Jsc of 14.75mA/cm{\texttwosuperior}, Voc of 0.76V and FF of 0.7. This is the first study to report a high power conversion efficiency of DSSC using a sol-gel synthesized titania and its comparison with other two synthesized materials. The high power conversion efficiency of the solar cell using TiO2 synthesized by sol-gel method is attributed to its characteristic properties such high surface area, larger pore diameter and larger pore volume and highest dye loading capacity.}, doi = {10.1016/j.apt.2017.08.012}, author = {Umale, Sanjivani V. and Tambat, Sneha N. and Vediappan, Sudhakar and Sontakke, Sharad M. and Krishnamoorthy, Kothandam} } @article {43335, title = {Facile synthesis of 3D anode assembly with Si nanoparticles sealed in highly pure few layer graphene deposited on porous current collector for long life Li-Ion battery}, journal = {Advanced Materials Interfaces}, volume = {4}, year = {2017}, month = {MAR}, pages = {Article Number: 1601043}, type = {Article}, abstract = {With its exceptional theoretical charge capacity, silicon holds great promise as an anode material for realization of high energy density Li-ion batteries. However, extensive volume expansion and poor cycle stability of silicon compromise its actual use. In an effort to tame volume expansion and structural disintegration during cycling, an innovative 3D electrode assembly is fabricated involving continuous layer of graphene coated on porous current collector and Si nanoparticles sealed in as an active material. Graphene deposition and pore formation in metal current collector is achieved in a unique single step synthesis. All the active components like current collector, reacting material, and conducting material are manipulated in a way to produce synergistic architecture in a chemical vapor deposition process. Highly pure graphene deposited in this process enables efficient electron transfer from allover of the surface of silicon nanoparticles and prevents continuous solid electrolyte interphase layer formation. This binder free anode assembly shows extremely stable lithium storage performance for over 1000 cycles with 88\% of initial capacity retention and 100\% Coulombic efficiency.}, doi = {10.1002/admi.201601043}, author = {Shelke, Manjusha V. and Gullapalli, Hemtej and Kalaga, Kaushik and Rodrigues, Marco and Devarapalli, Rami Reddy and Vajtai, Robert and Ajayan, Pulickel M.} } @article {44158, title = {Facile synthesis of unique cellulose triacetate based flexible and high performance gel polymer electrolyte for lithium ion batteries}, journal = {ACS Applied Materials \& Interfaces}, volume = {9}, year = {2017}, month = {OCT}, pages = {34773-34782}, type = {Article}, abstract = {Lithium ion batteries (LIBs) with polymer based electrolytes have attracted enormous attention due to the possibility of fabricating intrinsically safer and flexible devices. However, economical and eco-friendly sustainable technology is an oncoming challenge to fulfill the ever increasing demand. To circumvent this issue, we have developed a gel polymer electrolyte (GPE) based on renewable polymers like cellulose triacetate and poly (polyethylene glycol methacrylate) p(PEGMA) using a photo polymerization technique. Cellulose triacetate offers good mechanical strength with improved ionic conductivity, owing to its ether and carbonyl functional groups. It is observed that the presence of an open network has a critical impact on lithium ion transport. At room temperature, GPE PC exhibits an optimal ionic conductivity of 1.8 x 10(-3) S cm(-1) and transference number of 0.7. Interestingly, it affords an excellent electrochemical stability window up to 5.0 V vs Li/Li+. GPE PC shows a discharge capacity of 164 mAhg(-1) after the first cycle when evaluated in a Li/GPE/LiFePO4 cell at 0.5 C-rate. Interfacial compatibility of GPE PC with lithium metal improves the overall cycling performance. This system provides a guiding principle toward a future renewable and flexible electrolyte design for flexible LIBs (FLIBs).}, doi = {10.1021/acsami.7b07020}, author = {Nirmale, Trupti C. and Karbhal, Indrapal and Kalubarme, Ramchandra S. and Shelke, Manjusha V. and Varma, Anjani J. and Kale, Bharat B.} } @article {43948, title = {Heterogeneously catalyzed domino synthesis of 3-indolylquinones involving direct oxidative C-C coupling of hydroquinones and indoles}, journal = {ACS Omega}, volume = {2}, year = {2017}, month = {MAY}, chapter = {2238-2247}, abstract = {
Abstract Image

A domino synthesis of 3-indolylquinones was achieved successfully via direct oxidative C{\textendash}C coupling of hydroquinones with indoles over Ag2O and Fe3O4/povidone{\textendash}phosphotungstic acid (PVP{\textendash}PWA) catalysts using H2O2\ in tetrahydrofuran at room temperature. Ag2O catalyzed the in situ oxidation of hydroquinone and 3-indolylhydroquinone intermediates, whereas ferrite solid acid, Fe3O4/PVP{\textendash}PWA, with a 1:4:1 ratio of Fe3O4, PVP, and PWA, catalyzed the activation of quinones. The efficiency of this catalytic domino approach was established by a broad scope of substrates involving a variety of hydroquinones and quinones to give high yields (81{\textendash}97\%) of 3-indolylquinones. Fe3O4/PVP{\textendash}PWA was separated magnetically, whereas simple filtration could separate Ag2O, both of which could be recycled several times without losing their activities.

}, keywords = {Carbonyl compounds (organic); Electron microscopy; Fourier-transform spectroscopy; Redox reaction}, doi = {10.1021/acsomega.7b00201}, author = {Kamble, Sumit B.; and Vyas, Praneet P. and Jayaram, Radha V.; and Rode, Chandrashekhar V.} } @article {45662, title = {Hydrogenolysis of sorbitol over Ni, Pt and Ru supported on SBA-15}, journal = {Indian Journal of Chemistry. Section A: Inorganic, Physical, Theoretical \& Analytical Chemistry}, volume = {56 }, year = {2017}, month = {FEB}, pages = {226-231}, type = {Article}, abstract = {Hydrogenolysis of sorbitol (15\% aqueous solution) has been carried out in a batch reactor over Ni (6 wt\%), Pt (1 wt\%) and Ru (1 wt\%) supported on SBA-15 and carbon coated SBA-15 (SBA-15(C)). For comparison, the three metals have also been supported on activated carbon (AC). The catalysts are characterized by XRD, N-2 and H-2 adsorption measurements. Addition of Ca(OH)(2) to the reaction mixture increases conversion and selectivity for the dihydroxy compounds, 1,2-propanediol (PD) and ethylene glycol (EG). Based on yield of dihydric alcohols (PD+EG), the performance of the catalysts at 220 degrees C and 60 bar in the presence of Ca(OH)(2) is in the order: Ru-AC similar to Ru-SBA-15(C) > Ru-SBA-15 similar to Ni-SBA-15, the yields being 40, 39, 31 and 29 wt\%, respectively.}, url = {http://nopr.niscair.res.in/handle/123456789/40903}, author = {Banu, M. and Sankaranarayanan, T. M. and Venuvanalingam, P. and Magesh, G. and Sivasanker, S.} } @article {43826, title = {Identification of new anti-inflammatory agents based on nitrosporeusine natural products of marine origin}, journal = {European Journal of Medicinal Chemistry}, volume = {135}, year = {2017}, month = {JUL}, pages = {89-109}, type = {Article}, abstract = {Nitrosporeusines A and B are two recently isolated marine natural products with novel skeleton and exceptional biological profile. Interesting antiviral activity of nitrosporeusines and promising potential in curing various diseases, evident from positive data from various animal models, led us to investigate their anti-inflammatory potential. Accordingly, we planned and synthesized nitrosporeusines A and B in racemic as well as enantiopure forms. The natural product synthesis was followed by preparation of several analogues, and all the synthesized compounds were evaluated for in vitro and in vivo anti-inflammatory potential. Among them, compounds 25, 29 and 40 significantly reduced levels of nitric oxide (NO), reactive oxygen species (ROS) and pro-inflammatory cytokines. In addition, these compounds suppressed several pro-inflammatory mediators including inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2), nuclear factor-kappa B (NF -kappa B), and thereby can be emerged as potent anti-inflammatory compounds. Furthermore, all possible isomers of lead compound 25 were synthesized, characterized and profiled in same set of assays and found that one of the enantiomer (-)-25a was superior among them. (C) 2017 Elsevier Masson SAS. All rights reserved.}, doi = {10.1016/j.ejmech.2017.04.015}, author = {Philkhana, Satish Chandra and Verma, Abhishek Kumar and Jachak, Gorakhnath R. and Hazra, Bibhabasu and Basu, Anirban and Reddy, D. Srinivasa} } @article {43651, title = {Influence of thermocleavable functionality on organic field-effect transistor performance of small molecules}, journal = {Chemical Physics Letters}, volume = {678}, year = {2017}, month = {JUN}, pages = {139-145}, abstract = {Diketopyrrolopyrrole based donor-acceptor-donor conjugated small molecules using ethylene dioxythiophene as a donor was synthesized. Electron deficient diketopyrrolopyrrole unit was substituted with thermocleavable (tert-butyl acetate) side chains. The thermal treatment of the molecules at 160 degrees C eliminated the tert-butyl ester group results in the formation of corresponding acid. Optical and theoretical studies revealed that the molecules adopted a change in molecular arrangement after thermolysis. The conjugated small molecules possessed p-channel charge transport characteristics in organic field effect transistors. The charge carrier mobility was increased after thermolysis of tert-butyl ester group to 5.07 x 10(-5) cm(2)/Vs. (C) 2017 Elsevier B.V. All rights reserved.}, doi = {10.1016/j.cplett.2017.04.041}, author = {Mahale, Rajashree Y. and Dharmapurikar, Satej S. and Chini, Mrinmoy Kumar and Venugopalan, Vijay} } @article {45668, title = {An innovative approach to enhance methane hydrate formation kinetics with leucine for energy storage application}, journal = {Applied Energy}, volume = {188}, year = {2017}, month = {FEB}, pages = {190-199}, type = {Article}, abstract = {Natural gas storage in dathrate hydrates or solidified natural gas (SNG) offers the safest, cleanest and the most compact mode of storage aided by the relative ease in natural gas (NG) recovery with minimal cost compared to known conventional methods of NG storage. The stochastic nature of hydrate nucleation and the slow kinetics of hydrate growth are major challenges that needs to be addressed on the SNG production side. A deterministic and fast nucleation coupled with rapid crystallization kinetics would empower this beneficial technology for commercial application. We propose a hybrid combinatorial approach of methane hydrate formation utilizing the beneficial aspect of environmentally benign amino acid (leucine) as a kinetic promoter by combining stirred and unstirred reactor operation. This hybrid approach is simple, can easily be implemented and scaled-up to develop an economical SNG technology for efficient storage of natural gas on a large scale. Added benefits include the minimal energy requirement during hydrate growth resulting in overall cost reduction for SNG technology. }, doi = {10.1016/j.apenergy.2016.12.002}, author = {Veluswamy, H. P. and Kumar, A. and Kumar, R. and Linga, P.} } @article {44121, title = {Interfacial-active polymer nanoparticles, their assemblies, and SERS application}, journal = {Macromolecular Chemistry and Physics}, volume = {218}, year = {2017}, month = {DEC}, pages = {Article Number: 1700261}, type = {Article}, abstract = {In this work, surface-active polymer nanoparticles as well as polymer-polymer and polymer-metal nanoassembly particles are synthesized, and different parameters such as their size, morphologies, and assembling strength are studied. Nanoassembly particles are attractive because of the coupled properties with a large surface to volume ratio. A key challenge is to produce the core-shell polymer nanoparticles via single-step processes. To address this concern, here, microfluidics approach and precise interfacial reaction strategies are used, and hence different types of surface layered polymer nanoparticles are obtained in one-step processes. An inner core material is hydrophobic, whereas a hydrophilic surface layer (in situ formed during the polymerization process) swells in the aqueous environment. Moreover, three different reaction setups (batch, flow, and in situ) are applied in order to architect the nanoassembling hierarchical structures via layer-by-layer strategy. On the other side, polymer-metal nanoassembly particles as well as metal catalyzed metal deposited four layered nanoassembly particles of tuned size and compositions are produced. It is shown that these particles can be used as nanosensor particles for surface-enhanced Raman spectroscopy.}, doi = {10.1002/macp.201700261}, author = {Visaveliya, Nikunjkumar R. and Li, Xiang and Knauer, Andrea and Prasad, Bhagavatula L. V. and Kohler, Johann Michael} } @article {43741, title = {Interplaying anions in a supramolecular metallohydrogel to form metal organic frameworks}, journal = {Chemical Communications}, volume = {53}, year = {2017}, month = {APR}, pages = {3705-3708}, type = {Article}, abstract = {The remarkable effect of anions on the transition from supramolecular gels to crystalline phases has been described. An amino acid-based metallohydrogel was transformed into different metal-organic frameworks through the selective picking of anions. The metallohydrogel and the resulting metal-organic frameworks (MOFs) were thoroughly characterized. The results demonstrated controlled access over the binding of a particular anion to selectively form a particular MOF.}, doi = {10.1039/c7cc00539c}, author = {Karak, Suvendu and Kumar, Sushil and Bera, Saibal and Diaz Diaz, David and Banerjee, Subhrashis and Vanka, Kumar and Banerjee, Rahul} } @article {43942, title = {Investigation into the taxonomy of {\textquotedblleft} B. aminovorans{\textquotedblright} and its reclassification to the genus Domibacillus as Domibacillus aminovorans sp. nov.}, journal = {Systematic and Applied Microbiology}, volume = {40 }, year = {2017}, month = {AUG}, pages = {458-467}, type = {Article}, abstract = {The species "Bacillus aminovorans" was categorized as species Incertae Sedis meaning taxa with uncertain taxonomic position because of insufficient description of phenotypic properties and lack of understanding of its phylogenetic relationship (Claus and Berkeley [5]). In this study two strains "B. aminovorans" DSM 1314T and DSM 4337 were phenotypically and phylogenomically analyzed. The strains are Gram-staining-positive, spore forming rods and unable to utilize/ferment most of the sugars tested except glucose. The major fatty acids are anteiso-C15:0 and iso-C15:0. The major polar lipids are diphosphatidylglycerol, phosphatidylglycerol and an aminophosphoglycolipid. The cell wall peptidoglycan is of A1γ type with meso-Dpm as the diamino acid. The menaquinone type present is MK-6. The G+C content of the genomic DNA of the type strain is 40.8mol\%. These characteristics were found to be in line with description of the genus Domibacillus. Moreover phylogenetic analysis based on 16S rRNA gene sequence retrieved "B. aminovorans" within the genus Domibacillus with D. antri XD 80T as the closest relative. Additionally genome sequencing of the strains and their comparison with whole genome sequences of other Domibacillus spp. confirmed their distinctiveness and separate species status within the genus based on parameters of genome to genome distance calculator (GGDC) and average nucleotide identity (ANI) values. Therefore a novel species Domibacillus aminovorans sp. nov. (DSM 1314T =LMG 16796T) is proposed.}, keywords = {16S rRNA, Domibacillus aminovorans, MALDI-TOF, {\textquoteleft}{\textquoteleft}Bacillus aminovorans{\textquoteright}{\textquoteright}}, issn = {0723-2020}, doi = {10.1016/j.syapm.2017.07.003}, author = {Verma, Ashish and Ojha, Anup Kumar and Pal, Yash and Kumari, Parveen and Schumann, Peter and Gruber-Vodicka, Harald and Dastager, Syed Gulam and Natarajan, Ramesh Kumar and Mayilraj, Shanmugam and Krishnamurthi, Srinivasan} } @article {43276, title = {Iron-carbon nanohybrid particles as environmentally benign electrode for supercapacitor}, journal = {Journal of Solid State Electrochemistry }, volume = {21}, year = {2017}, month = {FEB}, pages = {1665-1674}, type = {Article}, abstract = {

In this work, we report the synthesis and electrode applications of iron-carbon nanohybrid particles prepared by carbonization of a nanocomposite of FeOOH nanoneedles and melamine-formaldehyde resin. The chemical composition and microstructure of the material have been characterized using ICP-AES, FT-IR, XRD, FESEM, TEM and XPS. The supercapacitor properties of the MF-Fe-C are studied in detail. A thorough comparison of the supercapacitor performances of MF-Fe-C and bare MF-C has been carried out through detailed electrochemical characterisations employing both two and three-electrode techniques. The nanohybrid showed an enhanced energy density of 127.75 WhKg$^{-}${\textonesuperior}, specific capacitance of \~{}408 F g$^{-}${\textonesuperior} at 1 mVs$^{-}${\textonesuperior} scan rate, and excellent cyclic stability even after 1000 charge-discharge cycles, making it an intriguing material for high energy density supercapacitor devices.

}, doi = {10.1007/s10008-017-3537-z}, author = {Ratha, Satyajit and Vernekar, Dnyanesh and Sivaneri, Kavin and Jagadeesan, Dinesh and Rout, Chandra Sekhar} } @article {44118, title = {Laboratory evaluation of synthetic blends of L-(+)-lactic acid, ammonia, and ketones as potential attractants for aedes aegypti}, journal = {Journal of the American Mosquito Control Association}, volume = {33}, year = {2017}, month = {DEC}, pages = {301-308}, type = {Article}, abstract = {Attraction of Aedes aegypti to various binary, trinary, and quaternary blends of lactic acid and ketones with or without ammonia was studied using a dual choice olfactometer. A dose dependent attraction was observed in cases of single compounds where cyclopentanone attracted the highest percentage (36.9 +/- 1.8\%) of Ae. aegypti when tested alone. No significant difference was observed between the attraction levels of trinary and binary blends of lactic acid and acetone or butanone when tested against clear air. However, in competitive bioassays, the trinary blend of lactic acid, acetone, and butanone was significantly preferred over binary blends of individual compounds (P < 0.05). Acetylacetone was weakly attractive when tested alone but showed additive attraction when blended with lactic acid. However, acetylacetone acted as an attraction inhibitor when blended with other compounds. Cyclopentanone was attractive, but enhancement of attraction was not observed when blended with other components. Addition of ammonia to binary or trinary blends of lactic acid, acetone, and/or butanone did not increase the attraction significantly. In competitive bioassays, the blends containing ammonia were significantly preferred over the blends lacking ammonia (P < 0.05). This highlights ammonia as an essential component of synthetic blends. A quaternary blend of lactic acid, ammonia, acetone, and butanone was most attractive (65 +/- 1.5\%) and preferred blend of all other combinations.}, doi = {doi.org/10.2987/16-6599.1}, author = {Venkatesh, P. M. and Sen, A.} } @article {44038, title = {Less frustration, more Activity{\textemdash}theoretical insights into frustrated lewis pairs for hydrogenation catalysis}, journal = {ChemCatChem}, volume = {9}, year = {2017}, month = {AUG}, pages = { 3013-3022}, type = {Journal Article}, abstract = {The field of frustrated Lewis pair (FLP) chemistry has seen rapid development in only a few years. FLPs have performed most spectacularly in hydrogenation catalysis: a wide variety of FLP-based systems can catalyze the hydrogenation of a range of different substrates, including imines, enamines, ketones, alkynes, and alkenes. However, FLP-based hydrogenation catalysts are yet to match the efficiency of their transition-metal counterparts. The current investigation reveals an important aspect of FLPs that can be exploited to improve their efficiency, that is, the more sterically hindered the FLP catalyst is, the lower is its turnover frequency. Full quantum chemical calculations with DFT for a family of different, experimentally known hydrogenation FLP catalysts shows that superior FLP catalysts can be designed by reducing the frustration (by reducing the steric demand and acid/base strength) in the FLP. However, as lowering the steric demand without reduction in the frustration can result in unwanted side reactions, the design of the most efficient FLP catalysts depends on tuning the system so that both the steric demand and the frustration are reduced appropriately.}, keywords = {Boranes, Hydrogenation, reaction mechanism, Steric Hindrance}, doi = {10.1002/cctc.201700289}, author = {Mane, M.V.}, editor = {Vanka, K.} } @article {43790, title = {Mapping architectural and transcriptional alterations in non-lesional and lesional epidermis in vitiligo}, journal = {Scientific Reports}, volume = {7}, year = {2017}, month = {AUG}, type = {Article}, abstract = {In vitiligo, chronic loss of melanocytes and consequent absence of melanin from the epidermis presents a challenge for long-term tissue maintenance. The stable vitiligo patches are known to attain an irreversible depigmented state. However, the molecular and cellular processes resulting in this remodeled tissue homeostasis is unclear. To investigate the complex interplay of inductive signals and cell intrinsic factors that support the new acquired state, we compared the matched lesional and non-lesional epidermis obtained from stable non-segmental vitiligo subjects. Hierarchical clustering of genome-wide expression of transcripts surprisingly segregated lesional and non-lesional samples in two distinct clades, despite the apparent heterogeneity in the lesions of different vitiligo subjects. Pathway enrichment showed the expected downregulation of melanogenic pathway and a significant downregulation of cornification and keratinocyte differentiation processes. These perturbations could indeed be recapitulated in the lesional epidermal tissue, including blunting of rete-ridges, thickening of stratum corneum and increase in the size of corneocytes. In addition, we identify marked increase in the putrescine levels due to the elevated expression of spermine/spermidine acetyl transferase. Our study provides insights into the intrinsic self-renewing ability of damaged lesional tissue to restore epidermal functionality in vitiligo.}, doi = {10.1038/s41598-017-10253-w}, author = {Singh, Archana and Gotherwal, Vishvabandhu and Junni, Paivi and Vijayan, Vinaya and Tiwari, Manisha and Ganju, Parul and Kumar, Avinash and Sharma, Pankaj and Fatima, Tanveer and Gupta, Aayush and Holla, Ananthaprasad and Kar, Hemanta K. and Khanna, Sangeeta and Thukral, Lipi and Malik, Garima and Natarajan, Krishnamurthy and Gadgil, Chetan J. and Lahesmaa, Riitta and Natarajan, Vivek T. and Rani, Rajni and Gokhale, Rajesh S.} } @article {43647, title = {Medium constituents mediated engineering for size and shape tuning of gold nanocrystallites}, journal = {Journal of Industrial and Engineering Chemistry}, volume = {51}, year = {2017}, month = {JUL}, pages = {288-294}, abstract = {The current investigation introduces the utilization of cell culture mediums as a novel source for the one plot synthesis as well as stabilization of metal nanoparticles. By varying the medium constituents we could control the size and shape distributions of the gold nanoparticles. Nanospheres of diameter 24 +/- 6 nm and 19 +/- 5 nm were produced using DMEM and M199 mediums respectively, nanoneedles of 150 +/- 50 nm using RPMI medium and nanoflowers of 60 +/- 25 nm using IMDM medium, with an overall yield of 91 +/- 2\%. A remarkable decrease in the reaction duration (<3 min) was noted, irrespective of the growth mediums used. Fourier transform infrared spectroscopy and zeta potential measurements revealed them to have a common protenacious encapping agent with different overall surface charges of -23 +/- 3, -21 +/- 1, -24 +/- 2, and -20 +/- 1 mV for Au@DMEM, Au@RPMI, Au@IMDM and Au@M199 respectively. X-ray diffraction confirmed the purity and crystallinity of the particles with Bragg peaks at (111), (200), (220) and (311) for gold nanocrystals. This approach could lead to the creative utilization of novel eco-friendly sources for the production and size/shape control of nanoparticles. Moreover, the adopted methodology is absolutely green, robust and facile, offering new insights for sustainable synthesis for various biomedical and engineering applications. (C) 2017 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.}, doi = {10.1016/j.jiec.2017.03.015}, author = {Suresh, Anil K. and Vijay, Veena and Hameed, Bahrudeen S. and Ramasamy, Sureshkumar and Sakthivel, Natarajan} } @article {44140, title = {Methylglyoxal attenuates insulin signaling and downregulates the enzymes involved in cholesterol biosynthesis}, journal = {Molecular Biosystems}, volume = {13}, year = {2017}, month = {NOV}, pages = {2338-2349}, type = {Article}, abstract = {

Methylglyoxal (MG) is a highly reactive dicarbonyl known to be elevated under the hyperglycemic conditions of diabetes and is implicated in the development of diabetic complications. Therefore, the current study investigates the role of MG in exacerbating insulin resistance at the insulin signaling level, as well as its effect on the global proteomic level. By using insulin sensitive rat muscle cells (L6) and Chinese hamster ovary (CHO) cells stably expressing the insulin receptor (IR) and a glucose transporter fused with green fluorescent protein (GLUT4-GFP), we have observed that MG impairs insulin signaling, inhibits GLUT4 translocation and reduces glucose uptake. SWATH MS analysis, a label-free quantitative mass spectrometric approach, showed altered expression of 99 proteins out of 2404 identified in response to MG treatment. These proteins are mainly involved in stress response, protein folding and proteolysis. Some of the deregulated proteins such as thioredoxin 2, glutathione S transferase, T complex protein 1 subunit beta (tcbp1), heat shock protein 90 and E3 ubiquitin ligase were previously reported to be associated with either diabetes or insulin resistance. Interestingly, aminoguanidine (AMG), a potent dicarbonyl scavenger, restored the deleterious effects of MG. For the first time, we report that MG induces downregulation of enzymes involved in cholesterol biosynthesis such as acetyl-CoA acetyltransferase, hydroxymethylglutaryl-CoA synthase, farnesyl pyrophosphate synthetase, squalene monooxygenase, and lanosterol synthase. GC MS analysis for sterol metabolites corroborated the proteomic results; MG significantly reduced cholesterol production whereas AMG treatment restored cholesterol production to levels similar to the control. Thus, MG leads to primary defects in insulin signaling and cellular abnormalities at the proteomic and metabolic levels, both of which may contribute to the development of insulin resistance.

}, doi = {10.1039/c7mb00305f}, author = {Deshmukh, Arati B. and Bai, Shakuntala and Aarthy, T. and Kazi, Rubina S. and Banarjee, Reema and Rathore, Rajeshwari and Vijayakumar, M. V. and H. V. Thulasiram and Bhat, Manoj Kumar and Kulkarni, Mahesh J.} } @article {43356, title = {Micelles versus Ribbons: how congeners drive the self-assembly of acidic sophorolipid biosurfactants}, journal = {ChemPhysChem}, year = {2017}, month = {MAR}, pages = {643-652}, type = {Journal }, abstract = {

Sophorolipids (SLs), a class of microbially derived biosurfactants, are reported by different research groups to have different self-assembled structures (either micelles or giant ribbons) under the same conditions. Here we explore the reasons behind these contradictory results and attribute these differences to the role of specific congeners that are present in minute quantities. We show that a sample composed of a majority of oleic acid (C18:1) sophorolipid in the presence of only 0.5 \% (or more) of congeners with stearic acid (C18:0) or linoleic acid (C18:2) results in the formation of micelles that are stable over long periods of time. Conversely, the presence of only 10 to 15 \% of congeners with a stearic acid chain gives fibrillar structures instead of micelles. To study the mechanisms responsible, oleic acid SLs devoid of any other congeners were prepared. Very interestingly, this sample can self-assemble into either micelles or fibers depending on minute modifications to the self-assembly conditions. The findings are supported by light scattering, small-angle X-ray scattering, transmission electron microscopy under cryogenic conditions, high-pressure liquid chromatography, and NMR spectroscopy.

}, doi = {10.1002/cphc.201601323}, author = {Dhasaiyan, Prabhu and Griel, Patrick Le and Roelants, Sophie and Redant, Emile and Bogaert, Inge N. A. Van and Prevost, Sylvain Francois and Prasad, Bhagavatula L. V. and Baccile, Niki} } @article {43878, title = {Mixed-stack charge transfer crystals of pillar[5]quinone and tetrathiafulvalene exhibiting ferroelectric features}, journal = {Chemistry- A European Journal }, volume = {23}, year = {2017}, month = {SEP}, chapter = {12630-12635}, abstract = {

Ferroelectric materials find extensive applications in the fabrication of compact memory devices and ultra-sensitive multifunctional detectors. Face-to-face alternate stacking of electron donors and acceptors effectuate long-range unidirectional ordering of charge-transfer (CT) dipoles, promising tunable ferroelectricity. Herein we report a new TTF-quinone system-an emerald green CT complex consisting pillar[5]quinone (P5Q) and tetrathiafulvalene (TTF). The CT crystals, as determined by single crystal synchrotron X-ray diffraction, adopt a 1:1 mixed-stack arrangement of donor and acceptor with alternating dimers of TTF and 1,4-dioxane encapsulated P5Q. The TTF-P5Q.dioxane crystal possesses a macroscopic polarization axis giving rise to ferroelectricity at room temperature. The CT complex manifests ferroelectric features such as optical polarization rotation, temperature-dependent phase transition and piezoelectric response in single crystals. Ferroelectric behavior observed in P5Q-based CT complex widens the scope for further work on this structurally intriguing and readily accessible cyclic pentaquinone.

}, keywords = {Acceptor, Charge-transfer complexes, Chemistry, Conductors, DDQ, Donor, ferroelectric, Macrocycles, Organic Metals, Pi-interaction, Pillar[5]quinone, salts, Transfer Complexes, Transport}, issn = {0947-6539}, doi = {10.1002/chem.201702577}, author = {Shivakumar, Kilingaru I. and Swathi, Kadaba and Goudappagouda and Das, Tamal C. and Kumar, Ashwani and Makde, Ravindra D. and Vanka, Kumar and Narayan, Kavassery S. and Babu, Sukumaran Santhosh and Sanjayan, Gangadhar J.} } @inbook {45781, title = {Model nanoparticles in catalysis}, booktitle = {Metal nanoparticles and clusters: advances in synthesis, properties and applications}, year = {2017}, pages = {165-199}, publisher = { Springer}, organization = { Springer}, edition = {1}, chapter = {Model nanoparticles in catalysis}, abstract = {

The importance of surface structure in catalysis is well documented by a large volume of surface science studies carried out on single crystal surfaces. Recent years has seen rapid strides in the synthesis of structured nanomaterials with varying morphologies and architecture. There is a growing interest in utilizing model nanoparticles like morphology-controlled nanostructures and core{\textendash}shell-like bimetallic nanoparticles in catalysis. Apart from showing unprecedented reactivity, they serve as a model surfaces to answer many fundamental question in catalysis and also to arrive at structure vs activity correlations in heterogeneous catalysis. This chapter gives an introduction to such nanomaterials and recent advances in utilizing these materials for catalytic applications.

}, issn = {978-3-319-68052-1}, doi = {10.1007/978-3-319-68053-8}, author = {Vinod, C. P. and Vysakh, A. B. and Sreedhala, S.} } @article {42995, title = {Molecular motifs for additives that retard PEO crystallization}, journal = {Polymer Engineering \& Science}, volume = {57}, year = {2017}, month = {AUG}, pages = {857-864}, type = {Article}, abstract = {

We investigate the influence of several bifunctional phenol additives (resorcinol: RES, hydroquinone: HYD, p-hydroxybenzoic acid: PHBA, and p-nitrophenol: PNP) on the crystallization of matrix polymer, polyethyleneoxide. We employ solid state Nuclear Magnetic Resonance spectroscopy (NMR), Differential Scanning Calorimetry (DSC), optical microscopy, and Small Angle X-ray Scattering (SAXS) to investigate crystallization of the additivated PEO and compare with Density Functional Theory (DFT) calculations of additive-PEO interactions. Additive-polymer interactions are a function of the functional groups on the additive. Temperature-dependent spherulitic growth rate measurements from optical microscopy and SAXS lamellar long spacings indicate a distinct trend in the effect of additives on PEO crystallization. Change in PEO crystallization is most pronounced with PNP, followed by PHBA and finally RES and HYD. This trend correlates qualitatively with the binding energies of additive-PEO interactions from DFT studies. Our results suggest that DFT calculations might be a useful screening tool to evaluate the influence of additives on polymer crystallization. POLYM. ENG. SCI., 2016. {\textcopyright} 2016 Society of Plastics Engineers

}, doi = {10.1002/pen.24462}, author = {Shrivastava, Sudhakar Dinesh and Eldho, Kavalakal Mathai and Rajamohanan, P. R. and Ajithkumar, Thalasseril G. and Vanka, Kumar and Kumaraswamy, Guruswamy} } @article {43940, title = {New pyrene cored small organic molecule with a flexible alkyl spacer: a potential solution processable blue emitter with bright photoluminescence}, journal = {New Journal of Chemistry}, volume = {41}, year = {2017}, month = {OCT}, pages = {11383-11390}, type = {Article}, abstract = {A new pyrene cored small organic molecule viz. 1,3,6,8-tetrakis(4-((5-(9H-carbazol-9-yl) pentyl)oxy) phenyl)pyrene (PY-II) was designed and synthesized. The carbazole moiety with an alkyl spacer was introduced at 1, 3, 6 and 8 positions of the pyrene core to improve the charge transport properties and solution processability. PY-II exhibited excellent solubility in common organic solvents and high thermal stability up to 345 degrees C. The photoluminescence quantum yield (PLQY) of PY-II in solution was found to be 0.9 with bright blue emission near 450 nm which is just appropriate for the human eye. The solution processed non-doped OLED device fabricated using PY-II as an emissive layer afforded a pure blue emission with CIE coordinates of 0.16 and 0.16, a power efficiency of 0.17 lm W-1, a maximum current efficiency of 0.41 cd A(-1) and a maximum brightness of 202 cd m(-2).}, doi = {10.1039/c7nj01921a}, author = {Valsange, Nitin G. and Wong, F. L. and Shinde, Durgaprasad and Lee, C. S. and Roy, V. A. L. and Manzhos, Sergei and Feron, K. and Chang, Samuel and Katoh, Ryuzi and Sonar, Prashant and Wadgaonkar, Prakash P.} } @article {43800, title = {Norepinephrine alkaloids as antiplasmodial agents: Synthesis of syncarpamide and insight into the structure-activity relationships of its analogues as antiplasmodial agents}, journal = {European Journal of Medicinal Chemistry}, volume = {138}, year = {2017}, month = {SEP}, pages = {1089-1105}, type = {Article}, abstract = {

Syncarpamide 1, a norepinephrine alkaloid isolated from the leaves of Zanthoxylum syncarpum (Rutaceae) exhibited promising antiplasmodial activities against Plasmodium falciparum with reported IC50 values of 2.04 mu M (D6 clone), 3.06 mu M (W2 clone) and observed by us 3.90 mu M (3D7 clone) and 2.56 mu M (K1 clone). In continuation of our work on naturally occurring antimalarial compounds, synthesis of syncarpamide 1 and its enantiomer, (R)-2 using Sharpless asymmetric dihydroxylation as a key step has been accomplished. In order to study structure-activity-relationship (SAR) in detail, a library of 55 compounds (3-57), which are analogues/homologues of syncarpamide 1 were synthesized by varying the substituents on the aromatic ring, by changing the stereocentre at the C-7 and/or by varying the acid groups in the ester and/or amide side chain based on the natural product lead molecule and further assayed in vitro against 3D7 and K1 strains of P. falciparum to evaluate their antiplasmodial activities. In order to study the effect of position of functional groups on antiplasmodial activity profile, a regioisomer (S)-58 of syncarpamide 1 was synthesized however, it turned out to be inactive against both the strains. Two compounds, (S)-41 and its enantiomer, (R)-42 having 3,4,5-trimethoxy cinnamoyl groups as side chains showed better antiplasmodial activity with IC50 values of 3.16, 2.28 mu M (3D7) and 1.78, 2.07 mu M (I(1), respectively than the natural product, syncarpamide 1. Three compounds (S)-13, (S)-17, (S)-21 exhibited antiplasmodial activities with IC50 values of 6.39, 6.82, 6.41 mu M against 3D7 strain, 4.27, 7.26, 2.71 mu M against K1 strain and with CC50 values of 147.72, 153.0, \>200 mu M respectively. The in vitro antiplasmodial activity data of synthesized library suggests that the electron density and possibility of resonance in both the ester and amide side chains increases the antiplasmodial activity as compared to the parent natural product 1: The natural product syncarpamide 1 and four analogues/homologues out of the synthesized library of 55, (S)-41, (R)-42, (S)-55 and (S)-57 were assayed in vivo assay against chioroquine-resistant P. yoelii (N-67) strain of Plasmodium. However, none of the five molecules, 1, (S)-41, (R)-42, (S)-55 and (S)-57 exhibited any promising in vivo antimalarial activity against P. yoelii (N-67) strain. Compounds 4, 6, 7 and 11 showed high cytotoxicities with CC50 values of 5.87, 5.08, 6.44 and 14.04 mu M, respectively. Compound 6 was found to be the most cytotoxic as compared to the standard drug, podophyllotoxin whereas compounds 4 and 7 showed comparable cytotoxicities to podophyllotoxin. (C) 2017 Elsevier Masson SAS. All rights reserved.

}, issn = {0223-5234}, doi = {10.1016/j.ejmech.2017.07.052}, author = {Aratikatla, Eswar K. and Valkute, Tushar R. and Puri, Sunil K. and Srivastava, Kumkum and Bhattacharya, Asish K.} } @article {45693, title = {Odd-even alternation in tautomeric porous organic cages with eceptional chemical stability}, journal = {Angewandte Chemie-International Edition}, volume = {56}, year = {2017}, month = {FEB}, pages = { 2123-2126}, type = {Article}, abstract = {Amine-linked (C-NH) porous organic cages (POCs) are preferred over the imine-linked (C= N) POCs owing to their enhanced chemical stability. In general, aminelinked cages, obtained by the reduction of corresponding imines, are not shape-persistent in the crystalline form. Moreover, they require multistep synthesis. Herein, a one-pot synthesis of four new amine-linked organic cages by the reaction of 1,3,5-triformylphloroglucinol (Tp) with different analogues of alkanediamine is reported. The POCs resulting from the odd diamine (having an odd number of -CH2 groups) is conformationally eclipsed, while the POCs constructed from even diamines adopt a gauche conformation. This odd-even alternation in the conformation of POCs has been supported by computational calculations. The synthetic strategy hinges on the concept of Schiff base condensation reaction followed by keto-enol tautomerization. This mechanism is the key for the exceptional chemical stability of cages and facilitates their resistance towards acids and bases.}, doi = {10.1002/anie.201611260}, author = {Bera, S. and Basu, A. and Tothadi, S. and Garai, B. and Banerjee, S. and Vanka, K. and Banerjee, R.} } @article {43879, title = {Pd-catalyzed regioselective mono-arylation: quinazolinone as the inherent directing group for C(sp(2))-H activation}, journal = {Journal of Organic Chemistry}, volume = {82}, year = {2017}, month = {JUN}, pages = {6366-6372}, type = {Article}, chapter = {6366-6372}, abstract = {

The Pd-catalyzed quinazolinone-directed regioselective monoarylation of aromatic rings by C-H bond activation is developed. A broad substrate scope is demonstrated for both quinazolinone as well as diary-liodonium triflates. The use of a base was found to be crucial for this transformation, unlike for the known nitrogen-directed arylations. All of the novel quinazolinones of biological interest were synthesized by using the operationally simple Pd(II)-catalyzed arylation reaction.

}, keywords = {Aromatic rings, catalysis, Chemical activation, Chemical reactions, Palladium compounds, Regioselectivity}, issn = {0022-3263}, doi = {10.1021/acs.joc.7b00948}, author = {Garad, Dnyaneshwar N. and Viveki, Amol B. and Mhaske, Santosh B.} } @article {45766, title = {Penicillin V acylases from gram-negative bacteria degrade N-acylhomoserine lactones and attenuate virulence in Pseudomonas aeruginosa}, journal = {Applied Microbiology and Biotechnology}, volume = {101}, year = {2017}, month = {MAR}, pages = {2383-2395}, type = {Article}, abstract = {

Virulence pathways in gram-negative pathogenic bacteria are regulated by quorum sensing mechanisms, through the production and sensing of N-acylhomoserine lactone (AHL) signal molecules. Enzymatic degradation of AHLs leading to attenuation of virulence (quorum quenching) could pave the way for the development of new antibacterials. Penicillin V acylases (PVAs) belong to the Ntn hydrolase superfamily, together with AHL acylases. PVAs are exploited widely in the pharmaceutical industry, but their role in the natural physiology of their native microbes is not clearly understood. This report details the characterization of AHL degradation activity by homotetrameric PVAs from two gram-negative plant pathogenic bacteria, Pectobacterium atrosepticum (PaPVA) and Agrobacterium tumefaciens (AtPVA). Both the PVAs exhibited substrate specificity for degrading long-chain AHLs. Exogenous addition of these enzymes into Pseudomonas aeruginosa greatly diminished the production of elastase and pyocyanin and biofilm formation and increased the survival rate in an insect model of acute infection. Subtle structural differences in the PVA active site that regulate specificity for acyl chain length have been characterized, which could reflect the evolution of AHL-degrading acylases in relation to the environment of the bacteria that produce them and also provide strategies for enzyme engineering. The potential for using these enzymes as therapeutic agents in clinical applications and a few ideas about their possible significance in microbial physiology have also been discussed.

}, keywords = {N-acylhomoserine lactone acylase, Ntn hydrolase, pathogenesis, Penicillin Vacylase, Quorum quenching}, issn = {0175-7598}, doi = {10.1007/s00253-016-8031-5}, author = {Sunder, Avinash Vellore and Utari, Putri Dwi and Ramasamy, Sureshkumar and van Merkerk, Ronald and Quax, Wim and Pundle, Archana} } @article {43922, title = {Pilot-scale pretreatments of sugarcane bagasse with steam explosion and mineral acid, organic acid, and mixed acids: synergies, enzymatic hydrolysis efficiencies, and structure-morphology correlations}, journal = {Biomass Conversion and Biorefinery}, volume = {7}, year = {2017}, month = {SEP}, pages = {179-189}, type = {Article}, abstract = {In lignocellulosic (LC) ethanol processes, to facilitate enzymatic hydrolysis of cellulose, a physical chemical pretreatment is vital. In this study, we explored a single as well as a two-step physical-chemical pretreatment involving steam and mixed acid on unwashed sugarcane bagasse at pilot-scale level in a continuous horizontal reactor. To serve as a large-scale model, pretreatments were carried out at high solid levels of 18{\textendash}20 \% w/w. For the pretreatment, partial replacement of corrosive sulfuric acid with a milder acid-like oxalic acid was explored to derive possible advantages and synergies accruing by using a mixture of mineral acid and organic acid. The results of this work showed that first-step pretreatment carried out by the mixing of sulfuric acid (1.5 \% w/w) and oxalic acid (1.5 \% w/w) at 150 {\textdegree}C followed by a second-step steam explosion pretreatment at 180 {\textdegree}C gave significant synergies and advantages over other variants of pretreatments investigated, such as lower inhibitor levels and lower reaction severity. On post-pretreated bagasse, this study conducted comparative enzymatic hydrolysis study using a simple lab enzyme and a robust commercial enzyme. It was found that the addition of Tween 80 to the lab enzyme improved its performance to match the performance of the commercial enzyme. Scanning electron microscopy (SEM) studies were further carried out to correlate the morphology of pretreated samples with efficiency of enzyme hydrolysis. Besides morphological study, Fourier transform infrared (FTIR) studies of pretreated samples showed higher syringyl/guaiacyl ratio for all pretreatments, indicating lower levels of pseudo-lignins, which is beneficial for improved enzyme hydrolysis.}, doi = {10.1007/s13399-016-0220-z}, author = {Pal, Siddhartha and Joy, Shereena and Kumbhar, Pramod S. and Trimukhe, Kalpana D. and Gupta, Rishi and Kuhad, Ramesh Chander and Varma, Anjani J. and Shankar, Sasi} } @article {43721, title = {Porous porphyrin organic polymer (PPOP) for visible light triggered hydrogen production}, journal = {Chemical Communications}, volume = {53}, year = {2017}, month = {APR}, pages = {4461-4464}, type = {Article}, chapter = {4461-4464}, abstract = {A visible light active porphyrin-based porous organic polymer having high chemical stability and surface area has been synthesized and its ability to influence the photocatalytic activity of large band gap-TiO2 nanoparticles has been tested. The resultant composite shows improved photocatalytic activity as compared to the parent precursors. This study provides insights into the photosensitizing ability of the polymer in addition to its ability to firmly harbor nanoparticles onto its surface.}, doi = {10.1039/c7cc00879a}, author = {Mukherjee, Gargi and Thote, Jayshri and Aiyappa, Harshitha Barike and Kandambeth, Sharath and Banerjee, Subhrashis and Vanka, Kumar and Banerjee, Rahul} } @article {44129, title = { Porous reduced graphene oxide modified electrodes for the analysis of protein aggregation. part 1: lysozyme aggregation at pH 2 and 7.4}, journal = {Electrochimica Acta}, volume = {254}, year = {2017}, month = {NOV}, pages = {375-383}, type = {Article}, abstract = {Protein instability due to misfolding and aggregation is of big concern for protein based therapeutics because it impacts the bioavailability and immunogenicity of such drugs. The development of simple and cost-effective methods for the analysis of pharmaceutical formulations, indicating the presence or absence of protein aggregates, is consequently of high importance. This work proposes a novel electrochemical interface based on porous reduced graphene oxide coated glassy carbon electrode (GC/prGO) allowing for the early and sensitive identification of protein aggregation by following the change in the oxidative current of the proteins. The novelty of this work lies in the exploration of the ability of GC/prGO interfaces to capture different aggregation behaviors. Lysozyme is used as a model to follow by electrochemistry its aggregation at two pH values, pH 2 and pH 7.4, leading to the formation of amyloid and amorphous aggregates, respectively. Comparing the oxidation peak of lysozyme by differential pulse voltammetry (DPV) for different electrode architectures allowed validating the higher sensitivity of the GC/prGO interface versus bare glassy electrodes or electrodes coated with non-porous reduced graphene oxide. Parallel experiments were performed by fluorescence with thioflavin T, size exclusion chromatography and Atomic Force Microscopy (AFM) imaging. These tests further highlighted the usefulness of GC/prGO electrode to visualize in a fast and reliable manner the changes in the protein structure and the differences between the processes occurring at pH 2 and pH 7.4. In particular, the ability to emphasize changes related to the first steps in aggregation that could be indicative of the aggregation course, recommend the GC/prGO electrode in combination with DPV as a new analytical tool for aggregation studies of biopharmaceuticals. Part 2 of this work will demonstrate later the utility of this approach for the analysis of a fast acting injectable human insulin formulation, Humulin R, used for diabetes treatment as well as for calcitonin. (C) 2017 Elsevier Ltd. All rights reserved.}, doi = {10.1016/j.electacta.2017.09.083}, author = {Vasilescu, Alina and Boulahneche, Samia and Chekin, Fereshteh and Gaspar, Szilveszter and Medjram, Mohamed Salah and Diagne, Abdou Aziz and Singh, Santosh K. and Kurungot, Sreekumar and Boukherroub, Rabah and Szunerits, Sabine} } @article {44124, title = { p-Selective (sp(2))-C-H functionalization for an acylation/alkylation reaction using organic photoredox catalysis}, journal = { Chemical Communications}, volume = {53}, year = {2017}, month = {NOV}, pages = {12337-12340}, type = {Article}, abstract = {p-Selective (sp(2))-C-H functionalization of electron rich arenes has been achieved for acylation and alkylation reactions, respectively, with acyl/alkylselenides by organic photoredox catalysis involving an interesting mechanistic pathway.}, doi = {10.1039/c7cc07529d}, author = {Pandey, Ganesh and Tiwari, Sandip Kumar and Singh, Bhawana and Vanka, Kumar and Jain, Shailja} } @article {45672, title = {Pyrethrin accumulation in elicited hairy root cultures of chrysanthemum cinerariaefolium}, journal = {Plant Growth Regulation}, volume = { 81 }, year = {2017}, month = {APR}, pages = {365-376}, type = {Article}, abstract = {The flowers of Pyrethrum (Chrysanthemum cinerariaefolium) are known to contain Pyrethrins that are naturally occurring potential insecticide. Hairy roots were induced from leaves of C. cinerariaefolium using Agrobacterium rhizogenes strain A4. The root clones were characterized in to four groups i.e. thick, unbranched (D2 and D5), thin, highly branched (D3), thick, branched (B2) and thick, highly branched (D1, D6). Six established hairy root clones showed the presence of pyrethrin and were selected for elicitation studies. Growth kinetics studies revealed highest growth index in hairy root clone D1 (592.0) followed by D6 and D3 on dry weight basis after 40 days of culture. The maximum pyrethrin content was found in the clone D3 (7.2 mg/g dw) which is comparable to the flowers obtained from the variety "Avadh". Hairy root clone D2 (5.2 mg/g dw) and D6 (1.3 mg/g dw) contained pyrethrin but in less amount as compared to clone D3. The PCR analysis showed the presence of rol B and rol C genes in all the six hairy root clones while rol A was detected only in D2 clone. The methanolic extract of D3 clone showed antifungal activities against phytopathogenic fungal strains which were found maximum against Curvuleria andropogonis followed by Colletotrichum acutatum and Rhizoctonia solani. Hairy root clones D2, D3 and D6 were elicited with culture filtrate of endophytic fungus (Fusarium oxysporum) and bacteria (Bacillus subtilis). The culture filtrate (4.0 \%v/v) of both the fungal and bacterial origin was found to be effective in enhancing the pyrethrin content in all the tested hairy root clones. Clone D3 showed maximum pyrethrin content on elicitation with F. oxysporum (9.7 mg/g dw) and B. subtilis (9.7 mg/g dw) culture filtrate, which is 32 \% higher than the non elicited D3 hairy roots (7.2 mg/g dw). F. oxysporum also enhanced the hairy root growth resulting into the higher biomass yield of D3 (50 \%) and D2 (76 \%) in comparison to control non elicited hairy root clones of D3 and D2, respectively leading to higher pyrethrin yield.}, doi = {10.1007/s10725-016-0213-8}, author = {Khan, Shamshad A. and Verma, Priyanka and Banerjee, Suchitra and Chaterjee, Arnab and Tandon, Sudeep and Kalra, Alok and Khaliq, Abdul and Rahman, Laiq Ur} } @article {43699, title = {Rearrangement of imine double bond in activated quinazolinones: synthesis of phaitanthrin E}, journal = {Indian Journal of Chemistry Section B-Organic Chemistry Including Medicinal Chemistry}, volume = {56}, year = {2017}, month = {MAY}, pages = {527-530}, abstract = {Wolff-Kishner reduction of tryptanthrin to indoloquinazolinone followed by lithium diisorpropylamide induced acylation of the active methylene group with methyl chloroformate directly furnishes the phaitanthrin E in very good yield. Similar acylations of indoloquinazolinone have also been performed with four different acyl chlorides. In all examples, facile rearrangement of imine double bond from quinazolinone to indole moiety to form the corresponding alpha,beta-unsaturated carbonyl system is observed.}, author = {Vaidya, Sagar D. and N. P. Argade} } @article {44011, title = {Repurposing Ivacaftor for treatment of staphylococcus aureus infections}, journal = {International Journal of Antimicrobial Agents}, volume = {50}, year = {2017}, month = {SEP}, pages = {389-392}, type = {Journal Article}, abstract = {

Drug repurposing of non-antimicrobials is a novel method to augment a seriously depleted drug pipeline for targeting drug{\textendash}resistant pathogens. This article highlights the potent antimicrobial activity of Ivacaftor against Staphylococcus aureus, including vancomycin{\textendash} and other multidrug{\textendash}resistant strains. The potent activity of Ivacaftor in vivo is also demonstrated in a murine neutropenic thigh infection model. Taken together, these results support the potential of Ivacaftor as an antimicrobial agent for the treatment of staphylococcal infections. {\textcopyright} 2017 Elsevier B.V. and International Society of Chemotherapy

}, doi = {10.1016/j.ijantimicag.2017.03.020}, author = {Thakare, R. and Das, S. and Vasudevan, N. and Jachak, G.R. and Reddy, D.S. and Dasgupta, A. and Chopra, S.}, editor = {Singh, A. K.} } @article {43782, title = {Review on cellulose and lignin based binders and electrodes: Small steps towards a sustainable lithium ion battery}, journal = {International Journal of Biological Macromolecules}, volume = {103}, year = {2017}, month = {OCT}, pages = {1032-1043}, type = {Article}, abstract = {Lithium ion batteries (LIB) are the most promising energy storage systems for portable electronics and future electric or hybrid-electric vehicles. However making them safer, cost effective and environment friendly is the key challenge. In this regard, replacing petro-derived materials by introducing renewable biomass derived cellulose derivatives and lignin based materials into the battery system is a promising approach for the development of green materials for LIB. These biomaterials introduce sustainability as well as improved safety in the final disposal of LIB batteries. In this review we introduce LIB materials technology in brief and recent developments in electrodes and binders based on cellulose and their derivatives and lignin for lithium ion batteries. (C) 2017 Elsevier B.V. All rights reserved.}, doi = {10.1016/j.ijbiomac.2017.05.155}, author = {Nirmale, Trupti C. and Kale, Bharat B. and Varma, Anjani J.} } @article {43726, title = {Secondary interactions arrest the hemiaminal intermediate to invert the modus operandi of schiff base reaction: a route to benzoxazinones}, journal = {Journal of Organic Chemistry}, volume = {82}, year = {2017}, month = {APR}, pages = {4342-4351}, type = {Article}, abstract = {Discovered by Hugo Schiff, condensation between amine and aldehyde represents one of the most ubiquitous reactions in chemistry. This classical reaction is widely used to manufacture pharmaceuticals and fine chemicals. However, the rapid and reversible formation of Schiff base prohibits formation of alternative products, of which benzoxazinones are an important class. Therefore, manipulating the reactivity of two partners to invert the course of this reaction is an elusive target. Presented here is a synthetic strategy that regulates the sequence of Schiff base reaction via weak secondary interactions. Guided by the computational models, reaction between 2,3,4,5,6-pentafluoro-benzaldehyde with 2-amino-6methylbenzoic acid revealed quantitative (99\%) formation of 5-methyl-2-(perfluoropheny01,2-dihydro-4H-benzo[d][1,3]oxazin-4-one (15). Electron donating and electron withdrawing ortho-substituents on 2-aminobenzoic acid resulted in the production of benzoxazinones 936. The mode of action was tracked using low temperature NMR, IN vis spectroscopy, and isotopic (O-18) labeling experiments. These spectroscopic mechanistic investigations revealed that the hemiaminal intermediate is arrested by the hydrogen-bonding motif to yield benzoxazinone. Thus, the mechanistic investigations and DFT calculations categorically rule out the possibility of in situ imine formation followed by ring-closing, but support instead hydrogen-bond assisted ring-closing to prodrugs. This unprecedented reaction represents an interesting and competitive alternative to metal catalyzed and classical methods of preparing benzoxazinone.}, doi = {10.1021/acs.joc.7b00352}, author = {Patel, Ketan and Deshmukh, Satej S. and Bodkhe, Dnyaneshwar and Mane, Manoj and Vanka, Kumar and Shinde, Dinesh and Rajamohanan, Pattuparambil R. and Nandi, Shyamapada and Vaidhyanathan, Ramanathan and Chikkali, Samir H.} } @article { ISI:000371453700057, title = {Self-exfoliated guanidinium-based ionic covalent organic nanosheets (iCONs)}, journal = {Journal of the American Chemical Society}, volume = {138}, number = {8}, year = {2017}, month = {MAR}, pages = {2823-2828}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Covalent organic nanosheets (CONs) have emerged as functional two-dimensional materials for versatile applications. Although pi-pi stacking between layers, hydrolytic instability, possible restacking prevents their exfoliation on to few thin layered CONs from crystalline porous polymers. We anticipated rational designing of a structure by intrinsic ionic linker could be the solution to produce self-exfoliated CONs without external stimuli. In an attempt to address this issue, we have synthesized three self-exfoliated guanidinium halide based ionic covalent organic nanosheets (iCONs) with antimicrobial property. Self-exfoliation phenomenon has been supported by molecular dynamics (MD) simulation as well. Intrinsic ionic guanidinium unit plays the pivotal role for both self-exfoliation and antibacterial property against both Gram-positive and Gram-negative bacteria. Using such iCONs, we have devised a Mixed matrix membrane which could be useful for antimicrobial coatings with plausible medical benefits.

}, issn = {0002-7863}, doi = {10.1021/jacs.5b13533}, author = {Mitra, Shouvik and Kandambeth, Sharath and Biswal, Bishnu P. and Khayum, Abdul M. and Choudhury, Chandan Kumar and Mehta, Mihir R. and Kaur, Gagandeep and Banerjee, Subhrashis and Prabhune, Asmita and Verma, Sandeep and Roy, Sudip and Kharul, Ulhas K. and Banerjee, Rahul} } @article {43892, title = {Sorption of metaldehyde using granular activated carbon}, journal = {Journal of Water Reuse and Desalination}, volume = {7}, year = {2017}, month = {SEP}, chapter = {280-287}, abstract = {

In this work, the ability of granular activated carbon (GAC) to sorb metaldehyde was evaluated. The kinetic data could be described by an intra-particle diffusion model, which indicated that the porosity of the sorbent strongly influenced the rate of sorption. The analysis of the equilibrium sorption data revealed that ionic strength and temperature did not play any significant role in the metaldehyde uptake. The sorption isotherms were successfully predicted by the Freundlich model. The GAC used in this paper exhibited a higher affinity and sorption capacity for metaldehyde with respect to other GACs studied in previous works, probably as a result of its higher specific surface area and high point of zero charge.

}, keywords = {Degradation, Diffusion-controlled Sorption, Environmental Pollution, Granular Activated Carbon, Metaldehyde, Sorption Adsorption}, issn = {2220-1319}, doi = {10.2166/wrd.2016.074}, author = {Salvestrini, S. and Vanore, P. and Bogush, A. and Mayadevi, S. and Campos, L. C.} } @article {45689, title = {Stability studies of cuticle degrading and mycolytic enzymes of myrothecium verrucaria for control of insect pests and fungal phytopathogens}, journal = {Indian Journal of Biotechnology}, volume = {16 }, year = {2017}, month = {JUN}, pages = {404-412}, type = {Article}, abstract = {Myrothecium verrucaria produced extracellularly hydrolytic enzymes which can hydrolyse the insect cuticle as well as fungal cell wall. The addition of polyols, such as glycerol, sorbitol, xylitol (1 M) during ultra -filtration or freeze- drying of enzyme mixture increased the recovery of the enzymes in a concentrated form. Polyols (5 M) increased the temperature and pH stability of the enzymes, in the presence of glycerol chitinase, beta-1,3-glucanase, lipase and protease retained 50-60\% of initial activities at 40 degrees C after 3 h. While xylitol (5 M) was effective in stabilizing activities at pH 5.0 and 7.5 at 25 degrees C for 7 d. In the freeze-dried powder form, > 90\% at 4 degrees C for 1 year and 80-85\% at 25 degrees C for 2 months enzyme activities were retained. The addition of glycerol (1 M) to the enzyme mixture protected enzyme activities under sunlight (60-65\% activity at RT) for 5 d. Because of glycerol (1 M), the efficacy of M verrucaria enzyme preparation to control Helicoverpa armigera infestation in chick pea was increased to 70 +/- 19\%. While without glycerol the efficacy was 55 +/- 23\%. The germination of peanut seeds infected with Sclerotium rolfsii was observed to be increased (70 +/- 5\%) in a pot irrigated with enzyme mixture.}, author = {Chavan, S. B and Vidhate, R. P. and Kallure, G. S. and Dandawate, N. L. and Khire, J. M. and Deshpande, M. V.} } @conference {44414, title = {Studies on use of sodium poly acrylate (SPA) for low salt animal skinpreservation}, booktitle = { IULTCS CONGRESS 2017}, year = {2017}, month = {FEB}, publisher = {Central Leather Research Institute}, organization = {Central Leather Research Institute}, address = { ITC CHOLA , CHENNAI}, abstract = {In this study, commercial sodium poly acrylate (SPA) is used along with sodium chloride for low salt skin preservation. SPA is a super-absorbent polymer which can absorb water many times of its own weight.}, author = {Sandhya, K. V. and Brindha, Velappan and Abinandan, Sudharsanam and Vedaraman, N. and John, Sundar V. and Suresha, P. R. and Badiger, Manohar and Chinnaraj, Velappan kandukalpatti and Muralidharan, C.} } @article {42973, title = {Synthesis and characterization of polyhydrazides and poly(1,3,4-oxadiazole)s containing multiple arylene ether linkages and pendent pentadecyl chains}, journal = {High Performance Polymers}, volume = {29}, year = {2017}, month = {SEP}, chapter = {836-848}, abstract = {

A new diacylhydrazide monomer, namely, 4-(4-(4-(4-(hydrazinocarbonyl)phenoxy)-2-pentadecylphenoxy)phenoxy) benzohydrazide (HPPDPB), was synthesized starting from 4-(4-hydroxyphenoxy)-3-pentadecylphenol. HPPDPB was polycondensed with terephthalic acid chloride (TPC), isophthalic acid chloride (IPC) and a mixture of TPC and IPC (50:50 mol\%) to obtain polyhydrazides containing multiple arylene ether linkages in the backbone and pendent pentadecyl chains. Polyhydrazides were subsequently cyclized in the presence of phosphorus oxychloride to obtain the corresponding poly(1,3,4-oxadiazole)s. Polyhydrazides and poly(1,3,4-oxadiazole)s exhibited inherent viscosities in the range 0.65{\textendash}0.72 dL g-1 and 0.54{\textendash}0.62 dL g-1, respectively, which indicated the formation of reasonably high-molecular weight polymers. Polyhydrazides were soluble in polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide (DMAc), 1-methyl-2-pyrrolidinone and pyridine whereas poly(1,3,4-oxadiazole)s exhibited excellent solubility even in common organic solvents such as chloroform, dichloromethane and tetrahydrofuran. Tough, transparent and flexible films of polyhydrazides and poly(1,3,4-oxadiazole)s could be cast from DMAc and chloroform solutions, respectively. X-Ray diffraction studies revealed amorphous nature of polyhydrazides and poly(1,3,4-oxadiazole)s and the formation of layered structure was observed due to ordered packing of pentadecyl chains. The 10\% decomposition temperature (T 10) values for poly(1,3,4-oxadiazole)s were in the range 425{\textendash}440{\textdegree}C indicating their good thermal stability. Glass transition temperature (T g) values of polyhydrazides and poly(1,3,4-oxadiazole)s were in the range 175{\textendash}192{\textdegree}C and 92{\textendash}103{\textdegree}C, respectively. The excellent solubility characteristics and the large gap between T g (92{\textendash}103{\textdegree}C) and T 10 (425{\textendash}440{\textdegree}C) values give poly(1,3,4-oxadiazole)-containing pendent pentadecyl chains better opportunities for processability.

}, doi = {10.1177/0954008316660368}, author = {Tawade, Bhausaheb V. and Valsange, Nitin G. and Wadgaonkar, Prakash P.} } @article {45705, title = {Synthesis, structure and DNA interaction studies of bisphosphoramides: theoretical and experimental insights}, journal = {Inorganica Chimica Acta}, volume = {461}, year = {2017}, month = {MAY }, pages = {84-91}, type = {Article}, abstract = {

New bisphosphoramides (having phenyl (EDAPOPh(2)) and ethoxy (EDADEP) substituents attached to phosphoryl groups bridged with ethylenediamine spacer) are synthesized and structurally characterized by spectroscopic techniques as well as elemental analysis. The molecular structure of EDAPOPh(2) was determined by single crystal X-ray diffraction technique. The interaction of these bisphosphoramides with calf thymus DNA (ct-DNA) is investigated using UV-Visible absorption and fluorescence spectral data as well as the DFT calculations. These studies reveal that EDAPOPh(2) and EDADEP interact with DNA in a partial intercalation mode. The intrinsic binding constants K-b of two different bisphosphoramides with ct-DNA were determined by fluorescence spectroscopy as 2.08 x 10(4) and 3.86 x 10(4) M-1 respectively. The results indicated that the two compounds bind to ct-DNA with different binding affinities, i.e. EDAPOPh(2) \> EDADEP. The binding mechanism of these bisphosphoramides to ct-DNA is also discussed. (C) 2017 Elsevier B.V. All rights reserved.

}, keywords = {Bisphosphoramides, crystal structure, DNA interaction, Molecular docking}, issn = {0020-1693}, doi = {10.1016/j.ica.2017.02.017}, author = {Goud, E. Veerashekhar and Sivaramakrishna, Akella and Vijayakrishna, Kari and Rao, C. V. S. Brahmmananda and Khedkar, Vijay M. and Jha, Prakash C.} } @article {45683, title = {Systematic comparison of the response properties of protein and RNA mediated gene regulatory motifs}, journal = {Molecular BioSystems}, volume = {13 }, year = {2017}, month = {JUN}, pages = {1235-1245}, type = {Article}, abstract = {We present a framework enabling the dissection of the effects of motif structure (feedback or feedforward), the nature of the controller (RNA or protein), and the regulation mode (transcriptional, post-transcriptional or translational) on the response to a step change in the input. We have used a common model framework for gene expression where both motif structures have an activating input and repressing regulator, with the same set of parameters, to enable a comparison of the responses. We studied the global sensitivity of the system properties, such as steady-state gain, overshoot, peak time, and peak duration, to parameters. We find that, in all motifs, overshoot correlated negatively whereas peak duration varied concavely with peak time. Differences in the other system properties were found to be mainly dependent on the nature of the controller rather than the motif structure. Protein mediated motifs showed a higher degree of adaptation i.e. a tendency to return to baseline levels; in particular, feedforward motifs exhibited perfect adaptation. RNA mediated motifs had a mild regulatory effect; they also exhibited a lower peaking tendency and mean overshoot. Protein mediated feedforward motifs showed higher overshoot and lower peak time compared to the corresponding feedback motifs.}, doi = {10.1039/c6mb00808a}, author = {Iyengar, Bharat Ravi and Pillai, Beena and Venkatesh, K. V. and Gadgil, Chetan J.} } @article {43984, title = {Unusual role of the aromatic solvent in single site Al(I) chemistry: insights from theory}, journal = {Chemistry - A European Journal}, volume = {23}, year = {2017}, month = {JUL}, pages = {13957-13963}, type = {Article}, abstract = {The single site activation of strong σ bonds (such as that of H-H, P-H and N-H) remains a significant challenge in main group chemistry, with only a few cases reported to date. In this regard, recent exciting experiments done with Al(I) complexes hold significance, because they, too, have been seen to activate a variety of strong σ bonds. Such chemistry is generally seen to occur in aromatic solvents. The current computational studies with density functional theory (DFT) reveal the interesting reason for this: it is seen that an explicit aromatic solvent molecule acts as a catalyst by converting the Al(I) complex to Al(III) during the process. Different cases of σ bond activation by Al(I) complexes have been investigated and the efficiency for the H-X (X=H, NHtBu, PPh2) bond activation in the presence of an explicit benzene solvent molecule has been seen to be orders of magnitude higher than in its absence. The current work therefore reveals the chemistry of Al(I) complexes to be richer and more complex than realized to date, and shows it to be dependent on metal-solvent cooperativity, the first known example of its kind in main group chemistry.}, doi = {10.1002/chem.201701642}, author = {Jain, Shailja and Vanka, Kumar} } @conference {45757, title = {VIMAL: A chemoinformatics toolkit for design of novel antiviral agents through textmining of scientific literature}, booktitle = {253rd National Meeting of the American-Chemical-Society (ACS) on Advanced Materials, Technologies, Systems, and Processes}, year = {2017}, month = {APR }, publisher = {Amer Chemical Soc, 1155 16TH ST, NW, Washington, DC 20036 USA}, organization = {Amer Chemical Soc, 1155 16TH ST, NW, Washington, DC 20036 USA}, address = {San Francisco, CA}, author = {Karthikeyan, Muthukumarasamy and Pahujani, Rakhi and Vyas, Renu} } @article {45688, title = {Visible-light active catechol-metal oxide carbonaceous polymeric material for enhanced photocatalytic activity}, journal = {Journal of Materials Chemistry A}, volume = {5}, year = {2017}, month = {JAN}, pages = {384-396}, type = {Article}, abstract = {

esigning new materials for sustainable energy and environmental applications is one of the prime focuses in chemical science. Here, an unprecedented visible-light active catechol-TiO2 carbonaceous polymer based organic-inorganic hybrid material was synthesized by a photosynthetic route. The visible light induced (\> 400 nm) photosynthetic polymerization of catechol led to the formation of carbonaceous polymeric deposits on the surface of TiO2. The band gap energy of hybrids was shifted to the visible region by orbital hybridization between 3d(Ti) of TiO2 and 2p(O), pi(C) of catechol. The Tauc plot clearly revealed that 1.0 wt\% catechol-TiO2 carbonaceous polymer remarkably tailored the optical band gap of TiO2 from 3.1 eV to 1.9 eV. The synthesized hybrid materials were thoroughly characterized and their photocatalytic activity was evaluated towards toxic Cr(VI) to relatively less toxic Cr(III) reduction under visible light irradiation (\> 400 nm), and solar light-driven H-2 production through water splitting. Very interestingly, the hybrid material showed 5- and 10-fold enhanced activity for photocatalytic Cr(VI) reduction and solar light-driven H-2 production respectively compared with pure TiO2. Moreover, the hybrid materials showed enhanced stability during photocatalysis. Thus, the simple photosynthetic strategy for developing light harvesting organic-inorganic hybrid materials can open up potential applications in energy and environmental remediation.

}, doi = {10.1039/c6ta07685h}, author = {Karthik, P. and Vinoth, R. and Selvam, P. and Balaraman, E. and Navaneethan, M. and Hayakawa, Y. and Neppolian, B.} } @article {44417, title = {Access to silicon(II)- and germanium(II)-indium compounds}, journal = {Organometallics}, volume = {37}, year = {2018}, month = {APR}, pages = {1206-1213}, abstract = {Despite the remarkable ability of N-heterocyclic silylene to act as a Lewis base and form stable Lewis adducts with group 13 elements such as boron, aluminum, and gallium, there has been no such comparable investigation with indium and the realization of a stable silylene-indium complex has still remained elusive. Similarly, a germylene-indium complex is also presently unknown. We describe herein the reactions of [PhC(NtBu)(2)SiN-(SiMe3)(2)] (1) and [PhC(NtBu)(2)GeN(SiMe3)(2)] (4) with InCl3 and InBr3 that have resulted in the first silylene-indium complexes, [PhC(NtBu)(2)Si{N(SiMe3)(2)}-> InCl3] (2) and [PhC(NtBu)(2)Si{N(SiMe3)(2)}-> InBr3] (3), as well as the first germylene-indium complexes, [PhC(NtBu)(2)Ge{N(SiMe3)(2)}-> InCl3] (5) and [PhC(NtBu)(2)Ge{N(SiMe3)(2)}-> InBr3] (6). The solid-state structures of all species have been validated by single-crystal X-ray diffraction studies. Note that 5 and 6 are the first structurally characterized organometallic compounds that feature a Ge-In single bond (apart from the compounds in Zintl phases). Theoretical calculations reveal that the Si(II)-> In bonds in 2 and 3 and the Ge(II)-> In bonds in 5 and 6 are dative bonds.}, doi = {10.1021/acs.organomet.8b00093}, author = {Pahar, Sanjukta and Karak, Suvendu and Pait, Moumita and Raj, K. Vipin and Vanka, Kumar and Sen, Sakya S.} } @article {45443, title = { Albumin abundance and its glycation Status determine hemoglobin glycation}, journal = {ACS Omega}, volume = {3}, year = {2018}, month = {OCT}, pages = {12999-13008}, type = {Article}, abstract = {Diabetes diagnosis and management majorly depend upon the measurement of glycated hemoglobin (HbAlc) levels. Various factors influence HbAlc levels such as the use of various analytical methods and the presence of various clinical conditions. Plasma albumin levels were known to be negatively associated with HbAlc. However, the precise mechanism by which they affect HbAlc is not well{\textquoteright} understood. Therefore, we have studied the influence of albumin levels and its glycation status on hemoglobin glycation using erythrocyte culture experiments. Erythrocytes maintained at low albumin concentration exhibited relatively increased albumin and hemoglobin glycation as compared to that in those maintained at higher albumin concentration. Increase in albumin glycation may decrease its ability to protect hemoglobin glycation. This was demonstrated by treatment of erythrocytes with N(epsilon-(carboxymethyl)lysine-modified serum albumin (CMSA), which failed to protect hemoglobin glycation; instead, it increased hemoglobin glycation. The inability of CMSA to reduce hemoglobin glycation was due to the lack of free lysine residues of albumin, which was corroborated by using N(epsilon-(acetyI)lysine serum albumin (AcSA) and clinical diabetic plasma. This is the first study which demonstrates that the modification of lysine residues of albumin impairs its ability to inhibit hemoglobin glycation. Furthermore, correlation studies between HbAlc and albumin levels or relative albumin fructosamine from clinical subjects supported our experimental finding that albumin abundance and its glycation status influence hemoglobin glycation. Therefore, we propose albumin level and its glycation status to be quantified in conjunction with HbAlc for better management of diabetes.}, doi = {10.1021/acsomega.8b01702}, author = {Jagadeeshaprasad, Mashanipalya G. and Venkatasubramani, Vinashya and Unnikrishnan, Ambika G. and Kulkarni, Mahesh J.} } @article {45350, title = {Alkaline earth metal compounds of methylpyridinato beta-diketiminate ligands and their catalytic application in hydroboration of aldehydes and ketones}, journal = {Organometallics }, volume = { 37}, year = {2018}, month = {DEC}, pages = {4576-4584}, type = {Article }, abstract = {

Ever increasing demand for green and sustainable chemical processes has set up a drive to replace transition metals with earth-abundant, nontoxic, and environmentally benign alternatives. In this regard, the alkaline earth metal complexes have attracted significant attention. Herein, we have used a beta-diketiminato ligand with methyl-pyridine side arm to synthesize magnesium (1) and calcium (2) compounds. The constitutions of 1 and 2 have been confirmed by single crystal X-ray studies, which show that the magnesium and calcium atom in 1 and 2 possesses octahedral geometry. Subsequently, we have used them as catalysts (1 mol \%) for hydroboration of a wide range of aldehydes using pinacolborane (HBpin) at room temperature. The strategy has further been extended to ketones with 2 mol \% catalyst loading. DFT calculations have been performed to understand the mechanism.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.8b00568}, author = {Yadav, Sandeep and Dixit, Ruchi and Bisai, Milan Kumar and Vanka, Kumar and Sen, Sakya S.} } @article {44229, title = {Application of genetic programming (GP) formalism for building disease predictive models from protein-protein interactions (PPI) data}, journal = {IEEE-ACM Transactions on Computational Biology and Bioinformatics}, volume = {15}, year = {2018}, month = {FEB}, pages = {27-37}, type = {Article}, abstract = {

Protein-protein interactions (PPIs) play a vital role in the biological processes involved in the cell functions and disease pathways. The experimental methods known to predict PPIs require tremendous efforts and the results are often hindered by the presence of a large number of false positives. Herein, we demonstrate the use of a new Genetic Programming (GP) based Symbolic Regression (SR) approach for predicting PPIs related to a disease. In this case study, a dataset consisting of 135 PPI complexes related to cancer was used to construct a generic PPI predicting model with good PPI prediction accuracy and generalization ability. A high correlation coefficient (CC) magnitude of 0.893, and low root mean square error (RMSE), and mean absolute percentage error (MAPE) values of 478.221 and 0.239, respectively, were achieved for both the training and test set outputs. To validate the discriminatory nature of the model, it was applied on a dataset of diabetes complexes where it yielded significantly low CC values. Thus, the GP model developed here serves a dual purpose: (a) a predictor of the binding energy of cancer related PPI complexes, and (b) a classifier for discriminating PPI complexes related to cancer from those of other diseases.

}, keywords = {Binding energy, cancer, Disease, genetic programming, machine learning, protein-protein interactions, symbolic regression}, issn = {1545-5963}, doi = {10.1109/TCBB.2016.2621042}, author = {Vyas, Renu and Bapat, Sanket and Goel, Purva and Karthikeyan, Muthukumarasamy and Tambe, Sanjeev S. and Kulkarni, Bhaskar D.} } @article {44624, title = {B(C6F5)(3): catalyst or initiator? insights from computational studies into surrogate silicon chemistry}, journal = {ACS Catalysis}, volume = {8}, year = {2018}, month = {JUL}, pages = {6163-6176}, type = {Article}, abstract = {

One of the most promising recent developments in catalysis has been the use of the metal-free Lewis acid B(C6F5)(3) as a catalyst for a range of different chemical transformations. Perhaps the most impressive achievement in this regard is the recently accomplished in situ generation of SiH4 from surrogates (Simonneau and Oestreich, Nat. Chem., 2015,7, 816). However, what the current computational work, with density functional theory, reveals is that this process, in addition to being catalyzed by B(C6F5)(3), is also significantly dominated by a series of autocatalytic reactions. The results are further corroborated by the use of the energetic span model, which shows that the turnover frequency is higher for the newly proposed autocatalytic pathway in comparison to the conventional B(C6F5)(3)-catalyzed pathway. The current work therefore provides interesting new insights into surrogate silicon chemistry. But, more importantly, the current studies indicate that B(C6F5)(3) is likely to function more as an initiator rather than a pure catalyst in many metal-free transformations that have been reported to date.

}, keywords = {autocatalysis, Density functional theory, ion-pair, Lewis acid catalysis, reaction mechanism, surrogate silicone chemistry, tris(pentafluorophenyl)borane}, issn = {2155-5435}, doi = {10.1021/acscatal.7b04489}, author = {Banerjee, Subhrashis and Vanka, Kumar} } @article {44204, title = {Beyond hydrofunctionalisation: a well-defined calcium compound catalysed mild and efficient carbonyl cyanosilylation}, journal = {Chemistry-A European Journal}, volume = {24}, year = {2018}, month = {JAN}, pages = {1269-1273}, type = {Article}, abstract = {

Organocalcium compounds have been reported as efficient catalysts for various transformations, for cases in which one of the substrates contained an E-H (E=B, N, Si, P) bond. Here, we look at the possibility of employing an organocalcium compound for a transformation in which none of the precursors has a polar E-H bond. This study demonstrates the utilization of a well-defined amidinatocalcium iodide, [PhC(NiPr)(2)CaI] (1) for cyanosilylation of a variety of aldehydes and ketones with Me3SiCN under ambient conditions without the need of any co-catalyst. The reaction mechanism involves a weak adduct formation between 1 and Me3SiCN leading to the activation of the Si-C bond, which subsequently undergoes sigma-bond metathesis with a C=O moiety. Such a mechanistic pathway is unprecedented in alkaline earth metal chemistry. Experimental and computational studies support the mechanism.

}, keywords = {Ca catalysis, carbonyls, cyanosilylation, Density functional calculations, transition-metal free}, issn = {0947-6539}, doi = {10.1002/chem.201705795}, author = {Yadav, Sandeep and Dixit, Ruchi and Vanka, Kumar and Sen, Sakya S.} } @conference {44599, title = {CCCTK (Compute Cure for Cancer ToolKit) an open source drug discovery platform for design of novel anti-cancer agents}, booktitle = {255th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nexus of Food, Energy, and Water}, year = {2018}, month = {MAR}, publisher = {ACS, 1155 16TH ST, NW, Washington, DC 20036 USA}, organization = {ACS, 1155 16TH ST, NW, Washington, DC 20036 USA}, address = {New Orleans, LA}, author = {Karthikeyan, Muthukumarasamy and Vyas, Renu} } @article {45421, title = {Convergent covalent organic framework thin sheets as flexible supercapacitor electrodes}, journal = {ACS Applied Material \& Interfaces}, volume = {10}, year = {2018}, month = {AUG}, pages = {28139-28146}, type = {Article}, abstract = {Flexible supercapacitors in modern electronic equipment require light-weight electrodes, which have a high surface area, precisely integrated redox moieties, and mechanically strong flexible free-standing nature. However, the incorporation of the aforementioned properties into a single electrode remains a great task. Herein, we could overcome these challenges by a facile and scalable synthesis of the convergent covalent organic framework (COF) free-standing flexible thin sheets through solid-state molecular baking strategy. Here, redox-active anthraquinone (Dq) and pi-electron-rich anthracene (Da) are judiciously selected as two different linkers in a beta-ketoenamine-linked two-dimensional (2D) COF. As a result of precisely integrated anthraquinone moieties, COF thin sheet exhibits redox activity. Meanwhile, pi-electron-rich anthracene linker assists to improve the mechanical property of the free-standing thin sheet through the enhancement of noncovalent interaction between crystallites. This binder-free strategy offers the togetherness of crystallinity and flexibility in 2D COF thin sheets. Also, the synthesized porous crystalline convergent COF thin sheets are benefited with crack-free uniform surface and light-weight nature. Further, to demonstrate the practical utility of the material as an electrode in energy-storage systems, we fabricated a solid-state symmetrical flexible COF supercapacitor device using a GRAFOIL peeled carbon tape as the current collector.}, doi = {10.1021/acsami.8b10486}, author = {Khayum, Abdul M. and Vijayakumar, Vidyanand and Karak, Suvendu and Kandambeth, Sharath and Bhadra, Mohitosh and Suresh, Karthika and Acharambath, Nikhil and Kurungot, Sreekumar and Banerjee, Rahul} } @article {44640, title = {Correlation trends in the magnetic hyperfine structure of atoms: a relativistic coupled-cluster case study}, journal = {Physical Review A}, volume = {98}, year = {2018}, month = {AUG}, type = {Article}, abstract = {

The role of electron correlation in the hyperfine structure of alkali metals and alkaline earth metal monopositive ions in their ground electronic configuration is investigated using the Z-vector method in a relativistic coupled-cluster regime within the singles and doubles approximation. The systematic effects of core-correlating functions, polarization of core electrons, and high-lying virtual functions on core electrons correlation are studied. The study reveals that the core-correlating function plays a significant role in core polarization and thus is very important for precise calculation of the wave function near the nuclear region. The inner-core electrons (1s-2p) require very high virtual energy functions for proper correlation. Therefore, the all-electron correlation treatment and the inclusion of higher-energy virtual functions are the key factors for precise calculation of the hyperfine structure constant of atoms. Our calculated values are in excellent agreement with the available experimental values, which also implies that the wave function produced by the Z-vector method is accurate enough for further calculation of the parity- and time-reversal symmetry-violating properties in atoms and molecules.

}, issn = {2469-9926}, doi = {10.1103/PhysRevA.98.022507}, author = {Talukdar, Kaushik and Sasmal, Sudip and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article {44596, title = {Cyclohexylation of resorcinol with cyclohexanol catalyzed by tungstophosphoric acid supported zirconia catalysts}, journal = {Journal of Nanoscience and Nanotechnology}, volume = {18}, year = {2018}, month = {APR}, pages = {2986-2992}, abstract = {

We demonstrate a highly active and reusable heterogeneous catalyst system, tungstophosphoric acid (TPA) supported on zirconia (ZrO2), for the cyclohexylation of resorcinol by cyclohexanol to produce value added chemicals such as 2-cyclohexyl resorcinol, 4-cyclohexyl resorcinol and 3-Hydroxy cyclohexyl phenyl ether under liquid phase reaction condition. TPA/ZrO2 catalysts prepared with different TPA loadings (5-30 wt.\%) by wet impregnation method and calcined in the temperature range of 650-850 degrees C were characterized by Nitrogen sorption analysis, XRD, FTIR, DTG and DTA, and P-31 MAS NMR spectroscopy. Among the catalysts studied, 15 wt.\% TPA/ZrO2 catalyst calcined at 750 degrees C gave the highest conversion of resorcinol (51.2\%) with the selectivities for 3-Hydroxy cyclohexyl phenyl ether (53.9\%) and 2-cyclohexyl resorcinol and 4-cyclohexyl resorcinol together (46.1\%) under optimum reaction conditions. However, the selectivity of the products were controlled by varying the reaction conditions. At higher conversion of resorcinol (78.9\%), only C-alkylated products were formed at 200 degrees C with 15 wt.\% TPA/ZrO2 catalyst calcined at 750 degrees C. The combination of TPA and ZrO2 coupled with calcination temperature offered an excellent platform for the conversion of resorcinol into O- or C-alkylated products.

}, keywords = {15\% TPA/ZrO2, Cyclohexanol, Cyclohexylation, Keggin TPA, Resorcinol}, issn = {1533-4880}, doi = {10.1166/jnn.2018.14342}, author = {Balasubramanian, V. V. and Devassay, B. M. and Halligudi, S. B. and Deepika, R. and Umbarakar, S. B. and Vinu, A.} } @article {44237, title = {Development of enhanced hypericin yielding transgenic plants and somaclones: high throughput direct organogenesis from leaf and callus explants of Hypericum perforatum}, journal = {Industrial Crops and Products}, volume = {111}, year = {2018}, month = {JAN}, pages = {544-554}, type = {Article}, abstract = {

Hypericum perforatum is well known for its anti-depressent properties due to the presence of hypericins and hyperforins. The direct regeneration protocol from leaf explants and Agrobacterium tumefaciens mediated genetic transformation is a prerequisite for gene transfer studies in this valuable plant system as H. perforatum has shown its recalcitrance to these studies previously. The aim of generating transgenic shoots or somaclones in the present study is to select high hypericine yielding H. perforatum plants. High throughput direct bud organogenesis from leaf explants has been achieved for the first time in this plant system on media combination of MS + 5.0 mg/l BAP + 1.0 mg/l. This medium interestingly also worked as the indirect regeneration media for generation of somaclones from callus cultures. Thus far optimized single media can be used for direct and indirect regeneration in H. perforatum. The direct regeneration frequency of plantlets from leaf explants was found to be 80\% while 100\% was the regeneration frequency noted for indirect plantlet regeneration from callus cultures. The optimized direct regeneration protocol from leaf explants was utilized for A. tumefaciens (harbouring pCAMBIA 1301) mediated genetic transformation studies with the aim of establishing transgenic lines of H. perforatum. The resultant study successfully gave rise to kanamycin resistant GUS positive shoots with transformation efficiency of 3136 +/- 3.6. A total of four transgenic H. perforatum clones namely T2, T3, T5 and T8 with different growth parameters were established, where highest of fivefold increase in hypericin content was recorded by T5 (276.8 +/- 9.2 mu g/g dry wt.) in comparison to control non transformed plants (35.6 +/- 2.7 mu g/g dry wt.). Interestingly the presence of serotonin and melatonin was also detected in transgenic plants on TLC basis. The transgenic nature of the plants was confirmed by PCR with amplification of uidA gene. Apart from it, from indirect regeneration from callus, total of ten somaclones were generated. The ISSR profiling of somaclones scored a total of 156 bands, among which 118 were polymorphic in nature. The glasshouse established soma clones showed up to twofold increase in hypericin content on HPLC analysis.

}, keywords = {Direct regeneration, Hypericin, Hypericum perforation, Indirect regeneration, ISSR, Somaclones, Transgenic plants}, issn = {0926-6690}, doi = {10.1016/j.indcrop.2017.11.032}, author = {Khan, Shamshad A. and Verma, Priyanka and Arbat, Akshata and Gaikwad, Sushma and Parasharami, Varsha A.} } @article {45367, title = {Distribution of water in the pores of periodic mesoporous organosilicates - a proton solid state MAS NMR study}, journal = {Physical Chemistry Chemical Physics }, volume = {20}, year = {2018}, month = {DEC}, pages = {29351-29361}, type = {Article}, abstract = {Solid state proton (H-1) magic angle spinning (MAS) NMR has been employed to study the distribution of confined water in ethane substituted periodic mesoporous organosilicate (PMOE) materials. Proton spectra acquired at different hydration levels are analysed and interpreted in terms of water clusters of various sizes and distributions of water layers on the pore surface. For comparison, we also performed similar experiments on SBA-15. The formation of larger clusters at lower hydration suggests that the pores of PMOE are getting filled with water at lower hydration levels than those in SBA-15. For PMOE, the simultaneous presence of two major resonances in the ranges 3.6-4.1 ppm and 4.4-5.2 ppm and their behaviour upon hydration imply a water layer distribution that is the sum of two contributions, corresponding to fully filled and partially filled pores or pore segments. Furthermore, the behaviour mentioned above suggests that both radial and axial filling mechanisms play a significant role in the hydration process. For SBA-15, as a function of hydration, we observed a smooth variation in the proton chemical shift of the main dynamic resonance. In accordance with previous studies, this is attributed to the gradual increase in the average thickness of water layers with an increase in hydration, and to a pore filling mechanism that is predominantly radial.}, issn = {1463-9076}, doi = { 10.1039/c8cp04902e}, author = {Veena, V. S. and Illath, Kavya and Lazar, Anish and Vinod, C. P. and Ajithkumar, T. G. and Jayanthi, S.} } @article {44458, title = {Easily accessible lithium compound catalyzed mild and facile hydroboration and cyanosilylation of aldehydes and ketones}, journal = {Chemical Communications}, volume = {54}, year = {2018}, month = {APR}, abstract = {Simple and readily accessible lithium compounds such as 2,6-ditertbutyl phenolate lithium (1a), 1,1{\textquoteright} dilithioferrocene (1b) and nacnac lithium (1c) are found to be efficient single site catalysts for hydroboration of...}, doi = {10.1039/C8CC02314J}, author = {Bisai, Milan and Das, Tamal and Vanka, Kumar and Sen, Sakya S.} } @article {45450, title = { Enhanced activity of Withania somnifera family-1 glycosyltransferase (UGT73A16) via mutagenesis}, journal = {World Journal Of Microbiology \& Biotechnology}, volume = {34}, year = {2018}, month = {OCT}, type = {Article }, abstract = {This work used an approach of enzyme engineering towards the improved production of baicalin as well as alteration of acceptor and donor substrate preferences in UGT73A16. The 3D model of Withania somnifera family-1 glycosyltransferase (UGT73A16) was constructed based on the known crystal structures of plant UGTs. Structural and functional properties of UGT73A16 were investigated using docking and mutagenesis. The docking studies were performed to understand the key residues involved in substrate recognition. In the molecular model of UGT73A16, substrates binding pockets are located between N- and C-terminal domains. Modeled UGT73A16 was docked with UDP-glucose, UDP-glucuronic acid (UDPGA), kaempferol, isorhamnetin, 3-hydroxy flavones, naringenin, genistein and baicalein. The protein-ligand interactions showed that His 16, Asp 246, Lys 255, Ala 337, Gln 339, Val 340, Asn 358 and Glu 362 amino acid residues may be important for catalytic activity. The kinetic parameters indicated that mutants A337C and Q339A exhibited 2-3 fold and 6-7 fold more catalytic efficiency, respectively than wild type, and shifted the sugar donor specificity from UDP-glucose to UDPGA. The mutant Q379H displayed large loss of activity with UDP-glucose and UDPGA strongly suggested that last amino acid residue of PSPG box is important for glucuronosylation and glucosylation and highly specific to sugar binding sites. The information obtained from docking and mutational studies could be beneficial in future to engineer this biocatalyst for development of better ones.}, issn = { 0959-3993}, doi = {10.1007/s11274-018-2534-4}, author = {Singh, Somesh and Patel, Krunal A. and Sonawane, Prashant D. and Vishwakarma, Rishi K. and Khan, Bashir M.} } @article {45419, title = { Enhanced selectivity of 3-D ordered macroporous Pt/Al2O3 catalysts in nitrites removal from water}, journal = {Applied Catalysis A-General}, volume = {564}, year = {2018}, month = {AUG}, pages = {26-32}, type = {Article}, abstract = {Tailored macroporous mesoporous alumina supports have been successfully prepared using a single hard templating approach. Pt nanoparticles, showing similar physico-chemical properties, were homogeneously dispersed throughout the different alumina frameworks as catalytic active phase for drinking water treatment. We demonstrated that careful modification of pore properties of the catalyst (size and connectivity) by pseudomorphic transformation can strongly modulate the reaction rate and selectivity through the limited access to Pt active sites within the alumina porous particles. Specifically, 3-D Ordered Macroporous Pt-Al2O3 catalysts with a high degree of interconnectivity yield to superior catalytic properties (enhanced activity and selectivity) over pure mesoporous counterparts in the hydrogenation of nitrites in water. We found that large pores (240 nm) interconnected with windows (110 nm) alleviate mass transfer limitations and clearly improve NZ selectivity. The findings of this study further suggest the possibility of engineering the pore architecture of the support to fine tune the selectivity for a particular reaction rather than investigating more on tuning the properties of the costly active metallic phase.}, doi = {10.1016/j.apcata.2018.07.014}, author = {Sekhar, A. C. Sunil and Zaki, A. and Troncea, S. and Casale, S. and Vinod, C. P. and Dacquin, J. P. and Granger, P.} } @article {44470, title = {Ethoxy-ester functionalized imidazolium based ionic liquids for lithium ion batteries }, journal = {ChemistrySelect}, volume = {3}, year = {2018}, month = {JUN}, pages = {6255-6261}, abstract = {Ethoxy ester functionalized imidazolium and bis(tri fluoromethanesulfonyl)imide based ionic liquids (ILs) are synthesized and considered as electrolyte for lithium ion batteries. The series of ethoxy ester functionalized ionic liquids were chosen with increase in ethoxy unit from one to three, followed by polymeric units. These ionic liquids provide both ester and ethoxy groups as interaction sites for Li+ ions enhancing the Li+ ion transportation, resulting in ionic conductivity of 10(-3) Scm(-1) at 25 degrees C, which is of 10(3) factor higher than ethoxy containing polyethylene oxide solid polymer electrolyte. It{\textquoteright}s noteworthy that the conductivity increases as ethoxy units are increased from one to three units, followed by a decrease for the polymeric ethoxy unit. Electrochemical stability window of these ionic liquids improves as the ethoxy groups are added to imidazolium cation. The Li/LiFePO4 cell fabricated with [ME(3)AMIm][TFSI] electrolyte shows good initial discharge capacity of 98.5 mAhg(-1) at 0.05 C-rate at room temperature, which gradually decreases with cycling. Systematic investigation of electrode surfaces by using SEM and EDX shows deposition of passivation layers on their surfaces. Ionic liquids fabricated by this facile method provide a promising model system for understanding the molecular interactions in promoting the lithium-ion conduction mechanism. The advantages and the limits associated to series of ionic liquid electrolytes are critically investigated.}, doi = {10.1002/slct.201800513}, author = {Nirmale, Trupti and Khupse, Nageshwar and Gore, Rohitkumar and Ambekar, Jalindar and Kulkarni, Milind and Varma, Anjanikumar and Kale, Bharat} } @article {44614, title = {Facile, environmentally benign and scalable approach to produce pristine few layers graphene suitable for preparing biocompatible polymer nanocomposites}, journal = {Scientific Reports}, volume = {8}, year = {2018}, month = {JUL}, pages = {11228}, abstract = {

The success of developing graphene based biomaterials depends on its ease of synthesis, use of environmentally benign methods and low toxicity of the chemicals involved as well as biocompatibility of the final products/devices. We report, herein, a simple, scalable and safe method to produce defect free few layers graphene using naturally available phenolics i.e. curcumin/tetrahydrocurcumin/ quercetin, as solid-phase exfoliating agents with a productivity of similar to 45 g/batch (D/G = 0.54 and D/D{\textquoteright} \<= 1.23). The production method can also be employed in liquid-phase using a ball mill (20 g/batch, D/G \<= 0.23 and D/D{\textquoteright} \<= 1.12) and a sand grinder (10 g/batch, D/G \<= 0.11 and D/D similar to = 0.78). The combined effect of p-p interaction and charge transfer (from curcumin to graphene) is postulated to be the driving force for efficient exfoliation of graphite. The yielded graphene was mixed with the natural rubber (NR) latex to produce thin film nanocomposites, which show superior tensile strength with low modulus and no loss of \% elongation at break. In-vitro and in-vivo investigations demonstrate that the prepared nanocomposite is biocompatible. This approach could be useful for the production of materials suitable in products (gloves/condoms/catheters), which come in contact with body parts/ body fluids.

}, issn = {2045-2322}, doi = {10.1038/s41598-018-28560-1}, author = {George, Gejo and Sisupal, Suja Bhargavan and Tomy, Teenu and Kumaran, Alaganandam and Vadivelu, Prabha and Suvekbala, Vemparthan and Sivaram, Swaminathan and Ragupathy, Lakshminarayanan} } @article {44616, title = {Flexible composite mechanical energy harvester from a ferroelectric organoamino phosphonium salt}, journal = {Angewandte Chemie-International Edition}, volume = {57}, year = {2018}, month = {JUL}, pages = {9054-9058}, abstract = {

A new binary organic salt diphenyl diisopropylamino phosphonium hexaflurophosphate (DPDPPF6) was shown to exhibit a good ferroelectric response and employed for mechanical energy harvesting application. The phosphonium salt crystallizes in the monoclinic noncentrosymmetric space group Cc and exhibits an H-bonded 1D chain structure due to N-HF interactions. Ferroelectric measurements on the single crystals of DPDPPF6 gave a well-saturated rectangular hysteresis loop with a remnant (P-r) polarization value of 6Ccm(-2). Further, composite devices based on polydimethylsiloxane (PDMS) films for various weight percentages (3, 5, 7, 10 and 20wt\%) of DPDPPF6 were prepared and examined for power generation by using an impact test setup. A maximum output peak-to-peak voltage (V-PP) of 8.5V and an output peak-to-peak current (I-PP) of 0.5A was obtained for the non-poled composite film with 10wt\% of DPDPPF6. These results show the efficacy of organic ferroelectric substances as potential micropower generators.

}, keywords = {binary phosphonium salts, energy conversion, ferroelectricity, hydrogen bonding, polymer composites}, issn = {1433-7851}, doi = {10.1002/anie.201805479}, author = {Vijayakanth, Thangavel and Srivastava, Anant Kumar and Ram, Farsa and Kulkarni, Priyangi and Shanmuganathan, Kadhiravan and Praveenkumar, Balu and Boomishankar, Ramamoorthy} } @proceedings {45574, title = {Framework for building a portfolio of disruptive technologies for sustainable mobility}, year = {2018}, month = {OCT}, publisher = {FISITA}, address = {Chennai; India}, abstract = {We provide a framework that would help the CTO to (a) assess the disruptive power of new technologies at an early stage (b) systematically track its evolution and (c) build a sustainable plan for the company to respond to the disruption. We have applied our framework to illustrate how the CTO of an automotive OEM can build a portfolio of disruptive technologies in electric, autonomous and connected vehicles to create sustainable mobility for the future. We describe qualitative and quantitative tools and metrics that would help the CTO to make investment decisions on new disruptive technologies and communicate to the stakeholders}, url = {https://www.scopus.com/inward/record.url?eid=2-s2.0-85057984300\&partnerID=40\&md5=9cdbb097550a6ed6e2d126140aba0ad3}, author = {Venugopal, S. and Shankar, S.} } @article {44034, title = {Genetic engineering approach using early Vinca alkaloid biosynthesis genes led to increased tryptamine and terpenoid indole alkaloids biosynthesis in differentiating cultures of catharanthus roseus}, journal = {Protoplasma}, year = {2018}, month = {AUG}, pages = {1-11}, type = {Article}, abstract = {

Catharanthus roseus today occupies the central position in ongoing metabolic engineering efforts in medicinal plants. The entire multi-step biogenetic pathway of its very expensive anticancerous alkaloids vinblastine and vincristine is fairly very well dissected at biochemical and gene levels except the pathway steps leading to biosynthesis of monomeric alkaloid catharanthine and tabersonine. In order to enhance the plant-based productivity of these pharma molecules for the drug industry, cell and tissue cultures of C. roseus are being increasingly tested to provide their alternate production platforms. However, a rigid developmental regulation and involvement of different cell, tissues, and organelles in the synthesis of these alkaloids have restricted the utility of these cultures. Therefore, the present study was carried out with pushing the terpenoid indole alkaloid pathway metabolic flux towards dimeric alkaloids vinblastine and vincristine production by over-expressing the two upstream pathway genes tryptophan decarboxylase and strictosidine synthase at two different levels of cellular organization viz. callus and leaf tissues. The transformation experiments were carried out using Agrobacterium tumefaciens LBA1119 strain having tryptophan decarboxylase and strictosidine synthase gene cassette. The callus transformation reported a maximum of 0.027\% dry wt vindoline and 0.053\% dry wt catharanthine production, whereas, the transiently transformed leaves reported a maximum of 0.30\% dry wt vindoline, 0.10\% catharanthine, and 0.0027\% dry wt vinblastine content. {\textcopyright} 2017 Springer-Verlag GmbH Austria

}, keywords = {Agroinfiltration, Strictosidine Synthase (CrSTR), Terpenoid Indole Alkaloids (TIAs)}, doi = {10.1007/s00709-017-1151-7}, author = {Sharma, A. and Verma, P. and Mathur, A. and Mathur, A.K.} } @article {45447, title = { Glucose isomerization catalyzed by bone char and the selective production of 5-hydroxymethylfurfural in aqueous media}, journal = {Sustainable Energy \& Fuels}, volume = {2}, year = {2018}, month = {OCT}, pages = { 2148-2153}, type = {Article}, abstract = {The selective production of 5-hydroxymethylfurfural (HMF) is important, and it is difficult with glucose substrates in a water solvent. Here we demonstrate a selective method for glucose-to-HMF conversion using the combined catalysis of bone char and 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate acidic ionic liquid catalysts with a high HMF selectivity (54\%) in water.}, issn = {2398-4902}, doi = {10.1039/c8se00339d}, author = {Matsagar, Babasaheb M. and Van Nguyen, Chi and Hossain, Md. Shahriar A. and Islam, Md. Tofazzal and Yamauchi, Yusuke and Dhepe, Paresh L. and Wu, Kevin C. -W.} } @article {44493, title = {High and reversible lithium ion storage in self-exfoliated triazole-triformyl phloroglucinol-basedcovalent organic nanosheets}, journal = {Advanced Energy Materials}, volume = {8}, year = {2018}, month = {MAR}, pages = {Article Number: 1702170}, abstract = {Covalent organic framework (COF) can grow into self-exfoliated nanosheets. Their graphene/graphite resembling microtexture and nanostructure suits electrochemical applications. Here, covalent organic nanosheets (CON) with nanopores lined with triazole and phloroglucinol units, neither of which binds lithium strongly, and its potential as an anode in Li-ion battery are presented. Their fibrous texture enables facile amalgamation as a coin-cell anode, which exhibits exceptionally high specific capacity of approximate to 720 mA h g(-1) (@100 mA g(-1)). Its capacity is retained even after 1000 cycles. Increasing the current density from 100 mA g(-1) to 1 A g(-1) causes the specific capacity to drop only by 20\%, which is the lowest among all high-performing anodic COFs. The majority of the lithium insertion follows an ultrafast diffusion-controlled intercalation (diffusion coefficient, D-Li(+) = 5.48 x 10(-11) cm(2) s(-1)). The absence of strong Li-framework bonds in the density functional theory (DFT) optimized structure supports this reversible intercalation. The discrete monomer of the CON shows a specific capacity of only 140 mA h g(-1) @50 mA g(-1) and no sign of lithium intercalation reveals the crucial role played by the polymeric structure of the CON in this intercalation-assisted conductivity. The potentials mapped using DFT suggest a substantial electronic driving-force for the lithium intercalation. The findings underscore the potential of the designer CON as anode material for Li-ion batteries.}, doi = {10.1002/aenm.201702170}, author = {Haldar, Sattwick and Roy, Kingshuk and Nandi, Shyamapada and Chakraborty, Debanjan and Puthusseri, Dhanya and Gawli, Yogesh and Ogale, Satishchandra and Vaidhyanathan, Ramanathan} } @article {44496, title = {Highly selective aqueous phase hydrogenation of phenols over nanostructured RuO2 on MCM-41 catalysts}, journal = {Nano-Structures \& Nano-Objects }, volume = {13}, year = {2018}, month = {FEB}, pages = {36-43}, abstract = {Selective aqueous phase hydrogenation of phenol as well as its derivatives is important for the synthesis of chemical intermediates which are crucial for the manufacture of high-tonnage commodities and a multitude of value added platform chemicals. Herein, we report a facile catalyst made of highly dispersed small RuO2 nanoparticles supported on mesoporous MCM-41 using one-pot approach. The optimal 5RuO2-MCM-41 catalyst with particle size 6-8 nm showed excellent activity and selectivity in aqueous phase hydrogenation of phenol and other functionalized substrates, which are building blocks of lignin, to corresponding cyclohexanol products without any additives. These catalysts showed better stability and can be reused several times without any significant drop in activity which proves the heterogeneity of the immobilized oxide catalyst.}, doi = {10.1016/j.nanoso.2017.11.004}, author = {Betsy, K. J. and Lazar, Anish and Vinod, C. P.} } @article {45385, title = {Highly stable COF-supported Co/Co(OH)(2) nanoparticles heterogeneous catalyst for reduction of nitrile/nitro compounds under mild conditions}, journal = {Small}, volume = {14}, year = {2018}, month = {SEP}, type = {Article}, abstract = {Ordered nanoporosity in covalent organic framework (COF) offers excellent opportunity for property development. Loading nanoparticles (nPs) onto them is one approach to introducing tailor-made properties into a COF. Here, a COF-Co/Co(OH)(2) composite containing about 16 wt\% of <6 nm sized Co/Co(OH)(2) nPs is prepared on a N-rich COF support that catalyzes the release of theoretical equivalence of H-2 from readily available, safe, and cheap NaBH4. Furthermore, the released H-2 is utilized for the hydrogenation of nitrile and nitro compounds to amines under ambient conditions in a facile one-pot reaction. The COF "by choice" is built from "methoxy" functionalized dialdehydes which is crucial in enabling the complete retention of the COF structure under the conditions of the catalysis, where the regular Schiff bonds would have hydrolyzed. The N-rich binding pockets in the COF ensure strong nP-COF interactions, which provides stability and enables catalyst recycling. Modeling studies reveal the crucial role played by the COF in exposing the active facets and thereby in controlling the activation of the reducing agent. Additionally, via density functional theory, we provide a rational explanation for how these COFs can stabilize nanoparticles which grow beyond the limiting pore size of the COF and yet result in a truly stable heterogeneous catalyst - a ubiquitous observation. The study underscores the versatility of COF as a heterogeneous support for developing cheap and highly active nonnoble metal catalysts.}, doi = {10.1002/smll.201801233}, author = {Mullangi, Dinesh and Chakraborty, Debanjan and Pradeep, Anu and Koshti, Vijay and Vinod, Chathakudath P. and Panja, Soumendranath and Nair, Sunil and Vaidhyanathan, Ramanathan} } @article {44497, title = {Identification of potent chromone embedded [1,2,3]-triazoles as novel anti-tubercular agents}, journal = {Royal Society Open Science}, volume = {5}, year = {2018}, month = {APR}, pages = {Article Number: 171750}, abstract = {A series of 20 novel chromone embedded [1,2,3]-triazoles derivatives were synthesized via an easy and convenient synthetic procedure starting from 2-hydroxy acetophenone. The in vitro anti-mycobacterial evaluation studies carried out in this work reveal that seven compounds exhibit significant inhibition against Mycobacterium tuberculosis H37Rv strain with MIC in the range of 1.56-12.5 mu g ml(-1). Noticeably, compound 6s was the most potent compound in vitro with a MIC value of 1.56 mu g ml(-1). Molecular docking and chemoinformatics studies revealed that compound 6s displayed drug-like properties against the enoyl-acyl carrier protein reductase of M. tuberculosis further establishing its potential as a potent inhibitor.}, doi = {10.1098/rsos.171750}, author = {Nalla, Viswanadh and Shaikh, Aslam and Bapat, Sanket and Vyas, Renu and Karthikeyan, M. and Yogeeswari, P. and Sriram, D. and Muthukrishnan, M.} } @article {44511, title = {Iron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process}, journal = {Journal of the American Chemical Society}, volume = {140}, year = {2018}, month = {MAR }, pages = {4430-4439}, abstract = {

Earth abundant, first row transition metals offer a cheap and sustainable alternative to the rare and precious metals. However, utilization of first row metals in catalysis requires harsh reaction conditions, suffers from limited activity, and fails to tolerate functional groups. Reported here is a highly efficient iron catalyzed hydroformylation of alkenes under mild conditions. This protocol operates at 10-30 bar syngas pressure below 100 degrees C, utilizes readily available ligands, and applies to an array of olefins. Thus, the iron precursor [HFe(CO)(4)](-)[Ph3PNPPh3](+) (1) in the presence of triphenyl phosphine catalyzes the hydroformylation of 1-hexene (S2), 1-octene (S1), 1-decene (S3), 1-dodecene (S4), 1-octadecene (S5), trimethoxy(vinyl)silane (S6), trimethyl(vinyl)silane (S7), cardanol (S8), 2,3-dihydrofuran (S9), allyl malonic acid (S10), styrene (S11), 4-methylstyrene (S12), 4-iBu-styrene (S13), 4-tBu-styrene (S14), 4-methoxy styrene (S15), 4-acetoxy styrene (S16), 4-bromo styrene (S17), 4-chloro styrene (S18), 4-vinylbenzonitrile (S19), 4-vinylbenzoic acid (S20), and allyl benzene (S21) to corresponding aldehydes in good to excellent yields. Both electron donating and electron withdrawing substituents could be tolerated and excellent conversions were obtained for S11-S20. Remarkably, the addition of 1 mol \% acetic acid promotes the reaction to completion within 16-24 h. Detailed mechanistic investigations revealed in situ formation of an iron-dihydride complex [H2Fe(CO)(2)(PPh3)(2)] (A) as an active catalytic species. This finding was further supported by cyclic voltammetry investigations and intermediacy of an Fe(0)-Fe(II) species was established. Combined experimental and computational investigations support the existence of an iron-dihydride as the catalyst resting state, which then follows a Fe(II) based catalytic cycle to produce aldehyde.

}, issn = {0002-7863}, doi = {10.1021/jacs.8b01286}, author = {Pandey, Swechchha and Raj, K. Vipin and Shinde, Dinesh R. and Vanka, Kumar and Kashyap, Varchaswal and Kurungot, Sreekumar and Vinod, C. P. and Chikkali, Samir H.} } @article {44589, title = {Judicious reduction of supported Ti catalyst enables access to disentangled ultrahigh molecular weight polyethylene}, journal = {Macromolecules}, volume = {51}, year = {2018}, month = {JUN }, pages = {4541-4552}, abstract = {

Heterogeneous Ziegler-Natta and homogeneous metallocene catalysts are known to produce ultrahigh molecular weight polyethylene (UHMWPE) in the entangled state. On the other hand, only (two) homogeneous single-site catalysts are reported to yield disentangled UHMWPE (dis-UHMWPE). This disparity between the two types of catalysts and the two states of polyethylene can be bridged if a heterogeneous single-site catalyst that can yield dis-UHMWPE is made accessible. Here, one-pot two-step synthesis of a MgCl2 supported [Ti(OEt)(4)] derived catalyst 1 with a two-stage activation strategy is reported to produce dis-UHMWPE. Second activation of catalyst 1 was performed by adding excess modified methylaluminoxane (MMAO12), and XPS analysis indicated that the catalyst existed in only Ti(III) state at [A1]/[Ti] ratio of 600. Catalyst 1 after second activation with MMAO12 was found to be highly active in ethylene polymerization and produced dis-UHMWPE. Polymerization conditions were tailored to obtain molecular weight (M-w) as high as 13 million g/mol PE. To the best of our knowledge, this is the first time a heterogeneous catalyst (catalyst 1) that displays pseudosingle site nature is able to produce dis-UHMWPE. The thus-prepared nascent polyethylene revealed a melting temperature of 141-144 degrees C, which is a characteristic melting transition for a dis-UHMVVPE. The disentangled state of the nascent PE and its M-w and MVVD were further authenticated by rheological investigations. Isothermal time, sweep oscillatory experiments in linear viscoelastic limit revealed a rapid rise in elastic modulus followed by equilibration to plateau modulus, which are characteristic features of the disentangled state. Thus, a pseudo-singlesite heterogeneous catalyst has been accessed, which upon second activation with excess MMAO12 led to the production of dis-UHMWPE.

}, issn = {0024-9297}, doi = {10.1021/acs.macromol.8b00590}, author = {Gote, Ravindra P. and Mandal, Dipa and Patel, Ketan and Chaudhuri, Krishnaroop and Vinod, C. P. and Lele, Ashish K. and Chikkali, Samir H.} } @article {44617, title = {Lower scaling approximation to EOM-CCSD: a critical assessment of the ionization problem}, journal = {International Journal of Quantum Chemistry}, volume = {118}, year = {2018}, month = {JUL}, pages = {e25594}, abstract = {

In this article, we investigate the performance of different approximate variants of the EOM-CCSD method for calculation of ionization potential (IP), as compared to EOM-CCSDT reference values. None of the lower scaling approximations to the EOM-CCSD method give a consistent performance for valence, inner valence, and core ionization, favoring one, or the other depending on the nature of the approximation used. The parent EOMIP-CCSD method gives superior performance for valence IP but can show large errors for inner valence and core ionization. The problem is particularly severe for core-ionization, where even the EOMIP-CCSDT method cannot provide quantitative accuracy.

}, keywords = {EOM-CCSD, Ionization potential, lower scaling}, issn = {0020-7608}, doi = {10.1002/qua.25594}, author = {Dutta, Achintya Kumar and Vaval, Nayana and Pal, Sourav} } @article {44354, title = {Magnetically tunable liquid dielectric with giant dielectric permittivity based on core-shell superparamagnetic iron oxide}, journal = {Nanotechnology}, volume = {29}, year = {2018}, month = {JUL}, pages = {Article Number: 265707}, type = {Article}, abstract = {A liquid dielectric based on a core-shell architecture having a superparamagnetic iron oxide core and a shell of silicon dioxide was synthesized. The frequency dependence of dielectric properties was evaluated for different concentrations of iron oxide. The dependence of magnetic field on the dielectric properties was also studied. Aqueous ferrofluid exhibited a giant dielectric constant of 6.4 x 10(5) at 0.1 MHz at a concentration of 0.2 vol\% and the loss tangent was 3. The large rise in dielectric constant at room temperature is modelled and explained using percolation theory and Maxwell-Wagner-Sillars type polarization. The ferrofluid is presumed to consist of nanocapacitor networks which are wired in series along the lateral direction and parallel along longitudinal direction. On the application of an external magnetic field, the chain formation and its alignment results in the variation of dielectric permittivity.}, doi = {10.1088/1361-6528/aabc4e}, author = {Vinayasree, S. and Nitha, T. S. and Tiwary, C. S. and Ajayan, P. M. and Joy, P. A. and Anantharaman, M. R.} } @article {44620, title = {Mechanism of nickel(II)-catalyzed C(2)-H alkynylation of indoles with alkynyl bromide}, journal = {Organometallics}, volume = {37}, year = {2018}, month = {JUL}, pages = {2037-2045}, abstract = {

The nickel system (THF)(2)NiBr2/phen has recently been shown as an efficient catalyst for the C-H bond alkynylation of diverse heteroarenes with (triisopropylsilyl)alkynyl bromide via monodentate chelation assistance. Herein, we report an extensive mechanistic investigation for the direct alkynylation of indoles involving the well-defined nickel catalyst, which features a coordinative insertion pathway of alkynyl bromide with the Ni(II) catalyst. Catalytic relevant nickel complexes, (phen)NiCl2 (5), (phen)(2)NiCl2 (6) and [(phen)(3)Ni].NiCl4 (7) were isolated, and the complexes 6 and 7 were structurally characterized. Well-defined complexes were as competent as the in situ generated catalyst system (THF)(2)NiBr2/phen for the alkynylation of indoles. Various controlled studies and reactivity experiments were performed to understand the probable pathway for the alkynylation reaction. Kinetics analysis highlights that the complex (phen)NiX2 acts as a precatalyst, and the involvement of substrate indole and LiO{\textquoteright}Bu are essential for the generation of the active catalyst. Deuterium labeling and kinetic studies suggest that the process involving C-H cleavage and carbo-nickelation of indole is a crucial rate influencing step. Reactivity study of various alkynyl compounds with nickel-species highlights a migratory insertion route for the reaction. DFT calculations firmly support the experimental findings and suggest the coordinative insertion pathway of alkynyl bromide rather than oxidative addition toward the nickel(II) center.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.8b00177}, author = {Khake, Shrikant M. and Jain, Shailja and Patel, Ulhas N. and Gonnade, Rajesh G. and Vanka, Kumar and Punji, Benudhar} } @article {44517, title = {Mechanistic aspects of pincer nickel(II)-catalyzed C-H bond alkylation of azoles with alkyl halides}, journal = {Organometallics}, volume = {37}, year = {2018}, month = {MAR}, pages = {1017-1025}, abstract = {

The quinolinyl-based pincer nickel complex, kappa(N),kappa(N),kappa(N)-{C9H6N-(mu-N)-C6H4-NMe2}NiCl [((NNNMe2)-N-Q)-NiCl; (1)] has recently been demonstrated to be an efficient and robust catalyst for the alkylation of azoles with alkyl halides under copper-free conditions. Herein, we report the detailed mechanistic investigation for the alkylation of azoles catalyzed by ((NNNMe2)-N-Q)NiCl (1), which highlights an iodine atom transfer (IAT) mechanism for the reaction involving a Ni-II/Ni-III process. Deuterium labeling experiments indicate reversible cleavage of the benzothiazole C-H bond, and kinetic studies underline a fractional negative rate order with the substrate benzothiazole. The involvement of an alkyl radical during the alkylation is validated by radical clock and external additive experiments. An active intermediate species ((NNNMe2)-N-Q)Ni(benzothiazolyl) (5a) has been isolated and structurally characterized. The complex ((NNNMe2)-N-Q)Ni(benzothiazoly1) (5a) is found to be the resting state of catalyst 1. Kinetic analysis of electronically different intermediates suggests that the step involving the reaction of 5a with alkyl iodide is crucial and a rate-influencing step. DFT calculations strongly support the experimental findings and corroborate an IAT process for the alkylation reaction.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.8b00025}, author = {Patel, Ulhas N. and Jain, Shailja and Pandey, Dilip K. and Gonnade, Rajesh G. and Vanka, Kumar and Punji, Benudhar} } @article {44520, title = {Mechano-responsive room temperature luminescence variations of boron conjugated pyrene in air}, journal = {Chemical Communications}, volume = {54}, year = {2018}, month = {JUN}, pages = {6028-6031}, abstract = {

Stimuli responsive tunable luminescence is a promising field of research. Even though mechanofluorescence is widely studied, mechanophosphorescence remains unexplored. Here we report the mechano-driven fluorescence and phosphorescence variations of a pyrene tetraboronic ester derivative. The fluorochromic and room temperature phosphorescence features are supported by theoretical studies and single crystal analysis. The mechanically ground fluorescence active but phosphorescence inactive pyrene tetraboronic ester exhibits room temperature phosphorescence in air withmechanical force. The efficient intermolecular electronic coupling in the dimer formed upon scratching enables a good communication between singlet and triplet states, hence resulting in room temperature mechanophosphorescence.

}, issn = {1359-7345}, doi = {10.1039/c8cc03494j}, author = {Wakchaure, Vivek C. and Ranjeesh, Kayaramkodath C. and Goudappagouda and Das, Tamal and Vanka, Kumar and Gonnade, Rajesh and Babu, Sukumaran S.} } @article {44522, title = {Mesoporous shell@macroporous core aluminosilicates as sustainable nanocatalysts for direct N-alkylation of amines}, journal = {Chemnanomat}, volume = {4}, year = {2018}, month = {JUN}, pages = {537-541}, abstract = {

Aluminosilicate spheres with a macroporous core and mesoporous shell (Si/Al ratio of 11) is synthesised by a sol-gel method utilizing cetyltrimethyl ammonium bromide (CTAB) as a structure directing agent in basic medium. The selective incorporation of aluminium in the silica matrix results in the formation of aluminosilicates with an overall acidity of 0.32mmol/g with interconnected pores. Direct N-alkylation reaction is a prototype of C-N bond formation reaction and meso- macroporous aluminosilicate is shown to catalyze this reaction with excellent yield. The catalyst is tested and found sustainable for five catalytic cycles even without any high temperature regeneration step.

}, keywords = {Aluminosilicates, macroporous, Mesoporous, N-alkylation, nanocatalysis}, issn = {2199-692X}, doi = {10.1002/cnma.201800081}, author = {Sekhar, Anandakumari C. Sunil and Ashokkumar, Anumol Erumpukuthickal and Cygnet, Choorapoikayil T. and Lakshmi, Saseendranpillai Vidhya and Deepak, Francis Leonard and Vinod, Chathakudath P.} } @article {44527, title = {Microbial synthesis of mammalian metabolites of spironolactone by thermophilic fungus thermomyces lanuginosus}, journal = {Steroids}, volume = {136}, year = {2018}, month = {MAY}, abstract = {Mesophilic fungi are well recognized as models of mammalian drug metabolism. Thermophilic fungi remained unexplored despite having a unique mechanism of growing at higher temperatures and performing wide diverse reactions. The present investigation is directed to isolate a promising thermophilic fungal strain capable of biotransformation using spironolactone as a model drug. Two-stage fermentation protocol was followed for the process. The transformation of spironolactone was identified by HPLC and structure elucidation of the metabolites was done with the help of LC-MS/MS analysis and previous reports. A strain of Thermomyces lanuginosus isolated from decomposed banana peel waste was found to be most promising in transforming spironolactone to 4 metabolites viz.7α-thiospironolactone (M1) canrenone (M2), 7α-thiomethylspironolactone (M3) and 6β-OH-7α-thiomethylspironolactone (M4), the major mammalian metabolites reported previously. The synthesis of metabolites of spironolactone by T.lanuginosus similar to mammals clearly states that this fungus possess enzyme system similar to mammals. Hence, this fungus has the potential to use as a model organism for studying drug metabolism.}, doi = {10.1016/j.steroids.2018.05.011}, author = {Sreelatha, B. and Prasad, G. Shyam and Vankudoth, Koteswara Rao and Sivadevuni, Girisham} } @article {44648, title = {Multi-step continuous flow synthesis of the cystic fibrosis medicine ivacaftor}, journal = {Reaction Chemistry \& Engineering}, volume = {3}, year = {2018}, month = {AUG}, pages = {520-526}, abstract = {

A continuous flow ozonolysis method combined with a multi-step flow sequence is developed for the synthesis of the drug ivacaftor for the first time. Safe ozonolysis, a continuous flow quadruple reaction to construct a quinolone scaffold, and inline extraction followed by continuous phase separation are the key features of the present work. The feasibility of using a continuous mixed flow reactor, commonly referred to as a continuous stirred tank reactor (CSTR), is also investigated for the relatively slow reaction step. The current integrated multi-step flow synthesis can produce 7.2 g of the drug ivacaftor per day on a laboratory scale, which is sufficient to treat 50 patients per day. The present route can also be used as a general route for the synthesis of other related drugs such as quinolone antibiotics.

}, issn = {2058-9883}, doi = {10.1039/c8re00025e}, author = {Vasudevan, N. and Sharma, Mrityunjay K. and Reddy, D. Srinivasa and Kulkarni, Amol A.} } @article {45474, title = { Nitrosporeusine analogue ameliorates Chandipura virus induced inflammatory response in CNS via NF kappa b inactivation in microglia}, journal = {PLOS Neglected Tropical Diseases}, volume = {12}, year = {2018}, month = {JUL}, type = {Article}, abstract = {Chandipura Virus (CHPV), a negative-stranded RNA virus belonging to the Rhabdoviridae family, has been previously reported to bring neuronal apoptosis by activating several factors leading to neurodegeneration. Following virus infection of the central nervous system, microglia, the ontogenetic and functional equivalents of macrophages in somatic tissues gets activated and starts secreting chemokines, thereby recruiting peripheral leukocytes into the brain parenchyma. In the present study, we have systemically examined the effect of CHPV on microglia and the activation of cellular signalling pathways leading to chemokine expression upon CHPV infection. Protein and mRNA expression profiles of chemokine genes revealed that CHPV infection strongly induces the expression of CXC chemokine ligand 10 (CXCL10) and CC chemokine ligand 5 (CCL5) in microglia. CHPV infection triggered the activation of signalling pathways mediated by mitogen-activated protein kinases, including p38, JNK 1 and 2, and nuclear factor kappa B (NF-kappaB). CHPV-induced expression of CXCL10 and CCL5 was achieved by the activation of p38 and NF-kappaB pathways. Considering the important role of inflammation in neurodegeneration, we have targeted NF-kappaB using a newly synthesised natural product nitrosporeusine analogue and showed incapability of microglial supernatant of inducing apoptosis in neurons after treatment.}, issn = {1935-2735}, doi = {10.1371/journal.pntd.0006648}, author = {Verma, Abhishek Kumar and Waghmare, Trushnal S. and Jachak, Gorakhnath R. and Philkhana, Satish Chandra and Reddy, D. Srinivasa and Basu, Anirban} } @article {45361, title = { One pot ligand exchange method for a highly stable Au-SBA-15 catalyst and its room temperature CO oxidation}, journal = {Chemical Communications}, volume = {54}, year = {2018}, month = {NOV}, pages = {12412-12415}, type = {Article}, abstract = {A modified deposition precipitation (DP) method has been developed to address a fundamental issue of supporting well dispersed Au nanoparticles on silica. Ammonium chloride (NH4Cl) plays an important role in in situ modifying the gold precursor (HAuCl(4)3H(2)O) solution allowing facile deposition of gold NPs in the channels of SBA-15. The Au-SBA-15 catalyst (2.8 wt\%) synthesized by this procedure showed 100\% conversion for CO oxidation at room temperature with excellent stability at room temperature and high temperature.}, issn = {1359-7345}, doi = {10.1039/c8cc06887a}, author = {Soni, Yogita and Kavya, I. and Ajithkumar, T. G. and Vinod, C. P.} } @article {44544, title = {Overexpression of tryptophan decarboxylase and strictosidine synthase enhanced terpenoid indole alkaloid pathway activity and antineoplastic vinblastine biosynthesis in Catharanthus roseus}, journal = {Protoplasma}, volume = {255}, year = {2018}, month = {SEP}, pages = {1281-1294}, type = {Article}, abstract = {

Terpenoid indole alkaloid (TIA) biosynthetic pathway of Catharanthus roseus possesses the major attention in current metabolic engineering efforts being the sole source of highly expensive antineoplastic molecules vinblastine and vincristine. The entire TIA pathway is fairly known at biochemical and genetic levels except the pathway steps leading to biosynthesis of catharanthine and tabersonine. To increase the in-planta yield of these antineoplastic metabolites for the pharmaceutical and drug industry, extensive plant tissue culture-based studies were performed to provide alternative production systems. However, the strict spatiotemporal developmental regulation of TIA biosynthesis has restricted the utility of these cultures for large-scale production. Therefore, the present study was performed to enhance the metabolic flux of TIA pathway towards the biosynthesis of vinblastine by overexpressing two upstream TIA pathway genes, tryptophan decarboxylase (CrTDC) and strictosidine synthase (CrSTR), at whole plant levels in C. roseus. Whole plant transgenic of C. roseus was developed using Agrobacterium tumefaciens LBA1119 strain having CrTDC and CrSTR gene cassette. Developed transgenic lines demonstrated up to twofold enhanced total alkaloid production with maximum ninefold increase in vindoline and catharanthine, and fivefold increased vinblastine production. These lines recorded a maximum of 38-fold and 65-fold enhanced transcript levels of CrTDC and CrSTR genes, respectively.

}, doi = {10.1007/s00709-018-1233-1}, author = {Sharma, Abhishek and Verma, Priyanka and Mathur, Archana and Mathur, Ajay} } @article {44242, title = {pH dependent sophorolipid assemblies and their influence on gelation of silk fibroin protein}, journal = {Materials Chemistry and Physics}, volume = {203}, year = {2018}, month = {JAN }, pages = {9-16}, type = {Article}, abstract = {

Sophorolipid (SL), a bio-derived surfactant is an excellent gelling agent for natural fibrous protein, silk fibroin (SF) leading to potential biomedical applications. Interaction of SF with SL has been shown to accelerate the formation of hydrogel with the rate being dependent on the form of SL used. Here, we examine the effect of pH on SL-SF interaction and gel formation by employing rheology, fluorescence spectroscopy, SANS and NMR. The results indicate that the size of SL assemblies decrease as pH increases from acidic to alkaline and significantly impacts the association of SL and SF. The association of SF and SL is mainly via hydrophobic interactions, with the SL molecules forming bead like structures along the SF chain. The increased charge on the acidic form of SL at higher pH results in greater repulsion between acidic SL molecules, which are bound to the hydrophobic sites of SF, leading to rapid chain unfolding and subsequent gelation. (C) 2017 Elsevier B.V. All rights reserved.

}, keywords = {Assemblies, Nuclear magnetic resonance spectroscopy, pH, Silk fibroin, Small angle neutron scattering, Sophorolipid}, issn = {0254-0584}, doi = {10.1016/j.matchemphys.2017.09.045}, author = {Dubey, Parul and Kumar, Sugam and Ravindranathan, Sapna and Vasudevan, Sahana and Aswal, Vinod K. and Rajamohanan, Pattuparambil R. and Nisal, Anuya and Prabhune, Asmita} } @article {44606, title = {Photophysical studies on curcumin-sophorolipid nanostructures: applications in quorum quenching and imaging}, journal = {Royal Society Open Science}, volume = {5}, year = {2018}, month = {FEB}, pages = {170865}, abstract = {

Sophorolipid biosurfactants are biodegradable, less toxic and FDA approved. The purified acidic form of sophorolipid is stimuli-responsive with self-assembling properties and used for solubilizing hydrophobic drugs. This study encapsulated curcumin (CU) with acidic sophorolipid (ASL) micelles and analysed using photophysical studies like UV-visible spectroscopy, photoluminescence (PL) spectroscopy and timecorrelated single photon counting (TCSPC). TEM images have revealed ellipsoid micelles of approximately 100nm size and were confirmed by dynamic light scattering. The bacterial fluorescence uptake studies showed the uptake of formed CUASL nanostructures into both Gram-positive and Gram-negative bacteria. They also showed quorum quenching activity against Pseudomonas aeruginosa. The results have demonstrated this system has potential theranostic applications.

}, keywords = {curcumin, photophysical, Quorum quenching, Sophorolipid}, issn = {2054-5703}, doi = {10.1098/rsos.170865}, author = {Vasudevan, Sahana and Prabhune, Asmita A.} } @article {44552, title = {Porous reduced graphene oxide modified electrodes for the analysis of protein aggregation. Part 2: Application to the analysis of calcitonin containing pharmaceutical formulation}, journal = {Electrochimica Acta}, volume = {266}, year = {2018}, month = {MAR }, pages = {364-372}, abstract = {

In part 1 (A. Vasilescu et al., Porous reduced graphene oxide modified electrodes for the analysis of protein aggregation. Part 1: Lysozyme aggregation at pH 2 and 7.4 Electrochem. Acta, 254 (2017) 375 -383) we proposed porous reduced graphene oxide coated glassy carbon electrode (GC/prGO) in combination with differential pulse voltammetry as a new analytical tool for aggregation studies of proteins. Lysozyme was used as a model to follow its aggregation by electrochemical means at pH 2 and pH 7.4, leading to the formation of amyloid and amorphous aggregates, respectively. Part 2 of this work widens the scope of this approach by investigating a biopharmaceutical product, as the aggregation of peptide based drugs affects their therapeutic activity and can induce allergic reactions in patients. The salmon polypeptide calcitonin (sCT) was chosen as an example of a bioactive peptide with limited pharmaceutical potential due to a tendency to form cytotoxic aggregates and amyloid fibrils. For practical applications, screen printed electrodes (SPE) and flexible electrodes (FE) modified with polydiallyldimethylammonium (PDDA) and prGO by using the layer-by-layer deposition technique have been developed for the detection of sCT. The results indicate that these electrodes can differentiate between formation of amyloid aggregates of calcitonin (2 mg mL(-1)) in citrate buffer to no aggregation in acetate buffer. It was further demonstrated that these electrodes are able to analyze a pharmaceutical drug product of low potency, Miacalcic (8.3 mu g mL(-1)), where no aggregation was observed. (C) 2018 Elsevier Ltd. All rights reserved.

}, keywords = {Calcitonin, Disposable electrodes, Electrochemistry, Porous reduced graphene oxide, Protein aggregation}, issn = {0013-4686}, doi = {10.1016/j.electacta.2018.02.038}, author = {Vasilescu, Alina and Ye, Ran and Boulahneche, Samia and Lamraoui, Sabrina and Jijie, Roxana and Medjram, Mohamed Salah and Gaspar, Szilveszter and Singh, Santosh K. and Kurungot, Sreekumar and Melinte, Sorin and Boukherroub, Rabah and Szunerits, Sabine} } @article {44373, title = {Rationally designed self-standing V2O5 electrode for high voltage non-aqueous all-solid-state symmetric (2.0 V) and asymmetric (2.8 V) supercapacitors}, journal = {Nanoscale}, volume = {10}, year = {2018}, month = {MAY}, pages = {8741-8751}, abstract = {The maximum capacitive potential window of certain pseudocapacitive materials cannot be accessed in aqueous electrolytes owing to the low dissociation potential of 1.2 V possessed by water molecules. However, the inferior pseudocapacitance exhibited by the commonly used electrode materials when integrated with non-aqueous electrolytes still remains a challenge in the development of supercapacitors (SC). Proper selection of materials for the electrode and a rational design process are indeed important to overcome these practical intricacies so that such systems can perform well with non-aqueous electrolytes. We address this challenge by fabricating a prototype all-solid-state device designed with high-capacitive V2O5 as the electrode material along with a Li-ion conducting organic electrolyte. V2O5 is synthesized on a pre-treated carbon-fibre paper by adopting an electrochemical deposition technique that effects an improved contact resistance. A judicious electrode preparation strategy makes it possible to overcome the constraints of the low ionic and electrical conductivities imposed by the electrolyte and electrode material, respectively. The device, assembled in a symmetrical fashion, achieves a high specific capacitance of 406 F g(-1) (at 1 A g(-1)). The profitable aspect of using an organic electrolyte is also demonstrated with an asymmetric configuration by using activated carbon as the positive and V2O5 as the negative electrode materials, respectively. The asymmetric device displays a wide working-voltage window of 2.8 V and delivers a high energy density of 102.68 W h kg(-1) at a power density of 1.49 kW kg(-1). Moreover, the low equivalent series resistance of 9.9 Omega and negligible charge transfer resistance are observed in the impedance spectra, which is a key factor that accounts for such an exemplary performance.}, doi = {10.1039/c8nr00805a}, author = {Ghosh, Meena and Vijayakumar, Vidyanand and Soni, Roby and Kurungot, Sreekumar} } @article {44588, title = {Role of oxygen vacancies and interstitials on structural phase transition, grain growth, and optical properties of Ga doped TiO2}, journal = {Journal of Applied Physics}, volume = {123}, year = {2018}, month = {JUN}, pages = {Article Number: 245702}, abstract = {A systematic study on the effect of gallium (Ga) doping (0 <= x <= 0.10) on the structural phase transition and grain growth of TiO2 is reported here. X-ray diffraction spectroscopy and Raman spectroscopy confirm that Ga doping inhibits the phase transition. Activation energy increases from 125 kJ/mol (x = 0.00) to 300 kJ/mol (x = 0.10) upon Ga incorporation. X-ray photoelectron spectroscopy shows the presence of Ti3+/Ga3+ interstitials, substitution (Ti4+ by Ga3+), and oxygen vacancies in the samples. At lower doping (x <= 0.05), interstitials play a more significant role over substitution and oxygen vacancies, thereby resulting in a considerable lattice expansion. At higher doping (x >= 0.05), the effect of interstitials is compensated by both the effect of substitution and oxygen vacancies, thereby resulting in relatively lesser lattice expansion. Inhibition of the phase transition is the result of this lattice expansion. The crystallite size (anatase) and particle size (rutile) both are reduced due to Ga incorporation. It also modifies optical properties of pure TiO2 by increasing the bandgap (from 3.06 to 3.09 eV) and decreasing the Urbach energy (from 58.59 to 47.25 meV). This happens due to regularization of the lattice by the combined effect of substitution/ interstitials and oxygen vacancies. Published by AIP Publishing.}, doi = {10.1063/1.5027672}, author = {Khatun, Nasima and Tiwari, Saurabh and Vinod, C. P. and Tseng, Chuan-Ming and Liu, Shun Wei and Biring, Sajal and Sen, Somaditya} } @article {44216, title = {Role of the (104) MgCl2 lateral cut in ziegler-natta catalysis: a computational investigation}, journal = {Journal of Physical Chemistry C}, volume = {122}, year = {2018}, month = {JAN}, pages = {285-296}, type = {Article}, abstract = {

Density functional theory (DFT) has been used for the study of ethylene polymerization in the Ziegler-Natta (ZN) olefin polymerization system for eight different alkoxy group containing titanium catalysts (Cat-A-h), Ti(III)Et(OR)(OR{\textquoteright}) (where R =-CH3,-Et,-tert-butyl, cyclohexane, R{\textquoteright} = CH3,-Et,-tert-butyl, cyclohexane). What is of significance is that the catalysts studied were all considered to be tethered to the (104) MgCl2 surface, which has traditionally been considered a {\textquoteleft}{\textquoteleft}dormant{\textquoteright}{\textquoteright} surface in Z-N catalysis systems, in contrast to the {\textquoteleft}{\textquoteleft}more active{\textquoteright}{\textquoteright} (110) MgCl2 surface. Our calculations indicate that the binding of all the catalysts to the (104) surface is favorable, even after taking entropic effects into account. For purposes of comparison, ethylene polymerization has been investigated for the Cat-C (TiEt(OEt)(2)) and the Cat-H (TiEt(CI)(OC4H8Cl)) (OC4H8Cl = the chlorobutoxy group) cases, for both the (i) (110) and the (ii) (104) MgCl2 surfaces. It has been seen that for both (i) and (ii)-the energy gap between insertion and the termination barriers (Delta X) was nearly the same for both the Cat-C and Cat-H eases, which shows that ethylene polymerization on the (104)MgCl2 surface is likely to be a ptoininent occurrence in Z-N catalysis, when alkoxy groups are bound to the titanium center. Additionally, for the Cat-C and the Cat-H cases, the regio-and stereoselective behavior of the propylene monomer on the titanium species present on the (110) and the (104) MgCl2 surfaces has also been investigated, and the results indicate that the (104) MgCl2 surface is only slightly less effective than the (110. However, the calculations also indicate that for Cat-H the (104) MgCl2 surface significantly improves the molecular weight of polypropylene in comparison to the (110) surface, further showcasing how the (104) surface (ignored until date) might be a major player in ZN catalysis. Given that a major portion of the MgCl2 support is made up of (104) lateral cuts, the current findings are of considerable relevance.

}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.7b07893}, author = {Kumawat, Jugal and Gupta, Virendra Kumar and Vanka, Kumar} } @article {44217, title = {Ru(II)-functionalized SBA-15 as highly chemoselective, acid free and sustainable heterogeneous catalyst for acetalization of aldehydes and ketones}, journal = {Catalysis Communications}, volume = {104}, year = {2018}, month = {JAN}, pages = {62-66}, type = {Article}, abstract = {

Combining electron deficient Ru(II) coordination sites with organofunctionalized SBA-15, (L)Ru(Il)@SBA-15, result in a mild, neutral, water scavenger free and chemo-selective acetalization catalyst for cyclic/acyclic acetals. Vacant coordination sites of ruthenium in (L)Ru(II)@SBA-15 activates protecting groups as well as reactants simultaneously and restricts the reverse acetalization reaction. Synthesized (L)Ru(Il)@SBA-15 catalyst has been thoroughly characterized and act as competitive catalyst compared to conventional acid catalysts. (L) RuaD@SBA-15 performs high catalytic activity as well as selectivity within 20 min with high TOF. The catalyst can be recycled and reaction parameters are optimized.

}, keywords = {Acetalization reactions, Acid free, chemo-selective, heterogeneous catalyst, Reusable, Ru(II) immobilized SBA-15}, issn = {1566-7367}, doi = {10.1016/j.catcom.2017.10.016}, author = {Lazar, Anish and Betsy, K. J. and Vinod, C. P. and Singh, A. P.} } @article {45438, title = {Ruthenium-catalyzed regioselective alkenylation/tandem hydroamidative cyclization of unmasked quinazolinones using terminal alkynes}, journal = {Journal of Organic Chemistry}, volume = {83}, year = {2018}, month = {AUG}, pages = {8906-8913}, type = {Article}, abstract = {

Ruthenium-catalyzed amide directed C-sp2-H activation of the quinazolinone scaffold has been demonstrated, leading to the selective mono- or dialkenylation in moderate to good yields to achieve medicinally important stilbene containing quinazolinones. The terminal allcyne is utilized as a coupling partner, which resulted in the selective trans-alkene formation. Electron-deficient phenylacetylenes facilitate alkenylation followed by tandem hydroamidation of the newly generated trans double bond to provide novel quinazolinone alkaloids related to the Luotonine class of natural products.

}, doi = {10.1021/acs.joc.8b01143}, author = {Viveki, Amol B. and Mhaske, Santosh B.} } @article {44639, title = {Selective oxidation of cyclohexane to cyclohexanone using chromium oxide supported mesoporous MCM-41 nanospheres: probing the nature of catalytically active chromium sites}, journal = {ChemCatChem}, volume = {10}, year = {2018}, month = {AUG}, pages = {3291-3298}, abstract = {

Highly dispersed chromium oxide supported mesoporous MCM-41 nanosphere catalysts have been synthesized using a simple wet impregnation method. This work is devoted to a systematic study to reveal the active Cr sites in chromium oxide supported MCM-41 nanosphere catalysts for the selective oxidation of cyclohexane to cyclohexanone. To probe the nature of the active species, we synthesized 0.5-10wt\% Cr loaded catalysts and characterized them by using XRD, UV/Vis spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near edge structure analysis, N-2 sorption analysis, FTIR spectroscopy, (SiNMR)-Si-29 spectroscopy, SEM, and TEM. The liquid-phase oxidation of cyclohexane to cyclohexanone (99\% selectivity) was performed under mild reaction conditions, and the results reveal clearly that the 5wt\% Cr loaded catalyst was optimum for the reaction. The initial composition of isolated Cr3+ species in the catalyst is the major factor that influences the enhanced activity for cyclohexane oxidation.

}, keywords = {chromium, heterogeneous catalysis, Nanostructures, Oxidation, supported catalysts}, issn = {1867-3880}, doi = {10.1002/cctc.201800309}, author = {Betsy, Kurisingal J. and Nayak, Chandrani and Lazar, Anish and Krishnan, Athira and Bhattacharyya, Dibyendu and Jha, Shambhu N. and Vinod, Chathakudath P.} } @article {44362, title = {Sensitive electrochemical detection of cardiac troponin I in serum and saliva by nitrogen-doped porous reduced graphene oxide electrode}, journal = {Sensors and Actuators B-Chemical}, volume = {262}, year = {2018}, month = {JUN}, pages = {180-187}, type = {Article}, abstract = {Cardiovascular diseases pose one of the highest mortality risks among all diseases in developed countries, steadily increasing the burden on the health systems. Early diagnosis of cardiovascular diseases has consequently become highly important to decrease mortality and to use more adapted therapeutic decisions. We demonstrate here the utility of nitrogen-doped reduced graphene oxide (N-prGO) for detecting and quantifying of cardiac troponin I (cTnI), a key human cardiac protein biomarker, under physiologically relevant conditions. Non-covalent modification of N-prGO by 1-pyrenecarboxylic acid (py-COOH) and poly(ethylene glycol) modified pyrene (py-PEG) ligands allowed the covalent integration of Tro4 aptamer, known for its high selectivity towards cTnI. Using differential pulse voltammetry (DPV), a label-free electrochemical sensor for cTnI for concentrations down to 1 pgmL(-1) in human serum could be obtained. This sensitive detection arises from the integration of a porous nanomaterial with excellent electrochemical properties being easily amendable to site-specific surface modification. (C) 2018 Elsevier B.V. All rights reserved.}, doi = {10.1016/j.snb.2018.01.215}, author = {Chekin, Fereshteh and Vasilescu, Alina and Jijie, Roxana and Singh, Santosh K. and Kurungot, Sreekumar and Iancu, Madalina and Badea, Gabriela and Boukherroub, Rabah and Szunerits, Sabine} } @article {44380, title = {Silk fibroin micro-particle scaffolds with superior compression modulus and slow bioresorption for effective bone regeneration}, journal = {Scientific Reports}, volume = {8}, year = {2018}, month = {MAY}, pages = {Article Number: 7235}, abstract = {Silk fibroin (SF), a natural polymer produced by Bombyx mori silkworms, has been extensively explored to prepare porous scaffolds for tissue engineering applications. Here, we demonstrate, a scaffold made of SF, which exhibits compression modulus comparable to natural cancellous bone while retaining the appropriate porosities and interconnected pore architecture. The scaffolds also exhibit high resistance to in-vitro proteolytic degradation due to the dominant beta sheet conformation of the SF protein. Additionally, the scaffolds are prepared using a simple method of microparticle aggregation. We also demonstrate, for the first time, a method to prepare SF micro-particles using a Hexafluoroisopropanol-Methanol solvent-coagulant combination. SF microparticles obtained using this method are monodisperse, spherical, non-porous and extremely crystalline. These micro-particles have been further aggregated together to form a 3D scaffold. The aggregation is achieved by random packing of these microparticles and fusing them together using a dilute SF solution. Preliminary in-vitro cell culture and in-vivo implantation studies demonstrate that the scaffolds are biocompatible and they exhibit the appropriate early markers, making them promising candidates for bone regeneration.}, doi = {10.1038/s41598-018-25643-x}, author = {Nisal, Anuya and Sayyad, Raeesa and Dhavale, Prachi and Khude, Bhakti and Deshpande, Rucha and Mapare, Vidhyashri and Shukla, Swati and Venugopalan, Premnath} } @article {45402, title = {Spatial-temporal spectroscopy characterizations and electronic structure of methylammonium perovskites}, journal = {MRS Communications}, volume = {8}, year = {2018}, month = {SEP}, pages = {961-969}, type = {Article}, abstract = {

Using time-resolved laser-scanning confocal microscopy and ultrafast optical pump/THz probe spectroscopy, we measure photoluminescence (PL) and THz-conductivity in perovskite micro-crystals and films. PL quenching and lifetime variations occur from local heterogeneity. Ultrafast THz-spectra measure sharp quantum transitions from excitonic Rydberg states, providing weakly bound excitons with a binding energy of similar to 13.5 meV at low temperatures. Ab-initio electronic structure calculations give a direct band gap of 1.64 eV, a dielectric constant of similar to 18, heavy electrons, and light holes, resulting in weakly bound excitons, consistent with the binding energies from the experiment. The complementary spectroscopy and simulations reveal fundamental insights into perovskite light-matter interactions.

}, doi = {10.1557/mrc.2018.114}, author = {Liu, Zhaoyu and Bhamu, K. C. and Luo, Liang and Shah, Satvik and Park, Joong-Mok and Cheng, Di and Long, Men and Biswas, Rana and Fungara, F. and Shiner, Ruth and Shiner, Joseph and Vela, Javier and Wang, Jigang} } @article {44186, title = {Streptomyces sp metabolite(s) promotes Bax mediated intrinsic apoptosis and autophagy involving inhibition of mTOR pathway in cervical cancer cell lines}, journal = {Scientific Reports}, volume = {8}, year = {2018}, month = {FEB}, pages = {2810}, type = {Article}, abstract = {

In cervical cancer, the association between HPV infection and dysregulation of phosphoinositide 3-kinase (PI3K)/protein kinase B (AKT)/mammalian target of rapamycin (mTOR) pathway (PI3K/AKT/mTOR pathway) places mTOR as an attractive therapeutic target. The failure of current treatment modalities in advanced stages of this cancer and drawbacks of already available mTOR inhibitors demand for novel drug candidates. In the present study we identified the presence of a mTOR inhibitor in an active fraction of the ethyl acetate extract of Streptomyces sp OA293. The metabolites(s) in the active fraction completely inhibited mTORC1 and thereby suppressed activation of both of its downstream targets, 4E-BP1 and P70S6k, in cervical cancer cells. In addition, it also stalled Akt activation via inhibition of mTORC2. The mechanism of mTOR inhibition detailed in our study overcomes significant drawbacks of well known mTOR inhibitors such as rapamycin and rapalogs. The active fraction induced autophagy and Bax mediated apoptosis suggesting that mTOR inhibition resulted in programmed cell death of cancer cells. The molecular weight determination of the components in active fraction confirmed the absence of any previously known natural mTOR inhibitor. This is the first report of complete mTOR complex inhibition by a product derived from microbial source.

}, issn = {2045-2322}, doi = {10.1038/s41598-018-21249-5}, author = {Dan, Vipin Mohan and Muralikrishnan, Balaji and Sanawar, Rahul and Vinodh, J. S. and Burkul, Bhushan Bapusaheb and Srinivas, Kalanghad Puthankalam and Lekshmi, Asha and Pradeep, N. S. and Dastager, Syed G. and Santhakumari, B. and Santhoshkumar, Thankayyan R. and Kumar, R. Ajay and Pillai, Madhavan Radhakrishna} } @article {44551, title = {Structure and function of a highly active Bile Salt Hydrolase (BSH) from Enterococcus faecalis and post-translational processing of BSH enzymes}, journal = {Biochim Biophys Acta.}, volume = {1866}, year = {2018}, month = {JAN}, pages = {507-518}, type = {Journal Article}, abstract = {Bile Salt Hydrolase (BSH), a member of Cholylglycine hydrolase family, catalyzes the de-conjugation of bile acids and is evolutionarily related to penicillin V acylase (PVA) that hydrolyses a different substrate such as penicillin V. We report the three-dimensional structure of a BSH enzyme from the Gram-positive bacteria Enterococcus faecalis (EfBSH) which has manifold higher hydrolase activity compared to other known BSHs and displays unique allosteric catalytic property. The structural analysis revealed reduced secondary structure content compared to other known BSH structures, particularly devoid of an anti-parallel β-sheet in the assembly loop and part of a β-strand is converted to increase the length of a substrate binding loop 2. The analysis of the substrate binding pocket showed reduced volume owing to altered loop conformations and increased hydrophobicity contributed by a higher ratio of hydrophobic to hydrophilic groups present. The aromatic residues F18, Y20 and F65 participate in substrate binding. Thus, their mutation affects enzyme activity. Docking and Molecular Dynamics simulation studies showed effective polar complementarity present for the three hydroxyl (-OH) groups of GCA substrate in the binding site contributing to higher substrate specificity and efficient catalysis. These are unique features characteristics of this BSH enzyme and thought to contribute to its higher activity and specificity towards bile salts as well as allosteric effects. Further, mechanism of autocatalytic processing of Cholylglycine Hydrolases by the excision of an N-terminal Pre-peptide was examined by inserting different N-terminal pre-peptides in EfBSH sequence. The results suggest that two serine residues next to nucleophile cysteine are essential for autocalytic processing to remove precursor peptide. Since pre-peptide is absent in EfBSH the mutation of these serines is tolerated. This suggests that an evolution-mediated subordination of the pre-peptide excision site resulted in loss of pre-peptide in EfBSH and other related Cholylglycine hydrolases.}, keywords = {autocatalytic processing, Bile salt hydrolase, molecular dynamics, Mutagenesis, Polar complementarity, X-ray crystallography}, issn = {15709639}, doi = {0.1016/j.bbapap.2018.01.003.}, author = {Chand, D.}, editor = {Panigrahi, P.} } @article {44542, title = {Substituent-induced deformed ni{\textendash}porphyrin as an electrocatalyst for the electrochemical conversion of water into dioxygen}, journal = {European Journal of Inorganic Chemistry}, volume = {14}, year = {2018}, month = {APR}, pages = {1549-1555}, type = {Article}, abstract = {

The electrochemical water oxidation ability of complexes 5,15-diphenylporphinatonickel(II) (A) and 5,15-bis(3,5-di-tert-butylphenyl)porphinatonickel(II) (B) in the oxygen evolution reaction (OER) have been investigated in an alkaline medium. Complex B was found to be kinetically and thermodynamically more active than complex A. The overpotential and Tafel slope of complex B are lower than those of complex A by 30 mV and around 45 mV/decade, respectively, which supports the higher activity of B. Moreover, stability tests endorse the sustainability of both samples under alkaline conditions. It has been found that the 3,5-di-tert-butylphenyl substituent in B plays a decisive role in achieving a better OER onset potential and current than that obtained with A, which is a result of the modulation of the structural parameters of B. Furthermore, the measured OER activities of A and B have been correlated with their molecular arrangement as well as differences in their bonding characteristics and dipole moments. For further insight, the obtained results have been confirmed by a theoretical study.

}, issn = {14341948}, doi = {10.1002/ejic.201701427}, author = {Krishna, J. V. S. and Krishna, Narra Vamsi and Singh, Santosh K. and Shaw, Pankaj K. and Dhavale, Vishal M. and Vardhaman, Anil Kumar and Giribabu, Lingamallu} } @article {44533, title = {Supramolecular complexes of poly(3-Hexylthiophene)-block (and random)-poly[3-(2-(6-carboxyhexyl)methyl)thiophene] copolymers with perylene bisimide}, journal = {Journal of Polymer Science Part A: Polymer Chemistry}, volume = {56}, year = {2018}, month = {MAY}, pages = {1574-1583}, type = {Journal Article}, abstract = {Block and random copolymers of poly(3-hexylthiophene) and poly[3-(2-(6-carboxyhexyl)methyl)thiophene] with side-chain carboxylic functionality ((P3HT-b-P3COOH) and (P3HT-r-P3COOH) were developed by Grignard Metathesis (GRIM) polymerization. The carboxylic functionality was introduced in the side chain via the oxazoline route. Both the block and random polythiophene copolymers were complexed with pyridine functionalized perylene bisimide to obtain supramolecular block and random polymer complexes. The complex formation in both systems was confirmed by 1H NMR, WXRD and SAXS studies. An expansion of d spacing upon complex formation was observed in both the block and random copolymer, which could be traced by WXRD. Hole and electron mobilities measured for the supramolecular complexes indicated values which were higher by an order of magnitude for the supramolecular block complex (μh ≈ 2.9 {\texttimes} 10-4 cm2/Vs; μe ≈ 3.1 {\texttimes} 10-6 cm2/Vs) as compared to the random (μh ≈ 1.4 {\texttimes} 10-5 cm2/Vs; μe ≈ 4.7 {\texttimes} 10-7 cm2/Vs) copolymer. These results are indicative of the higher degree of disorder prevailing in the films of random copolymer system compared to the block copolymer.}, keywords = {block and random polythiophene, perylene bisi-mide, Self-assembly}, issn = {0887624X}, doi = {10.1002/pola.29042}, author = {Shinde, Shekhar}, editor = {Vijayan, Raaghesh} } @article {44529, title = {Surface colonized silver nano particles over chitosan poly-electrolyte micro-spheres and their multi-functional behavior}, journal = {Materials Research Express}, volume = {5}, year = {2018}, month = {FEB }, pages = { 025032}, type = {Journal Article}, abstract = {hitosan/tripolyphosphate polyelectrolyte (TPP) microspheres, decorated and surface functionalized with silver nanoparticles (NPs) of average diameter of 15 nm, were synthesized following a simple two-step procedure. These Ag NP-functionalized polyelectrolyte microspheres (Ag-CSPMs) are found to be biocompatible and enhancing the reactive oxygen species in curcumin with excellent anti-bacterial activity for selected Gram-positive and negative bacterial strains, making them much attractive relative to bare surface counterparts; the well-stabilized silver NPs do not form any agglomerations on the surface of the chitosan microspheres. They also show excellent cytotoxic behavior towards MCF7 cell lines, showing a half-maximal inhibitory concentration (IC50) of 32 μg ml-1. Therefore, Ag-CSPMs exhibit multi-functional ability having potential towards theranostics applications.}, keywords = {antibacterial properties, Chitosan, Cytotoxicity, reactive oxygen species, silver nanoparticles, theranostics}, issn = {20531591}, doi = { 10.1088/2053-1591/aaa3c6}, author = {Prakash, B.}, editor = {Asha, S.} } @article {45549, title = {Synthesis and anticancer studies of michael adducts and heck arylation products of sesquiterpene lactones, zaluzanin D and zaluzanin C from vernonia arborea}, journal = {RSC Advances}, volume = {8}, year = {2018}, month = {NOV}, pages = {38289-38304}, type = {Article}, abstract = {Sesquiterpene lactones containing α-methylene-γ-lactones, zaluzanin D 1 and zaluzanin C 2 were isolated from the leaves of Vernonia arborea. Several diverse Michael adducts (3{\textendash}22) and Heck arylation analogs (23{\textendash}34) of 1 have been synthesized by reacting with various amines and aryl iodides, respectively and were assayed for their in vitro anticancer activities against human breast cancer cell lines MCF7 and MDA-MB-231. Among all the synthesized analogs, Michael adducts 9 and 10 showed better anticancer activities as compared to 1. However, among these compounds, only 10 has minimal cytotoxic effect on normal breast epithelial MCF10A cells. Our detailed mechanistic studies reveal that compounds 9 and 10 execute their antiproliferative activity through induction of apoptosis and thereby inhibit the cancer cells proliferation and compound 10 could be a lead compound for designing potential anti-cancer compound.}, doi = {10.1039/c8ra06238b}, author = {Valkute, T.R. and Aratikatla, E.K. and Gupta, N.A. and Ganga, S. and Santra, M.K. and Bhattacharya, A.K.} } @article {44498, title = {Synthesis, biological evaluation, and molecular docking study of pyridine clubbed 1,3,4-oxadiazoles as potential antituberculars}, journal = {Synthetic Communications}, volume = {48}, year = {2018}, month = {JAN}, pages = {524-540}, type = {Journal Article}, abstract = {

A series of pyridine clubbed 1,3,4-oxadiazole derivatives were efficiently synthesized, characterized by standard spectral techniques and evaluated for their in vitro antitubercular activity against Mycobacterium tuberculosis (MTB) H37Ra and Mycobacterium bovis BCG in active and dormant state using an established methods. Compounds 5a, 5m, and 5t were identified as the most active compounds against MTB. Molecular docking was performed against MTB enoyl-ACP (CoA) reductase (FabI/ENR/InhA) enzyme to predict the binding modes and affinity. The theoretical predictions from molecular docking could establish a link between the observed biological activity and the binding affinity shedding light into specific bonded and non-bonded interactions influencing the activity. The active compounds were studied for cytotoxicity against three cell lines and were found to be non-cytotoxic. Specificity of these compounds was checked by screening them for their antibacterial activity against four bacterial strains.

}, keywords = {antibacterial activity, antituberculosis activity, cytotoxicity activity}, issn = {397911}, doi = {10.1080/00397911.2017.1410892}, author = {Desai, N. C.}, editor = {Trivedi, Amit} } @article {44468, title = {Transition metal free regio-selective C{\textendash}H hydroxylation of chromanones towards the synthesis of hydroxyl-chromanones using PhI(OAc)2 as the oxidant}, journal = {Chemical Communications}, volume = {54}, year = {2018}, month = {FEB}, pages = {2252-2255}, type = {Journal Article}, abstract = {

The chromanone scaffold is considered as a privileged structure in drug discovery. Herein, we report a highly efficient PhI(OAc)2 mediated regioselective, direct C{\textendash}H hydroxylation of chromanones. This method offers easy access to substituted 6-hydroxy chromanones in moderate to good isolated yields, thus paving the way for their pharmaceutical studies.

}, issn = {13597345}, doi = {10.1039/C7CC08588E}, author = {Viswanadh, N.}, editor = {Ghotekar, Ganesh S.} } @article {45437, title = {Tuning the basicity of Cu-based mixed oxide catalysts towards the efficient conversion of glycerol to glycerol carbonate}, journal = {Molecular catalysis}, volume = {460}, year = {2018}, month = {DEC}, pages = {53-62}, type = {Article}, abstract = {A series of efficient and robust Cu based mixed oxides were synthesized by a simple co-precipitation method and utilized for the production of glycerol carbonate (GC) via transesterification of glycerol with dimethyl carbonate (DMC). The synthesized materials were characterized using XRD, UV-vis spectroscopy, SEM, TEM, N-2 sorption, CO2-TPD, and XPS. The addition of Cu on Mg/Al mixed oxides exhibits significant changes in its physicochemical properties and catalytic activity. The obtained mixed oxides showed remarkably high transesterification activity towards the efficient conversion of glycerol to GC under economical reaction conditions without using any solvent. Among all the catalysts employed, highest catalytic activity was observed over MAC-0.6 catalyst with glycerol conversion of 96.4\% and GC yield of 91.2\%. The improved catalytic performance was observed mainly due to the optimized catalyst molar ratio and strong surface basicity. The strong surface basic sites were greatly attributed to the incorporation of Cu2+ cations in the MgAl (O) periclase that efficiently catalyzed the transesterification of glycerol with DMC. Furthermore, the reported catalyst was robust and could be recycled for more than five times without any significant loss in its catalytic activity.}, issn = {2468-8231}, doi = {10.1016/j.mcat.2018.09.002}, author = {Manikandan, Marimuthu and Prabu, Marimuthu and Kumar, S. K. Ashok and Sangeetha, Palanivelu and Vijayaraghavan, Rajagopalan} } @article {45374, title = { Twelve-armed hexaphenylbenzene-based giant supramolecular framework for entrapping guest molecules}, journal = {ChemPlusChem}, volume = {83}, year = {2018}, month = {NOV}, pages = {1032-1037}, type = {Article}, abstract = {

Host-guest chemistry is a functional model in supramolecular chemistry for understanding specific process occurring in biological systems. Herein, we describe a rationally designed giant multiarmed hexaphenylbenzene (HPB)-based supramolecular frameworks which encapsulate a variety of guest molecules in the voids of their crystal lattice through the cooperative interplay of multivalency, noncovalent forces and backbone rigidity. In this connection, pseudo-axially substituted twelve-armed hexaphenylbenzene was synthesized and its molecular entrapping nature was studied by varying number of H-bond donor-acceptor sites in the arms. The per-methyl esterified HPB acted as a cavitand to include nonpolar and polar aprotic guests in its crystal structure via C-H center dot center dot center dot pi, C-H center dot center dot center dot O and C-H center dot center dot center dot N interactions. The corresponding amidated HPB showed unprecedented inclusion of ammonia and segregation of the guest molecules according to their polarity in the lattice. Furthermore, this molecular entrapping system has been used to obtain the crystal structure of a hitherto unproven 2-azaallenium intermediate, which had been proposed to be involved in aminomethylation of activated arenes.

}, issn = { 2192-6506}, doi = {10.1002/cplu.201800478}, author = {Madhu, Suresh and Gonnade, Rajesh G. and Das, Tamal and Vanka, Kumar and Sanjayan, Gangadhar J.} } @article {45429, title = {Understanding conformational dynamics of complex lipid mixtures relevant to biology}, journal = {Journal of membrane biology}, volume = {251}, year = {2018}, month = {DEC}, pages = {609-631}, type = {Article}, abstract = {This is a perspective article entitled "Frontiers in computational biophysics: understanding conformational dynamics of complex lipid mixtures relevant to biology" which is following a CECAM meeting with the same name.}, issn = {0022-2631 }, doi = {10.1007/s00232-018-0050-y}, author = {Friedman, Ran and Khalid, Syma and Aponte-Santamaria, Camilo and Arutyunova, Elena and Becker, Marlon and Boyd, Kevin J. and Christensen, Mikkel and Coimbra, Joao T. S. and Concilio, Simona and Daday, Csaba and van Eerden, Floris J. and Fernandes, Pedro A. and Graeter, Frauke and Hakobyan, Davit and Heuer, Andreas and Karathanou, Konstantina and Keller, Fabian and Lemieux, M. Joanne and Marrink, Siewert J. and May, Eric R. and Mazumdar, Antara and Naftalin, Richard and Pickholz, Monica and Piotto, Stefano and Pohl, Peter and Quinn, Peter and Ramos, Maria J. and Schiott, Birgit and Sengupta, Durba and Sessa, Lucia and Vanni, Stefano and Zeppelin, Talia and Zoni, Valeria and Bondar, Ana-Nicoleta and Domene, Carmen} } @article {44352, title = {Understanding interactions between lignin and ionic liquids with experimental and theoretical studies during catalytic depolymerisation}, journal = {Catalysis Today}, volume = {309}, year = {2018}, month = {JUL}, pages = {98-108}, type = {Article}, abstract = {Compared to H2SO4, Bronsted acidic ionic liquid (BAIL, [C3SO3HMIM][HSO4]) catalyzed depolymerization of lignin yielded higher concentration of low molecular weight products under mild conditions (120 degrees C) as proven by GC and GC-MS. To comprehend this disparity in catalytic activity among H2SO4 and BAIL (at similar H+ concentration), experimental techniques [1D(H-1) NMR, 2D(N-15/H-1 HMBC) NMR and RAMAN] have been employed. Based on these studies, it has been proven that the transfer of electron density from substrate to the electron deficient imidazolium ring via formation of hydrogen bond between -OH/OCH3 (substrate) and -N1C2H2N3-(cation) is possible, while the anion plays an important role. Further, density functional theory (DFT) calculations also corroborated this fact by showing a change in the bond angle and decrease in bond length (C-2-H-2 in imidazole), due to the presence of weak and strong hydrogen bonding between the substrate and IL.}, doi = {10.1016/j.cattod.2017.09.050}, author = {Singh, Sandip Kumar and Banerjee, Subhrashis and Vanka, Kumar and Dhepe, Paresh Laxmikant} } @article {45449, title = {Water-in-acid gel polymer electrolyte realized through a phosphoric acid-enriched polyelectrolyte matrix toward solid-state supercapacitors}, journal = {ACS Sustainable Chemistry \& Engineering}, volume = {6}, year = {2018}, month = {OCT}, pages = {12630-12640}, type = {Article}, abstract = {A new concept of water-in-acid gel polymer electrolytes (GPEs) is introduced. The simple and scalable UV-light-assisted synthesis of a copolymer matrix possessing polyelectrolyte behavior, followed by swelling in minimally diluted H3PO4 (15.1 M/88 wt \% aqueous solution), effects formation of a high proton-conducting, self-standing, and mechanically stable polyelectrolyte GPE (PGPE). Retention of high mechanical stability despite the presence of a large amount of liquid species makes it a promising candidate for replacing conventional GPEs. The high proton conductivity (9.8 X 10(-2) S cm(-1)) of the PGPE at an ambient temperature of 303 K is attributed to the high concentration of the conducting species present in the polymer matrix. The PGPE-based polyaniline (PANI) supercapacitor device (PANI-1) with a mass loading of 1 mg cm(-2) exhibits a high specific gravimetric capacitance of 385 F g(-1) at a current density of 0.25 mA cm(-2). At the same current density, the PANI-5 device retains high gravimetric and areal capacitance values of 258 F g(-1) and 1288 mF cm(-2), respectively. The low equivalent series resistance value of 0.78 Omega (for the PANI-5 device) further proves the excellent electrode-electrolyte interface formed by the water-in-acid GPE. A 100\% capacitance retention even after 9000 continuous charge-discharge cycles strongly indicates the feasibility of adopting water-in-acid GPEs in future supercapacitors.}, issn = {2168-0485}, doi = {10.1021/acssuschemeng.8b01175}, author = {Vijayakumar, Vidyanand and Ghosh, Meena and Torris, Arun A. T. and Chandran, Nikhil M. K. and Nair, Sanoop B. and Badiger, Manohar V. and Kurungot, Sreekumar} } @article {44558, title = {What drives the H-abstraction reaction in bio-mimetic oxoiron-bTAML complexes? A computational investigation}, journal = {Physical Chemistry and Chemical Physics}, volume = {20}, year = {2018}, month = {APR }, pages = {13845-13850 }, type = {Journal Article}, abstract = {Monomeric iron-oxo units have been confirmed as intermediates involved in the C{\textendash}H bond activation in various metallo-enzymes. Biomimetic oxoiron complexes of the biuret modified tetra-amido macrocyclic ligand (bTAML) have been demonstrated to oxidize a wide variety of unactivated C{\textendash}H bonds. In the current work, density functional theory (DFT) has been employed to investigate the hydrogen abstraction (HAT) reactivity differences across a series of bTAML complexes. The cause for the differences in the HAT energy barriers has been found to be the relative changes in the energy of the frontier molecular orbitals (FMOs) induced by electronic perturbation.}, issn = {14639076}, doi = {10.1039/C8CP01333K}, author = {Mukherjee, Anagh}, editor = {Pattanayak, Santanu} } @article {46326, title = {Ag nanoparticles supported on a resorcinol-phenylenediamine-based covalent organic framework for chemical fixation of CO2}, journal = {Chemistry-An Asian Journal }, year = {2019}, month = {OCT}, type = {Article; Early Access}, abstract = {

Covalent organic frameworks are a new class of crystalline organic polymers possessing a high surface area and ordered pores. Judicious selection of building blocks leads to strategic heteroatom inclusion into the COF structure. Owing to their high surface area, exceptional stability and molecular tunability, COFs are adopted for various potential applications. The heteroatoms lining in the pores of COF favor synergistic host-guest interaction to enhance a targeted property. In this report, we have synthesized a resorcinol-phenylenediamine-based COF which selectively adsorbs CO2 into its micropores (12 angstrom). The heat of adsorption value (32 kJ mol(-1)) obtained from the virial model at zero-loading of CO2 indicates its favorable interaction with the framework. Furthermore, we have anchored small-sized Ag nanoparticles (approximate to 4-5 nm) on the COF and used the composite for chemical fixation of CO2 to alkylidene cyclic carbonates by reacting with propargyl alcohols under ambient conditions. Ag@COF catalyzes the reaction selectively with an excellent yield of 90 \%. Recyclability of the catalyst has been demonstrated up to five consecutive cycles. The post-catalysis characterizations reveal the integrity of the catalyst even after five reaction cycles. This study emphasizes the ability of COF for simultaneous adsorption and chemical fixation of CO2 into corresponding cyclic carbonates.

}, keywords = {CO2 capture, covalent organic frameworks, cyclic carbonates, Propargyl alcohols, silver nanoparticles}, issn = {1861-4728}, doi = {10.1002/asia.201901157}, author = {Chakraborty, Debanjan and Shekhar, Pragalbh and Singh, Himan Dev and Kushwaha, Rinku and Vinod, C. P. and Vaidhyanathan, Ramanathan} } @article {46205, title = {All-organic composites of ferro- and piezoelectric phosphonium salts for mechanical energy harvesting application}, journal = {Chemistry of Materials}, volume = {31}, year = {2019}, month = {AUG}, pages = { 5964-5972}, type = {A}, abstract = {

Molecular ferroelectrics owing to their lightweight, flexibility, and phase stability are drawing attention in the fields of flexible electronics, optical devices, and energy materials. In this paper, we report a series of binary organoamino phosphonium salts containing triphenyl isopropylaminophosphonium (TPAP), diphenyl diisopropylaminophosphonium (DPDP), phenyl triisopropylaminophosphonium (PTAP), and tetraisopropylaminophosphonium (TIAP) cations supported by lower symmetric tetrahedral BF4-, ClO4-, and IO4- anions. The P-E hysteresis loop measurements on these polar organic salts gave high remnant polarization (P-r) values of 35.36, 21.83, and 21.12 mu C cm(-2) for the DPDP center dot BF4, DPDP center dot ClO4, and DPDP center dot IO4 salts, respectively, having 1D hydrogen-bonded chain structures built from strong N-H center dot center dot center dot X (X = F or 0) interactions. For the first time, highly flexible composite devices have been prepared for the piezoelectric salts TPAP center dot BF4, DPDP center dot BF4, and TIAR center dot BF4 using thermoplastic polyurethane (TPU) as the matrix. The observed maximum peak-to-peak output voltages (V-pp) for the 10 wt \% composite devices of TPAP center dot BF4/TPU, DPDP center dot BF4/TPU, and TIAP center dot BF4/TPU are found to be 7.37, 8.95, and 4.75 V, respectively. These composite devices exhibit excellent durability, cycling stability, and viscoelastic properties. They also show the capacitor charging capabilities reaching their maximum charging points within 60 s.

}, doi = {10.1021/acs.chemmater.9b02409}, author = {Vijayakanth, Thangavel and Ram, Farsa and Praveenkumar, Balu and Shanmuganathan, Kadhiravan and Boomishankar, Ramamoorthy} } @article {47176, title = {Aqueous-phase differentiation and speciation of Fe3+ and Fe2+ using water-stable photoluminescent lanthanide-based metal-organic framework}, journal = {ACS Applied Nano Materials}, volume = {2}, year = {2019}, month = {AUG}, pages = {5169-5178}, type = {Article}, abstract = {

Fe2+ is vital to O-2 transportation and photosynthesis regulated by oxidases and reductases. On the other hand, Fe3+ is detrimental due to its irreversible binding to O-2. Hence there is a need for selective identification of Fe3+ from aqueous systems in the presence of Fe2+. However, given their close chemical nature, it is not straightforward to differentiate them. Fe2+ and Fe3+ are typically sensed and differentiated using magnetic measurements, Mossbauer, X-ray absorption spectroscopy, or EXAFS, which are complex and equipment intensive techniques. In comparison, the fluorescence technique is advantageous in terms of time and accessibility. Although readily available lanthanide salts exhibit fluorescence, they are weak, and to serve as an optical probe, their luminescence has to be enhanced via ligand design. Hence we have designed a chromophoric ligand that can covalently bind to lanthanides and enhance its fluorescence intensity, and it binds selectively to Fe3+ through its nitrogen centers. It detects Fe3+ from low concentration (similar to 100 mu M) aqueous solutions, with fast response time (\<1 min) and with a detection limit of 3.6 ppm. Importantly, the Fe3+ adsorbed MOF can be readily reactivated for the next cycle by merely washing with an aqueous ascorbic acid solution and can be used for multiple cycles without any appreciable loss in activity. This makes the Ln-MOF an environmentally benign, cost-effective, scalable, and recyclable probe.

}, keywords = {Fe3+ differentiation and speciation, flexible ligand, fluorescent MOF, iron speciation, Metal-organic framework, water sorption}, issn = {2574-0970}, doi = {10.1021/acsanm.9b01047}, author = {Maity, Rahul and Chakraborty, Debanjan and Nandi, Shyamapada and Yadav, Ankit Kumar and Mullangi, Dinesh and Vinod, C. P. and Vaidhyanathan, Ramanathan} } @article {46072, title = {Aromatic polyesters containing pendant azido groups: synthesis, characterization, chemical modification and thermal cross-linking}, journal = {European Polymer Journal}, volume = {116}, year = {2019}, month = {JUL}, pages = {180-189}, type = {Article}, abstract = {

A partially bio-based bisphenol containing pendant azido group viz., 4,4{\textquoteright}-(5-azidopentane-2,2-diyl) diphenol (AZBPA) was synthesized starting from 4,4{\textquoteright}-bis (4-hydroxyphenyl) pentanoic acid. AZBPA was reacted with isophthaloyl chloride (IPC), terephthaloyl chloride (TPC) and a mixture of IPC/TPC (50:50 mol\%) by phase transfer-catalyzed interfacial polycondensation route to obtain aromatic polyesters containing pendant azido groups. Copolyesters containing pendant azido groups were also synthesized by polycondensation of different molar proportions of AZBPA and commercially available 4,4{\textquoteright}-(1-phenylethane-1,1-diyl) diphenol (BPA-AP) with IPC. Inherent viscosities and number average molecular weights of (co)polyesters were in the range 0.85-1.64 dL/g and 58,900-190,400, respectively, indicating the formation of reasonably high molecular weight polymers. Tough, transparent, and flexible films could be cast from chloroform solutions of these polyesters. X-Ray diffraction analysis showed that (co)polyesters were amorphous in nature. (Co)polyesters were characterized using FT-IR, H-1 NMR spectroscopy, XRD, TGA and DSC analysis. The chemical modification of a representative copolyester containing pendant azido groups was carried out quantitatively using copper-catalyzed azide-alkyne cycloaddition (CuAAC) with two alkynes viz., phenyl acetylene (PA) and ethynyl-4-nitrobenzene (ENB). Additionally, (co)polyesters containing pendant azido groups were thermally cross-linked (170 degrees C/12 h) leading to the formation of network structures based on azide to nitrene decomposition and subsequent reactions on polyester backbone. The selected cross-linked polyesters were characterized by stress-strain measurements. The cross-linked polymers exhibited higher tensile strength and Young{\textquoteright}s modulus and lower \% elongation at break compared to corresponding pristine polyesters containing pendant azido groups.

}, keywords = {Aromatic polyester, Chemical modification, Click chemistry, Pendant azido group, Thermal cross-linking}, issn = {0014-3057}, doi = {10.1016/j.eurpolymj.2019.04.019}, author = {Nagane, Samadhan S. and Verma, Savita and Tawade, V, Bhausaheb and Sane, Prakash S. and Dhanmane, Sushilkumar A. and Wadgaonkar, Prakash P.} } @article {46167, title = {Au based Ni and Co bimetallic core shell nanocatalysts for room temperature selective decomposition of hydrous hydrazine to hydrogen}, journal = {ChemistrySelect}, volume = {4}, year = {2019}, month = {MAR }, pages = {2734-2740}, type = {Article}, abstract = {

Nickel and Cobalt bimetallic catalysts with Au as core metal has been synthesized and demonstrated for hydrazine decomposition reaction for producing hydrogen. Gold-cobalt and gold nickel bimetallic system belonging to the class of strained structures with high lattice mismatch of approximately 14\% are demonstrated for synergistic effects atypical of monometallic counterparts for the selective decomposition of hydrous hydrazine to H-2 with N-2 as the other product at room temperature.

}, keywords = {(HDR), Au@Co., Au@Ni., Bimetallic, catalyst., core, decomposition, Hydrazine, nanoparticles., reaction, shell}, issn = {2365-6549}, doi = {10.1002/slct.201900483}, author = {Jain, P. and Anila, K. A. and Vinod, C. P.} } @article {46228, title = {Bioactivities and molecular networking-based elucidation of metabolites of potent actinobacterial strains isolated from the Unkeshwar geothermal springs in India}, journal = {RSC Advances}, volume = {9}, year = {2019}, month = {MAR}, pages = {9850-9859}, type = {Article}, abstract = {

The bioactive potential of Actinobacteria endemic to hot springs has rarely been investigated. This study highlights the cultivable diversity and bioactivities of Actinobacteria associated with the Unkeshwar hot springs, India. Potent strains were evaluated for their biosynthetic potentials and metabolite analysis was performed using effective dereplication molecular networking tools. A total of 86 actinobacterial strains were isolated and grouped into 21 distinct genera, based on 16S rRNA gene sequence analysis. These strains included rare members such as Micromonospora, Marmoricola, Actinomadura, Cellulomonas, Cellulosimicrobium, Janibacter, Rothia, Barrentisimonas, Dietzia and Glycomyces. In antimicrobial screening, Micromonospora sp. strain GH99 and Streptomyces sp. strain GH176 were found to be potent antimicrobial strains. The metabolic extracts of these strains exhibited strong antimicrobial activity against Staphylococcus epidermidis (NCIM 2493), Shigella flexneri (NCIM 5265), Klebsiella pneumonia (NCIM 2098), and Salmonella abony (NCIM 2257). The extracts also displayed strong anti-biofilm and anticancer activities against Pseudomonas aeruginosa (NCIM 5029), Acinetobacter junii (NCIM 5188) and breast cancer cell line MCF7, respectively. Both strains also tested positive for the presence of the PKS biosynthetic gene cluster in their genomes. To effectively delineate the secondary metabolites, the extracts were subjected to MS/MS-guided molecular networking analysis. Structurally diverse compounds including the polyketides 22-dehydroxymethyl-kijanolide (GH99 strain) and Abyssomicin I (GH176 strain) were detected in the extracts. Interestingly, Brevianamide F was detected in the extract of Micromonospora, which has previously been mostly found in fungal species. Other compounds such as cyclic tripeptides, Cyclo(l-Pro-d-Ile) and Cyclo(d-Pro-l-Phe), were also identified in this strain. In summary, for the first time, we explored the diversity of Actinobacteria and evaluated their bioactive potential from the Unkeshwar hot springs. The potent strains isolated in the study could be useful in drug discovery programs.

}, doi = {10.1039/c8ra09449g}, author = {Mehetre, Gajanan T. and Vinodh, J. S. and Burkul, Bhushan B. and Desai, D. and Santhakumari, B. and Dharne, Mahesh S. and Dastager, Syed G} } @article {46295, title = {Can the solvent enhance the rate of chemical reactions through C-H/pi interactions? insights from theory}, journal = {Physical Chemistry Chemical Physics}, volume = {21}, year = {2019}, month = {JUL}, pages = {14821-14831}, type = {Article}, abstract = {

The current computational study with density functional theory (DFT) shows that the rate of chemical reactions can be influenced through non-covalent C-H/p interactions between substrates and the solvent. It is shown that intramolecular carbon-carbon interaction and CO2 activation by a low valent silicon complex are both favourably affected by the explicit presence of the solvent toluene, due to C-H/p interactions between toluene and the silicon complex. Furthermore, ab initio molecular dynamics (AIMD) simulations demonstrate that even if the C-H/p interacting solvent molecule is displaced from the complex, another would quickly take its place, thus maintaining the interaction. Hence, the current work shows how non-covalent interactions between solvent and substrate can enhance the rate of the reaction and expands our understanding of the role and influence of the solvent in effecting important chemical transformations.

}, issn = {1463-9076}, doi = {10.1039/c9cp02646k}, author = {Jain, Shailja and Vanka, Kumar} } @article {46294, title = {Carbon derived from soft pyrolysis of a covalent organic framework as a support for small-sized RuO2 showing exceptionally low overpotential for oxygen evolution reaction}, journal = {ACS Omega}, volume = {4}, year = {2019}, month = {AUG}, pages = {13465-13473}, type = {Article}, abstract = {

Electrochemical water splitting is the most energy-efficient technique for producing hydrogen and oxygen, the two valuable gases. However, it is limited by the slow kinetics of the anodic oxygen evolution reaction (OER), which can be improved using catalysts. Covalent organic framework (COF)-derived porous carbon can serve as an excellent catalyst support. Here, we report high electrocatalytic activity of two composites, formed by supporting RuO2 on carbon derived from two COFs with closely related structures. These composites catalyze oxygen evolution from alkaline media with overpotentials as low as 210 and 217 mV at 10 mA/cm(2), respectively. The Tafel slopes of these catalysts (65 and 67 mV/dec) indicate fast kinetics compared to commercial RuO2. The observed activity is the highest among all RuO2-based heterogeneous OER catalysts-a touted benchmark OER catalyst. The high catalytic activity arises from the extremely small-sized (similar to 3-4 nm) RuO2 nanoparticles homogeneously dispersed in a micro-mesoporous (BET = 517 m(2)/g) COF-derived carbon. The porous graphenic carbon favors mass transfer, while its N-rich framework anchors the catalytic nanoparticles, making it highly stable and recyclable. Crucially, the soft pyrolysis of the COF enables the formation of porous carbon and simultaneous growth of small RuO2 particles without aggregation.

}, issn = {2470-1343}, doi = {10.1021/acsomega.9b01777}, author = {Chakraborty, Debanjan and Nandi, Shyamapada and Illathvalappil, Rajith and Mullangi, Dinesh and Maity, Rahul and Singh, Santosh K. and Haldar, Sattwick and Vinod, Chathakudath P. and Kurungot, Sreekumar and Vaidhyanathan, Ramanathan} } @article {46117, title = {Cu/Cu2O nanoparticles supported on a phenol-pyridyl COF as a heterogeneous catalyst for the synthesis of unsymmetrical diynes via glaser-hay coupling}, journal = {ACS Applied Materials \& Interfaces}, volume = {11}, year = {2019}, month = {MAY }, pages = {15670-15679}, type = {Article}, abstract = {

Covalent organic frameworks (COFs) are a new class of porous crystalline polymers with a modular construct that favors fiinctionalization. COF pores can be used to grow nanoparticles (nPs) with dramatic size reduction, stabilize them as dispersions, and provide excellent nP access. Embedding substrate binding sites in COFs can generate host-guest synergy, leading to enhanced catalytic activity. In this report, Cu/Cu2O nPs (2-3 nm) are grown on a COF, which is built by linking a phenolic trialdehyde and a triamine through Schiff bonds. Their micropores restrict the nP to exceptionally small sizes (similar to 2-3 nm), and the pore walls decorated with strategically positioned hydrogen-bonding phenolic groups anchor the substrates via hydrogen-bonding, whereas the basic pyridyl sites serve as cationic species to stabilize the [CuclusterCl2](2-) type reactive intermediates. This composite catalyst shows high activity for Glaser-Hay heterocoupling reactions, an essential 1,3-diyne yielding reaction with widespread applicability in organic synthesis and material science. Despite their broad successes in homocoupled products, preparation of unsymmetrical 1,3-diynes is challenging due to poor selectivity. Here, our COF-based Cu catalyst shows elevated selectivity toward heterocoupling product(s) (Cu nP loading 0.0992 mol \%; turn over frequency: similar to 4S-50; turn over number: similar to 17S-190). The reversible redox activity at the Cu centers has been demonstrated by carrying out X-ray photoelectron spectroscopy on the frozen reactions, whereas the crucial interactions between the substrates and the binding sites in their optimized configurations have been modeled using density functional theory methods. This report emphasizes the utility of COFs in developing a heterogeneous catalyst for a truly challenging organic heterocoupling reaction.

}, keywords = {Copper nanoparticles, Covalent organic framework, Glaser-Hay heterocoupling, heterogeneous catalysis, unsymmetrical diynes}, issn = {1944-8244}, doi = {10.1021/acsami.9b02860}, author = {Chakraborty, Debanjan and Nandi, Shyamapada and Mullangi, Dinesh and Haldar, Sattwick and Vinod, Chathakudath P. and Vaidhyanathan, Ramanathan} } @article {46280, title = {Cyclic tetrapeptides from nature and design: a review of synthetic methodologies, structure, and function}, journal = {Chemical Reviews}, volume = {119}, year = {2019}, month = {SEP}, pages = { 10318-10359}, type = {Article}, abstract = {

Small cyclic peptides possess a wide range of biological properties and unique structures that make them attractive to scientists working in a range of areas from medicinal to materials chemistry. However, cyclic tetrapeptides (CTPs), which are important members of this family, are notoriously difficult to synthesize. Various synthetic methodologies have been developed that enable access to natural product CTPs and their rationally designed synthetic analogues having novel molecular structures. These methodologies include the use of reversible protecting groups such as pseudoprolines that restrict conformational freedom, ring contraction strategies, on-resin cyclization approaches, and optimization of coupling reagents and reaction conditions such as temperature and dilution factors. Several fundamental studies have documented the impacts of amino acid configurations, N-alkylation, and steric bulk on both synthetic success and ensuing conformations. Carefully executed retrosynthetic ring dissection and the unique structural features of the linear precursor sequences that result from the ring dissection are crucial for the success of the cyclization step. Other factors that influence the outcome of the cyclization step include reaction temperature, solvent, reagents used as well as dilution levels. The purpose of this review is to highlight the current state of affairs on naturally occurring and rationally designed cyclic tetrapeptides, including strategies investigated for their syntheses in the literature, the conformations adopted by these molecules, and specific examples of their function. Using selected examples from the literature, an in-depth discussion of the synthetic techniques and reaction parameters applied for the successful syntheses of 12-, 13-, and 14-membered natural product CTPs and their novel analogues are presented, with particular focus on the cyclization step. Selected examples of the three-dimensional structures of cyclic tetrapeptides studied by NMR, and X-ray crystallography are also included.

}, author = {Sarojini, Vijayalekshmi and Cameron, Alan J. and Varnava, Kyriakos G. and Denny, William A. and Sanjayan, Gangadhar} } @article {45609, title = {C-F bond activation by saturated NHC: mesoionic compound formation and its unprecedented adduct with B(C6F5)3}, journal = {Angewandte Chemie - International Edition}, volume = {58}, year = {2019}, month = {FEB}, pages = {2804-2808}, type = {Article}, abstract = {

The reaction of SIPr, [1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene] (1), with C6F6 led to the formation of an unprecedented mesoionic compound (2). The formation of 2 is made accessible by deprotonation of the SIPr backbone with simultaneous elimination of HF. The C-F bond para to the imidazolium ring in 2 is only of 1.258(4) {\r A}, which is the one of the shortest structurally authenticated C-F bonds known to date. The liberation of HF during the reaction is unequivocally proved by the addition of one more equivalent of SIPr, which leads to the imidazolium salt with the HF2- anion. To functionalize 2, the latter reacted with B(C6F5)3 to give an unusual donor{\textendash}acceptor compound, where the fluoride atom from the C6F5 moiety coordinates to B(C6F5)3 and the carbanion moiety remains unaffected. Such coordination susceptibility of the fluoride atom of a nonmetallic system to a main-group Lewis acid (Fnon-metal{\textrightarrow}BR3) is quite unprecedented.

}, keywords = {C-F activation, carbanions, N-heterocyclic carbenes, structure elucidation, Ylides}, issn = {1433-7851}, doi = {10.1002/anie.201814616}, author = {Pait, M. and Kundu, G. and Tothadi, S. and Karak, S. and Jain, S. and Vanka, K. and Sen, S. S.} } @article {46255, title = {Dendrite growth suppression by Zn2+-integrated nafion ionomer membranes: beyond porous separators toward aqueous Zn/V2O5 batteries with extended cycle life }, journal = {Energy Technology}, volume = {7}, year = {2019}, month = {SEP}, type = {Article}, abstract = {

The dendritic/irregular growth of zinc deposits in the anode surface is often considered as a major intricacy limiting the lifespan of aqueous zinc-ion batteries. The effect of separators on the evolution of the surface morphology of the anode/cathode is never thoroughly studied. Herein, for the first time, the efficacy of the Zn2+-integrated Nafion ionomer membrane is demonstrated as a separator to effectively suppress the growth of irregular zinc deposits in the metallic anode of an aqueous Zn/V2O5 battery. The Zn2+-ions coordinated with the SO3- moieties in Nafion result in a high transference number of the Zn2+ cation, all the while facilitating a high ionic conductivity. The Zn2+-integrated Nafion membrane enables the Zn/V2O5 cell to deliver a high specific capacity of 510 mAh g(-1) at a current of 0.25 A g(-1), which is close to the theoretical capacity of anhydrous V2O5 (589 mAh g(-1)). Moreover, the same cell exhibits an excellent cycling stability of 88\% retention of the initial capacity even after 1800 charge-discharge cycles, superior to that of the Zn/V2O5 cells comprising conventional porous separators.

}, doi = {10.1002/ente.201900442}, author = {Ghosh, Meena and Vijayakumar, Vidyanand and Kurungot, Sreekumar} } @article {46232, title = {Development of low-cost plant probiotic formulations of functional endophytes for sustainable cultivation of Coleus forskohlii}, journal = {Microbiological Research}, year = {2019}, month = {AUG}, type = {Article}, abstract = {

Deployment of plant endophytes at field level is reported to make an impact on agricultural crop productivity; development and deployment of suitable crop specific plant probiotics in a suitable delivery matrix is a value-added task. In our study, we attempted to develop bioformulations of native, fungal endophytes of Coleus forskohlii to improve plant yield using two different carrier-based materials (talc and wheat bran). Initially, fungal endophytes (RF1, SF1, and SF2) were grown on sterilized wheat bran under solid state condition and their growth kinetics and pattern were analyzed by ergosterol content and scanning electron microscope, respectively. 10-day-grown fungal endophytic cultures were used for the development of two types of formulations (wheat bran and talc-based formulations) and tested for their efficacy on host plant, C. forskohlii under field conditions. Interestingly, application of wheat bran-based endophytic formulations significantly (p \< 0.01) enhanced plant height (12-29\%), number of branches (51-63\%), root biomass (26-33\%), photosynthetic pigments (32-101\%), and forskolin content (35-56\%) compared to talc-based formulations under field conditions. Shelf life of endophytes (RF1, SF1, and SF2) in both formulations revealed spore viability in wheat bran-based formulations for 6 months storage period as compared to talc-based formulations. Overall, the present investigation envisages developing plant probiotic bioformulations of functional endophytes of C. forskohlii to enhance root biomass and in planta forskolin content.

}, doi = {10.1016/j.micres.2019.126310}, author = {Mastan, Anthati and Rane, Digeshwar and Dastager, Syed and VivekBabu, C. S.} } @article {46322, title = {Diastereoselective multi-component tandem condensation: synthesis of 2-amino-4-(2-furanone)-4H-chromene-3-carbonitriles}, journal = {Organic \& Biomolecular Chemistry}, volume = {17}, year = {2019}, month = {OCT}, pages = {8853-8857}, type = {Article}, abstract = {

A general strategy for a one-pot stereoselective synthesis of 2-amino-4-(2-furanone)-4H-chromene-3-carbonitriles by reaction of salicylaldehyde, malononitrile and butenolides via a tandem Knoevenagel/Pinner/vinylogous Michael condensation is presented. The beta,gamma-butenolides gave a syn-selective MCR adduct with a dr up to 11.5 : 1. The mechanistic insight into the MCR was obtained by DFT calculations.

}, issn = {1477-0520}, doi = {10.1039/c9ob01345h}, author = {Gupta, Vijay and Sahu, Debashish and Jain, Shailja and Vanka, Kumar and Singh, Ravi P.} } @article {46197, title = {Direct Z-scheme g-C3N4/FeWO4 nanocomposite for enhanced and selective photocatalytic CO2 reduction under visible light}, journal = {ACS Applied Materials \& Interfaces}, volume = {11}, year = {2019}, month = {FEB }, pages = {6174-6183}, type = {Article}, abstract = {

Photocatalytic reduction of CO2 to renewable solar fuels is considered to be a promising strategy to simultaneously solve both global warming and energy crises. However, development of a superior photocatalytic system with high product selectivity for CO2 reduction under solar light is the prime requisite. Herein, a series of nature-inspired Z-scheme g C3N4/FeWO4 composites are prepared for higher performance and selective CO2 reduction to CO as solar fuel under solar light. The novel direct Z-scheme coupling of the visible light-active FeWO4 nanoparticles with C3N4 nanosheets is seen to exhibit excellent performance for CO production with a rate of 6 mu mol/g/h at an ambient temperature, almost 6 times higher compared to pristine C3N4 and 15 times higher than pristine FeWO4. More importantly, selectivity for CO is 100\% over other carbon products from CO, reduction and more than 90\% over. H-2 products from water splitting. Our results clearly demonstrate that the staggered band structure between FeWO4 and C3N4 reflecting the nature-inspired Z-scheme system not only favors superior spatial separation of the electron hole pair in g-C3N4/FeWO4 but also shows good reusability. The present work provides unprecedented insights for constructing the direct Z-scheme by mimicking the nature for high performance and selective photocatalytic CO2 reduction into solar fuels under solar light.

}, keywords = {C3N4, CO2 reduction, FeWO4, Photocatalysis, solar fuels, Z-scheme}, issn = {1944-8244}, doi = {10.1021/acsami.8b22434}, author = {Bhosale, Reshma and Jain, Srashti and Vinod, Chathakudath Prabhakaran and Kumar, Santosh and Ogale, Satishchandra} } @inbook {47468, title = {Distribution and bioprospecting potential of actinobacteria from Indian mangrove ecosystems}, booktitle = {Microbial Diversity in Ecosystem Sustainability and Biotechnological Applications}, year = {2019}, pages = {319-353}, publisher = {Springer, Singapore}, organization = {Springer, Singapore}, abstract = {Actinobacteria are the ecologically and economically important prokaryotes with the unprecedented ability to produce novel metabolites. They are widely distributed in nature due to their physiological and metabolic versatility. Actinobacteria from marine ecosystem are recognized as a promising source for novel bioactive metabolites. Notably, mangroves are the most fertile and productive marine ecosystem due to their ecophysiological conditions and vast microbial diversity. At the global level, there are many novel actinobacteria which have been reported from mangrove ecosystems and also explored for their bioprospecting potential. However, in India, microbiologists have explored actinobacteria from selected mangrove ecosystems for the past five decades with special reference to culturable diversity and antimicrobial, antimycobacterial, anticancer, and enzymatic activities. So far, around 22 rare actinobacterial genera have been reported from the Indian mangrove ecosystems. However, several other novel actinobacteria with promising bioprospecting potential are yet to be explored. Hence, research on actinobacteria in the Indian mangrove ecosystem is still in its infancy. This chapter will describe the exploratory research work carried out on the importance, diversity, antimicrobial and enzymatic activity, biodegradation, and nanotechnological potency of actinobacteria from the Indian mangrove ecosystems. This chapter will enable researchers to identify the gaps to be bridged for further research on Indian mangrove actinobacteria and exploit their potential to the maximum benefit to mankind.}, isbn = {978-981-13-8315-1}, doi = {10.1007/978-981-13-8315-1_11}, author = {Manikkam, Radhakrishnan and Pati, Premalata and Thangavel, Shanmugasundaram and Venugopal, Gopikrishnan and Joseph, Jerrine and Ramasamy, Balagurunathan and Dastager, Syed G.} } @article {46170, title = {Efficient bifunctional reactivity of K-doped CrO(OH) nanosheets: exploiting the combined role of Cr(iii) and surface -OH groups in tandem catalysis}, journal = {Catalysis Science \& Technology}, volume = {9}, year = {2019}, month = {MAR }, pages = {1154-1164}, type = {Article}, abstract = {

This work reports the bifunctional catalytic activity of layered K-doped alpha-CrO(OH). The combined action of the redox active Cr(III) and the surface hydroxyl groups was efficiently used to carry out 2-3 oxidation reactions in tandem followed by condensation/coupling reactions in one pot. Oxidation of benzyl alcohol followed by Knoevenagel condensation or coupling reactions forming C-C and C-N linkages in one pot is demonstrated. The catalyst has been characterized using XRD, IR, TGA, CO2-TPD, cyclic voltammetry, XPS and microscopic techniques to gain insight into the nature of active sites. The role of O- and O2- on the CrO(OH) catalyst in the bifunctional activity was studied using analytical techniques. Recyclability and leaching tests confirmed that K-alpha-CrO(OH) is a stable and environmentally safe catalyst.

}, issn = {2044-4753}, doi = {10.1039/c8cy02345j}, author = {Vernekar, Dnyanesh and Ratha, Satyajit and Rode, Chandrashekhar and Jagadeesan, Dinesh} } @article {46298, title = {Estrogen receptor activation in response to Azadirachtin A stimulates osteoblast differentiation and bone formation in mice}, journal = {Journal of Cellular Physiology}, volume = {234}, year = {2019}, month = {DEC}, pages = {23719-23735}, type = {Article}, abstract = {

The positive effectsof the sex hormone in sustaining bone homeostasis areexercised by maintaining the equilibrium betweencell activity and apoptosis. In this regard, the importance of estrogen receptors in maintaining the bone is that it is anattractive drug target,if devoid of known side effects. In this study, we show that a natural pure compound Azadirachtin A (Aza A) isolated from Azadirachta indica binds selectively to a site in the estrogen receptor, identifying itself to bea selective tissue modifier. Using computational and medicinal chemistry, we show that Aza A binds potentially and selectively to estrogen receptor-alpha (ER alpha) as compared with ER beta. This preferential binding of Aza A to ER alpha with good pharmacokinetic distribution in the body forms metabolites, showing that it is well absorbed. In in vivo estrogen deficiency models for osteoporosis, Aza A at a much lower dose enhances new bone formation at both sites of the trabecular and cortical bone with increased bone strength and presentswith no hyperplastic effect in the uterus.

}, keywords = {ALP, Gene expression, micro-CT, mineralization, osteoblast cells}, issn = {0021-9541}, doi = {10.1002/jcp.28940}, author = {Kushwaha, Priyanka and Ahmad, Naseer and Dhar, V. Yogeshwar and Verma, Ashwni and Haldar, Saikat and Mulani, Fayaj A. and Trivedi, Prabodh K. and Mishra, Prabhat R. and Thulasiram, V. Hirekodathakallu and Trivedi, Ritu} } @article {46266, title = {Experimental and density functional theory investigations of catechol sensing properties of ZnO/RGO nanocomposites}, journal = {Applied Surface Science}, year = {2019}, month = {NOV}, type = {Article}, abstract = {

Catechol, an essential industrial feedstock is one of the major environmental pollutant which causes several health issues including skin irritation, eye damage and genetic defects. In this work, we have investigated the catechol sensing performance of ZnO/RGO composites for its quantitative detection. ZnO/RGO composite showed superior electron transfer kinetics, sensitivity (162.04 mu A mM cm(-2)) and lower detection limit (47 nM) than that of bare ZnO nanoparticles. Further, the change in the zeta potential towards the lower negative demonstrated the strong electrostatic interaction between ZnO-RGO and catechol where it is converted as 1, 2 Benzoquinone through redox reactions. By using state of the art of Density Functional Theory simulations, we have demonstrated the interaction of catechol molecule on various ZnO clusters and RGO supported ZnO clusters. The strong bonding between p orbital of O atom of catechol and d orbital of Zn atom and its charge transfer facilitate the oxidation of catechol molecule. In the presence of RGO, the binding energy of catechol and charge transfer increases which qualitatively infer that RGO/ZnO exhibits higher sensitivity compared to bare ZnO and in consistency with the experimental observations.

}, doi = {10.1016/j.apsusc.2019.143588}, author = {Ponnusamy, Rajeswari and Venkatesan, Rajiu and Gangan, Abhijeet and Samal, Rutuparna and Chakraborty, Brahmananda and Late, Dattatray J. and Rout, Chandra Sekhar} } @article {46225, title = {Exploring energy profiles of protein-protein interactions (PPIs) Using DFT method}, journal = {Letters in Drug Design \& Discovery}, volume = {16}, year = {2019}, month = {JUN}, pages = {670-677}, type = {Article}, abstract = {

Background: Large-scale energy landscape characterization of protein-protein interactions (PPIs) is important to understand the interaction mechanism and protein-protein docking methods. The experimental methods for detecting energy landscapes are tedious and the existing computational methods require longer simulation time.

Objective: The objective of the present work is to ascertain the energy profiles at the interface regions in a rapid manner to analyze the energy landscape of protein-protein interactions

Methods: The atomic coordinates obtained from the X-ray and NMR spectroscopy data are considered as inputs to compute cumulative energy profiles for experimentally validated protein-protein complexes. The energies computed by the program were comparable to the standard molecular dynamics simulations.

Results: The PPI Profiler not only enables rapid generation of energy profiles but also facilitates the detection of hot spot residue atoms involved therein.

Conclusion: The hotspot residues and their computed energies matched with the experimentally determined hot spot residues and their energies which correlated well by employing the MM/GBSA method. The proposed method can be employed to scan entire proteomes across species at an atomic level to study the key PPI interactions.

}, doi = {10.2174/1570180815666180815151141}, author = {Bapat, Sanket and Vyas, Renu and Karthikeyan, Muthukumarasamy} } @article {46215, title = { Freestanding borophene and Its hybrids }, journal = {Advanced Materials}, volume = {31}, year = {2019}, month = {JULY}, type = {Article}, abstract = {

Borophene, an elemental metallic Dirac material is predicted to have unprecedented mechanical and electronic character. Need of substrate and ultrahigh vacuum conditions for deposition of borophene restricts its large-scale applications and significantly hampers the advancement of research on borophene. Herein, a facile and large-scale synthesis of freestanding atomic sheets of borophene through a novel liquid-phase exfoliation and the reduction of borophene oxide is demonstrated. Electron microscopy confirms the presence of beta(12), X-3, and their intermediate phases of borophene; X-ray photoelectron spectroscopy, and scanning tunneling microscopy, corroborated with density functional theory band structure calculations, validate the phase purity and the metallic nature. Borophene with excellent anchoring capabilities is used for sensing of light, gas, molecules, and strain. Hybrids of borophene as well as that of reduced borophene oxide with other 2D materials are synthesized, and the predicted superior performance in energy storage is explored. The specific capacity of borophene oxide is observed to be approximate to 4941 mAh g(-1), which significantly exceeds that of existing 2D materials and their hybrids. These freestanding borophene materials and their hybrids will create a huge breakthrough in the field of 2D materials and could help to develop future generations of devices and emerging applications.

}, doi = { 10.1002/adma.201900353}, author = {Ranjan, Pranay and Sahu, Tumesh Kumar and Bhushan, Rebti and Yamijala, Sharma S. R. K. C. and Late, Dattatray J and Kumar, Prashant and Vinu, Ajayan} } @article {46177, title = {High-performing PGM-free AEMFC cathodes from carbon-supported cobalt ferrite nanoparticles}, journal = {Catalysts}, volume = {9}, year = {2019}, month = {MAR}, pages = {264}, type = {Article}, abstract = {

Efficient and durable non-precious metal electrocatalysts for the oxygen reduction reaction (ORR) are highly desirable for several electrochemical devices, including anion exchange membrane fuel cells (AEMFCs). Here, cobalt ferrite (CF) nanoparticles supported on Vulcan XC-72 carbon (CF-VC) were created through a facile, scalable solvothermal method. The nano-sized CF particles were spherical with a narrow particle size distribution. The CF-VC catalyst showed good ORR activity, possessing a half-wave potential of 0.71 V. Although the intrinsic activity of the CF-VC catalyst was not as high as some other platinum group metal (PGM)-free catalysts in the literature, where this catalyst really shined was in operating AEMFCs. When used as the cathode in a single cell 5 cm(-2) AEMFC, the CF-VC containing electrode was able to achieve a peak power density of 1350 mW cm(-2) (iR-corrected: 1660 mW cm(-2)) and a mass transport limited current density of more than 4 A cm(-2) operating on H-2/O-2. Operating on H-2/Air (CO2-free), the same cathode was able to achieve a peak power density of 670 mW cm(-2) (iR-corrected: 730 mW cm(-2)) and a mass transport limited current density of more than 2 A cm(-2). These peak power and achievable current densities are among the highest reported values in the literature to date.

}, keywords = {AEMFC, cobalt, Ferrite, high-performing, non-PGM, vulcan}, issn = {2073-4344}, doi = {10.3390/catal9030264}, author = {Peng, Xiong and Kashyap, Varchaswal and Ng, Benjamin and Kurungot, Sreekumar and Wang, Lianqin and Varcoe, John R. and Mustain, William E.} } @article {46348, title = {Imidazole-linked crystalline two-dimensional polymer with ultrahigh proton-conductivity}, journal = {Journal of the American Chemical Society}, volume = {141}, year = {2019}, month = {SEP}, pages = {14950-14954}, type = {Article}, abstract = {

Proton-exchange membrane fuel cells are promising energy devices for a sustainable future due to green features, high power density, and mild operating conditions. A facile proton-conducting membrane plays a pivotal role to boost the efficiency of fuel cells, and hence focused research in this area is highly desirable. Major issues associated with the successful example of Nafion resulted in the search for alternate proton conducting materials. Even though proton carrier loaded crystalline porous organic frameworks have been used for protonconduction, the weak host-guest interactions limited their practical use. Herein, we developed a crystalline 2D-polymer composed of benzimidazole units as the integral part, prepared by the condensation of aryl acid and diamine in polyphosphoric acid medium. The imidazole linked-2D-polymer exhibits ultrahigh proton conductivity (3.2 X 10(-2) S cm(-1)) (at 95\% relative humidity and 95 degrees C) in the pristine state, which is highest among the undoped porous organic frameworks so far reported. The present strategy of a crystalline proton-conducting 2D-polymer will lead to the development of new high performing crystalline solid proton conductor.

}, issn = {0002-7863}, doi = {10.1021/jacs.9b06080}, author = {Ranjeesh, Kayaramkodath Chandran and Ilathvalappil, Rajith and Veer, Sairam Dnyaneshwar and Peter, Joseph and Wakchaure, Vivek Chandrakant and Goudappagouda and Raj, K. Vipin and Kurungot, Sreekumar and Babu, Sukumaran Santhosh} } @article {46226, title = {Immobilization studies of Candida Antarctica lipase B on gallic acid resin-grafted magnetic iron oxide nanoparticles}, journal = {International Journal of nanomedicine}, volume = {14}, year = {2019}, month = {MAY}, pages = {3235-3244}, type = {Article}, abstract = {

Purpose: Here, we present the successful preparation of a highly efficient gallic acid resin grafted with magnetic nanoparticles (MNPs) and containing a branched brush polymeric shell.

Methods: Using a convenient co-precipitation method, we prepared Fe3O4 nanoparticles stabilized by citric acid. These nanoparticles underwent further silica modification and amino functionalization followed by gallic acid functionalization on their surface. Under alkaline conditions, we used a condensation reaction that combined formaldehyde and gallic, to graft the gallic acid-formaldehyde resin on the surface. We then evaluated the polymer-grafted MNPs to assay the Candida Antarctica B lipase(Cal-B) immobilization via physical adsorption.

Conclusion: Furthermore, during optimization of parameters that defined conditions of immobilization, we found that the optimum immobilization was achieved in 15 mins Also, optimal immobilization temperature and pH were 38 degrees C and 7.5, respectively. In addition, the reusability study of immobilized lipase polymer-grafted MNPs was done by isolating the MNPs from the reaction medium using magnetic separation, which showed that grafted MNPs reached 5 cycles with 91\% activity retention.

}, doi = {10.2147/IJN.S203547}, author = {SreeHarsha, Nagaraja and Ghorpade, Ravindra, V. and Alzahrani, Abdullah Mossa and Al-Dhubiab, Bandar E. and Venugopala, Katharigatta N.} } @article {46276, title = {Insights into the origin of life: did it begin from HCN and H2O?}, journal = {Acs Central Science}, volume = {5}, year = {2019}, month = {SEP}, pages = {1532-1540}, type = {Article}, abstract = {

The seminal Urey-Miller experiments showed that molecules crucial to life such as HCN could have formed in the reducing atmosphere of the Hadean Earth and then dissolved in the oceans. Subsequent proponents of the "RNA World" hypothesis have shown aqueous HCN to be the starting point for the formation of the precursors of RNA and proteins. However, the conditions of early Earth suggest that aqueous HCN would have had to react under a significant number of constraints. Therefore, given the limiting conditions, could RNA and protein precursors still have formed from aqueous HCN? If so, what mechanistic routes would have been followed? The current computational study, with the aid of the ab initio nanoreactor (AINR), a powerful new tool in computational chemistry, addresses these crucial questions. Gratifyingly, not only do the results from the AINR approach show that aqueous HCN could indeed have been the source of RNA and protein precursors, but they also indicate that just the interaction of HCN with water would have sufficed to begin a series of reactions leading to the precursors. The current work therefore provides important missing links in the story of prebiotic chemistry and charts the road from aqueous HCN to the precursors of RNA and proteins.

}, doi = {10.1021/acscentsci.9b00520}, author = {Das, Tamal and Ghule, Siddharth and Vanka, Kumar} } @article {46192, title = {Ionic pyridinium-oxazole dyads: design, synthesis, and application in mitochondrial imaging}, journal = {Journal of Organic Chemistry}, volume = {84}, year = {2019}, month = {FEB }, pages = {1766-1777}, type = {Article}, abstract = {

We recently developed an oxidative intramolecular 1,2-amino-oxygenation reaction, combining gold(I)/gold(III) catalysis, for accessing structurally unique ionic pyridinium-oxazole dyads (PODs) with tunable emission wavelengths. On further investigation, these fluorophores turned out to be potential biomarkers; in particular, the one containing -NMe2 functionality (NMe2-POD) was highly selective for mitochondrial imaging. Of note, because of mitochondria{\textquoteright}s involvement in early-stage apoptosis and degenerative conditions, tracking the dynamics of mitochondrial morphology with such imaging technology has attracted much interest. Along this line, we wanted to build a library of such PODs which are potential mitochondria trackers. However, Au/Selecfluor, our first-generation catalyst system, suffers from undesired fluorination of electronically rich PODs resulting in an inseparable mixture (1:1) of the PODs and their fluorinated derivatives. In our attempt to search for a better alternative to circumvent this issue, we developed a second-generation approach for the synthesis of PODs by employing Cu(II)/PhI(OAC)(2)-mediated oxidative 1,2-amino-oxygenation of alkynes. Thes newly synthesized PODs exhibit tunable emissions as well as excellent quantum efficiency up to 0.96. Further, this powerful process gives rapid access to a library of NMe2-PODs which are potential mitochondrial imaging agents. Out of the library, the randomly chosen POD-3g was studied for cell-imaging experiments which showed high mitochondrial specificity, superior photostability, and appreciable tolerance to microenvironment changes with respect to commercially available MitoTracker green.

}, issn = {0022-3263}, doi = {10.1021/acs.joc.8b02528}, author = {Shaikh, Aslam C. and Varma, Mokshada E. and Mule, Ravindra D. and Banerjee, Somsuvra and Kulkarni, Prasad P. and Patil, Nitin T.} } @article {46124, title = {Lipid composition and salt concentration as regulatory factors of the anion selectivity of VDAC studied by coarse-grained molecular dynamics simulations}, journal = {Chemistry and Physics of Lipids}, volume = {220}, year = {2019}, month = {MAY}, pages = {66-76}, type = {Article}, abstract = {

The voltage-dependent anion channel (VDAC) is a mitochondrial outer membrane protein whose fundamental function is to facilitate and regulate the flow of metabolites between the cytosol and the mitochondrial inter membrane space. Using coarse-grained molecular dynamics simulations, we investigated the dependence of VDAC selectivity towards small inorganic anions on two factors: the ionic strength and the lipid composition. In agreement with experimental data we found that VDAC becomes less anion selective with increasing salt concentration due to the screening of a few basic residues that point into the pore lumen. The molecular dynamics simulations provide insight into the regulation mechanism of VDAC selectivity by the composition in the lipid membrane and suggest that the ion distribution is differently modulated by POPE compared to the POPC bilayer. This occurs through the more persistent interactions of acidic residues located at both rims of the beta-barrel with head groups of POPE which in turn impact the electrostatic potential and thereby the selectivity of the pore. This mechanism occurs not only in POPE single component membranes but also in a mixed POPE/POPC bilayer by an enrichment of POPE over POPC lipids on the surface of VDAC. Thus we show here that computationally-in-expensive coarse-grained simulations are able to capture, in a semi-quantitative way, essential features of VDAC anion selectivity and could pave the way toward a molecular level understanding of metabolite transport in natural membranes.

}, keywords = {Coarse-grained molecular, Membrane channel, Protein-lipid interactions, VDAC}, issn = {0009-3084}, doi = {10.1016/j.chemphyslip.2018.11.002}, author = {Van Liefferinge, F. and Krammer, E. -M. and Sengupta, D. and Prevost, M.} } @article {46289, title = {Lithium compounds as single site catalysts for hydroboration of alkenes and alkynes}, journal = {Chemical Communications}, volume = {55}, year = {2019}, month = {OCT }, pages = {11711-11714}, type = {Article}, abstract = {

The hydroboration of alkenes and alkynes using easily accessible lithium compounds [2,6-di-tert-butyl phenolatelithium (1a) and 1,1 {\textquoteleft} dilithioferrocene (1b)] has been achieved with good yields, high functional group tolerance and excellent chemoselectivity. Deuterium-labeling experiments confirm the cis-addition of pinacolborane. The methodology has been further extended to myrcene, which undergoes selective 4,3-hydroboration. DFT calculations provide insights into the mechanism.

}, issn = {1359-7345}, doi = {10.1039/c9cc05783h}, author = {Bisai, Milan Kumar and Yadav, Sandeep and Das, Tamal and Vanka, Kumar and Sen, Sakya S.} } @article {46320, title = {Mechanistic insights into the pathways of phenol hydrogenation on Pd nanostructures}, journal = {ACS Sustainable Chemistry \& Engineering}, volume = {7}, year = {2019}, month = {OCT}, pages = {17126-17136}, type = {Article}, abstract = {

Product selectivity in aqueous phase phenol hydrogenation on well-defined supported Pd nanostructures (spheres, cubes, and octahedra) was studied using defined experiments and density functional theory (DFT) simulations. On Pd spheres and octahedra, the reaction initially showed high selectivity (in the first 3 h, at 363 K and 5 bar H-2 pressure) toward the partially hydrogenated product cyclohexanone. On prolonged operation (\>20 h of reaction time), a shift in the product selectivity (up to 100\%) toward the completely hydrogenated product cyclohexanol was observed on Pd spheres and octahedra. In contrast, the reaction on Pd cubes, which only had {100} facets, showed a high selectivity (similar to 90\%) toward the product cyclohexanone even after 40 h, at the same reaction conditions. Since the {111} facets are expected to be the majority sites on a spherical particle, we attribute the selectivity trend observed on spherical Pd particles to be primarily controlled by the selectivity trend on the Pd{111} facets. This observation was further confirmed on performing the hydrogenation reaction on a mixture of Pd cube and Pd octahedron particles in a ratio of 25:75 (representing the site ratio of a spherical particle). DFT simulations provided a mechanistic insight into the reactivity of the two different facets ({100} and {111}) toward phenol hydrogenation. The calculations revealed that the selectivity significantly depended on the activation barriers involved in cyclohexanone hydrogenation on the Pd{111} facets (77 and 57 kJ/mol) as compared to those on the Pd{100} facets (97 and 101 kJ/mol).

}, keywords = {Cyclohexanol, cyclohexanone, facet-dependent reactivity, phenol hydrogenation}, issn = {2168-0485}, doi = {10.1021/acssuschemeng.9b03392}, author = {Porwa, Govind and Gupta, Shelaka and Sreedhala, S. and Elizabeth, Joes and Ithan, Tuhin Suvra and Haider, M. Ali and Vinod, C. P.} } @article {46194, title = {Metal-free regioselective cross dehydrogenative coupling of cyclic ethers and aryl carbonyls}, journal = {Journal of Organic Chemistry}, volume = {84}, year = {2019}, month = {FEB }, pages = {2039-2047}, type = {Article}, abstract = {

A highly regioselective, efficient, and metal-free oxidative cross dehydrogenative coupling (CDC) of aryl carbonyls with cyclic ethers has been developed. This method offers easy access to substituted alpha-arylated cyclic ethers with a high functional group tolerance in good to excellent yields. The regioselectivity of this CDC reaction was confirmed by density functional theory (DFT)-based calculations.

}, issn = {0022-3263}, doi = {10.1021/acs.joc.8b03048}, author = {Mane, Kishor D. and Mukherjee, Anagh and Vanka, Kumar and Suryavanshi, Gurunath} } @article {46120, title = {Microbacterium enclense sp. nov., isolated from sediment sample (vol 65, pg 2064, 2015)}, journal = {International Journal of Systematic and Evolutionary Microbiology}, volume = {69}, year = {2019}, month = {MAY}, pages = {1528}, type = {Correction}, issn = {1466-5026}, doi = {10.1099/ijsem.0.003331}, author = {Mawlankar, Rahul R. and Mual, Poonam and Sonalkar, Vidya V. and Thorat, Meghana N. and Verma, Ashish and Srinivasan, Krishnamurthi and Dastager, Syed G.} } @article {46278, title = {MnO2@Fe3O4 Magnetic Nanoparticles as Efficient and Recyclable Heterogeneous Catalyst for Benzylic sp(3) C-H Oxidation}, journal = {Chemistry-An Asian Journal}, year = {2019}, month = {SEP}, type = {Article}, abstract = {

Herein, we report a highly chemoselective and efficient heterogeneous MnO2@Fe3O4 MNP catalyst for the oxidation of benzylic sp(3) C-H group of ethers using TBHP as a green oxidant to afford ester derivatives in high yield under batch/continuous flow module. This catalyst was also effective for the benzylic sp(3) C-H group of methylene derivatives to furnish the ketone in high yield which can be easily integrated into continuous flow condition for scale up. The catalyst is fully characterized by spectroscopic techniques and it was found that 0.424 \% MnO2@Fe3O4 catalyzes the reaction; the magnetic nanoparticles of this catalyst could be easily recovered from the reaction mixture. The recovered catalyst was recycled for twelve cycles without any loss of the catalytic activity. The advantages of MnO2@Fe3O4 MNP are its catalytic activity, easy preparation, recovery, and recyclability, gram scale synthesis with a TOF of up to 14.93 h(-1) and low metal leaching during the reaction.

}, doi = {10.1002/asia.201900810}, author = {Pandey, Akanksha M. and Agalave, Sandip G. and Vinod, Chathakudath P. and Gnanaprakasam, Boopathy} } @article {47473, title = {Morphological and molecular characterization of Penicillium rubens sp.nov isolated from poultry feed}, journal = {Indian Phytopathology}, volume = {72}, year = {2019}, month = {SEP}, pages = {461{\textendash}478}, type = {Article}, abstract = {Fungi are the second largest group of eukaryotic organisms, estimates ranging from 2.2 to 3.8 million and 120,000 currently accepted species. Unfortunately, identification of Penicillium species is an overwhelming task even for taxonomic experts. In the current study, we isolated identified and morphologically characterized Penicillium rubens strain NCIM-1397. Molecular characterization of P. rubens by multilocus sequence analysis (MLSA) of internal transcribed spacer (ITS) region, β-tubulin (BenA), calmodulin (CaM), NL (D1/D2 region) and LR (large subunit region) gene. Conversely, BenA gene differentiated P. rubens from P. chrysogenum. Moreover, Vitek MS, Matrix-assisted laser desorption ionization{\textendash}time of flight mass spectrometer (MALDI-TOF{\textendash}MS) failed to discriminate to strain level. Metabolic profiling of P. rubens enable to produce roquefortine C, chrysogine, meleagrine, sorbicillin and non-producers for industrially important metabolite, penicillin determined by LC{\textendash}MS. Even, In addition, even molecular detection of penicillin biosynthetic pathway genes, PcbC, PenDE and Phl were negative by PCR. Nevertheless, P. rubens showed 90{\textendash}100\% toxicity/pathogenicity on seed germination of sorghum (Sorghum bicolor) and no further development of coleoptiles, radicle and leaf length observed. Also, it showed non-toxic to animal cell determined on Human foreskin fibroblast (HFF) cell line by In-Vitro.}, doi = {10.1007/s42360-019-00165-2}, author = {Sawant, Amol M. and Vankudoth, Ramu and Navale, Vishwambar and Kumavat, Rajkamal and Kumari, Prabla and Santhakumari, B. and Vamkudoth, Koteswara Rao} } @article {47152, title = {Morphology of ammonium perchlorate in the presence of ethylene glycol as an additive: a first principle study}, journal = {Crystengcomm}, volume = {21}, year = {2019}, month = {DEC}, pages = {7519-7527}, type = {Article}, abstract = {

Ammonium perchlorate (AP) is an extensively used crystalline oxidizer in high energy materials and their compositions. A desired morphology of AP is crucial for the high burn rates of solid propellants. We have examined the habit modification of AP crystals in the absence and presence of ethylene glycol as an impurity by means of important parameters such as interaction and surface energies to predict the resultant morphology. On the basis of first principles density functional theory (DFT) calculations of the binding and surface energies before and after the adsorption of the surface-capping agent (ethylene glycol) on the AP surfaces, we have shown that the relative stability of all the important surfaces (100), (101), (011), (001) and (210) rationalize the habit modification of AP crystals. In accordance with the surface energy calculations, the stability order of the five crystallographic surfaces of AP was found to be (001) \> (210) \> (101) \> (100) \> (011) in the absence of additive molecules, i.e., in the clean surfaces. This result is in concurrence with the fact that AP crystals richly contain (001) planes when grown in the absence of an additive. The computational methodology applied for the determination of surface energies was found to be reliable as it has well reproduced the stability trend of AP surfaces. However, the trend, (210) \> (001) \> (101) \> (011) \> (100), was observed when these surfaces were capped with a known additive molecule, i.e., ethylene glycol. The crystal habit of AP in the presence of ethylene glycol is such that the intensity of the lattice plane (2 1 0) of the modified AP was remarkably high leading to the shape of hexahedral, which is in excellent agreement with the experimental results. A linear fit correlation was also observed between surface energies and interaction energy values for the additive adsorbed AP surfaces.

}, issn = {1466-8033}, doi = {10.1039/c9ce01262a}, author = {Khan, Md Abdul Shafeeuulla and Vijayalakshmi, R. and Singh, Avtar and Nandi, Amiya Kumar and Talawar, M. B.} } @article {46038, title = {MWCNTs-ZnO-SiO2 mesoporous nano-hybrid materials for CO2 capture}, journal = {Journal of Alloys and Compounds}, volume = {800}, year = {2019}, month = {SEP}, pages = {279-285}, type = {Article}, abstract = {

Carbon nanostructures and metal nanoparticles based nanohybrid materials have been established as one of advantageous materials for various applications. Here, we present hydrothermal and sol-gel process at low temperature for the synthesis of (3-Aminopropyl) triethoxysilane (APTES)-ZnO-multi-walled carbon nanotubes (MWCNTs) mesoporous nanohybrid materials. TEM and XPS measurements show that uniform size and quasi-spherical ZnO nanoparticles were anchored to the surface of the MWCNTs. SEM observation exhibits that the aggregation of ZnO nanoparticles is greatly reduced due to the steric repulsion of grafted organic groups. The maximum CO2 adsorption capacity at 273 K was 1.32 mmol/g for MWCNTs-APTES-ZnO-B nanohybrid. An increase in the density of ZnO nanoparticles on the surface of MWCNTs resulted in a higher affinity towards CO2 at low pressure. This work provides new research directions for making further advances toward practical utilization of MWCNTs-based CO2 adsorbents. (C) 2019 Published by Elsevier B.V.

}, keywords = {CO2 capture, Mesoporous, MWCNTs, Nanohybrid, TEM, XPS}, issn = {0925-8388}, doi = {10.1016/j.jallcom.2019.06.011}, author = {Jena, Kishore K. and Panda, Amulya Prasad and Verma, Savita and Mani, Ganesh Kumar and Swain, S. K. and Alhassan, Saeed M.} } @article {46173, title = {Negative axicon tip-based fiber optic interferometer cavity sensor for volatile gas sensing}, journal = {Optics Express}, volume = {27}, year = {2019}, month = {MAR }, pages = {7277-7290}, type = {Article}, abstract = {

In this research work we demonstrated negative axicon optical fiber tip filled with Polydimethylsiloxane (PDMS) as a sensor platform for volatile organic gases detection at room temperature. The response of the sensor was measured with various Volatile Organic Compounds (VOCs) such as Chloroform, Hexane, Isopropanol, Acetone, Toluene and Methanol in the concentration ranging from 5 to 200 ppm. The corresponding sensitivity and limit of detection (LOD) of the developed sensor for the measured VOCs were observed between the order of around 23.7 to 3.2 pm/ppm and 0.84 to 6.10 ppm, respectively. The response and recovery time of sensor were found between the order of 30 to 57 seconds and 8 to 25 seconds respectively for the measured VOCs. Thermal stability of the developed sensor was also studied at 30-70 degrees C with intervals of 10 degrees C. The principle of sensing is based on change in the length of the Fabry-Perot Interferometric (FPI) cavity in the presence of varied concentrations of VOCs, which results in changes in the shift in wavelength of an interference pattern attributed to the change in PDMS filling the cavity length (swelling). The experimentally observed trends in the relative swelling of PDMS with VOCs are found in agreement with the theoretically calculated values obtained from the Hansen solubility parameter (HSP). The developed gas sensor has the potential to fulfill the demands of industrial applications.

}, issn = {1094-4087}, doi = {10.1364/OE.27.007277}, author = {Kanavvade, Rajesh and Kumar, Ajay and Pawar, Dnyandeo and Vairagi, Kaushal and Late, Dattatray and Sarkar, Sudipta and Sinha, Ravindra K. and Mondal, Samir} } @article {46137, title = {Neural anti-inflammatory natural product periconianone A: total synthesis and biological evaluation}, journal = {European Journal of Organic Chemistry}, year = {2019}, month = {APR }, pages = {2376-2381}, type = {Article}, abstract = {

Total synthesis of periconianone A, an eremophilane-type sesquiterpenoid with impressive neural anti-inflammatory potential, has been accomplished. Diels-Alder/aldol strategy to construct tetrahydro-naphthalene-2,6-dione scaffold, allylic oxidation of dienone using DBU/O-2 and postulated biomimetic aldol reaction to construct 6/6/6 tricyclic system are the highlights of the present synthesis. Furthermore, the synthesized (+/-)-periconianone A and two close analogs were tested for their neural anti-inflammatory activity using various assays. In the course of our study we found a structurally simplified analog is superior to (+/-)-periconianone A.

}, keywords = {Aldol, Allylic oxidation, Biological evaluation, Cytotoxicity, Diels-Alder, Periconianone A}, issn = {1434-193X}, doi = {10.1002/ejoc.201900048}, author = {Kalmode, Hanuman P. and Patil, Suhag S. and Handore, Kishor L. and Athawale, Paresh R. and Dandela, Rambabu and Verma, Abhishek Kumar and Basu, Anirban and Reddy, D. Srinivasa} } @article {46249, title = {New porous high surface area, tio2 anatase/sapo-35 mild bronsted acidic nanocomposite: synthesis, characterization and studies on it{\textquoteright}s enhanced photocatalytic activity.}, journal = {ChemistrySelect}, volume = {4}, year = {2019}, month = {AUG}, pages = {9135-9142}, type = {Article}, abstract = {

Anatase TiO2 and Levyne type microporous silico alumino phosphate SAPO-35 are synthesized by using hydrothermal method. TiO2/SAPO-35 nanocomposites were prepared by sol-gel method with different weight ratios. The synthesized materials were characterized by various analytical techniques such as PXRD, SEM/EDAX, TG/DTA, BET-Surface area, FT-IR, UV-Vis, XPS, MAS-NMR and photocatalytic study. From PXRD results it clearly evidenced that, the TiO2 anatase peaks and SAPO-35 combined peaks are in the composite. The spherical shaped TiO2 nanoparticles were found to be dispersed over the rhombohedral SAPO-35 particles, which was analysed by SEM. BET-surface area analysis revealed that, the calcined SAPO-35 has the surface area of 448 m(2)/g, was decreased to 222 m(2)/g for composite which is due to the presence of TiO2 particles having surface area of 85 m(2)/g on the surface of SAPO-35. The oxidation state and co-ordination of various elements present in nanocomposite was composed by X-ray photoelectron spectroscopy. MAS-NMR analysis has shown that SAPO-35 has tetrahedral Al, P and Si oxides. Eventhough Al is unique Si and P are in two different environment namely one in S6R and another in D6R with double intensity. The photocatalytic performance of methylene blue degradation under sunlight radiation by the synthesized TiO2/SAPO-35 was analyzed. The TiO2/SAPO-35 composites degrade the methylene blue under sunlight irradiation in 25 minutes against 90 minuts for pure TiO2 anatase. A plausible mechanism on photocatalytic activity is also proposed.

}, doi = {10.1002/slct.201902134}, author = {Siliveri, Suresh and Chirra, Suman and Tyagi, Chinkit and Gandamalla, Ambedkar and Adepu, Ajay Kumar and Goskula, Srinath and Gujjula, Sripal Reddy and Venkatathri, Narayanan} } @article {46323, title = {Nickel-catalyzed C(2)-H arylation of indoles with aryl chlorides under neat conditions}, journal = {Journal of Organic Chemistry}, volume = {84}, year = {2019}, month = {OCT}, pages = {12800-12808}, type = {Article}, abstract = {

Nickel-catalyzed regioselective C(2)-H arylation of indoles and pyrroles with aryl chlorides is achieved under neat conditions. This method allows the efficient coupling of diverse aryl chlorides employing a user-friendly and inexpensive Ni(OAc)(2)/dppf catalyst system at 80 degrees C. Numerous functionalities, such as halides, alkyl ether, fluoro-alkyl ether, and thioether, and substituted amines, including heteroarenes like benzothiazolyl, pyrrolyl, indolyl, and carbazolyl, are well tolerated under the reaction conditions. The preliminary mechanistic study highlights a single-electron transfer (SET) pathway for the arylation reaction.

}, issn = {0022-3263}, doi = {10.1021/acs.joc.9b01375}, author = {Pandey, Dilip K. and Vijaykumar, Muniyappa and Punji, Benudhar} } @article {46311, title = {Nickel-catalyzed C-H alkylation of indoles with unactivated alkyl chlorides: evidence of a Ni(i)/Ni(iii) pathway}, journal = {Chemical Science}, volume = {10}, year = {2019}, month = {NOV}, pages = {9493-9500}, type = {Article}, abstract = {

A mild and efficient nickel-catalyzed method for the coupling of unactivated primary and secondary alkyl chlorides with the C-H bond of indoles and pyrroles is described which demonstrates a high level of chemo and regioselectivity. The reaction tolerates numerous functionalities, such as halide, alkenyl, alkynyl, ether, thioether, furanyl, pyrrolyl, indolyl and carbazolyl groups including acyclic and cyclic alkyls under the reaction conditions. Mechanistic investigation highlights that the alkylation proceeds through a single-electron transfer (SET) process with Ni(i)-species being the active catalyst. Overall, the alkylation follows a Ni(i)/Ni(iii) pathway involving the rate-influencing two-step single-electron oxidative addition of alkyl chlorides.

}, issn = {2041-6520}, doi = {10.1039/c9sc01446b}, author = {Pandey, Dilip K. and Ankade, Shidheshwar B. and Ali, Abad and Vinod, C. P. and Punji, Benudhar} } @article {45528, title = {Nickel-catalyzed straightforward and regioselective C-H alkenylation of indoles with alkenyl bromides: scope and mechanistic aspect}, journal = {ACS Catalysis}, volume = {9}, year = {2019}, month = {JAN}, pages = {431-441}, type = {Article}, abstract = {

Nickel-catalyzed regioselective C-H bond alkenylation of indoles and related heteroarenes with alkenyl bromides is accomplished under relatively mild conditions. This method allows the straightforward synthesis of C-2 alkenylated indoles employing an air-stable and well-defined nickel catalyst, (bpy)NiBr2, providing a solution to the limitations associated with hydroindolation and oxidative alkenylation. The reaction conceded the coupling of indole derivatives with various alkenyl bromides, such as aromatic and heteroaromatics, alpha- and beta-substituted as well as exo- and endo-cyclic alkenyl compounds. An extensive mechanistic investigation, including controlled study, reactivity experiments, kinetics and labeling studies, and EPR and XPS analyses, highlights that the alkenylation proceeds through a single-electron transfer process comprising an odd-electron oxidative addition of alkenyl bromide. Furthermore, the alkenylation operates via a probable Ni(I)/Ni(III) pathway involving the rate-limiting C-H nickelation of indole.

}, keywords = {alkenylation, C-H activation, indoles, Mechanism, Nickel, single-electron transfer}, issn = {2155-5435}, doi = {10.1021/acscatal.8b04267}, author = {Jagtap, Rahul A. and Vinod, C. P. and Punji, Benudhar} } @article {46172, title = {Nuclear parity- and time-reversal-symmetry violation in the (HgH)-Hg-201 molecule}, journal = {Physical Review A}, volume = {99}, year = {2019}, month = {MAR }, pages = {032503}, type = {Article}, abstract = {

Investigation of the nuclear magnetic quadrupole moment (MQM) is an excellent way to reveal the new physics in the hadron sector of matter. Therefore, we investigate the violation of parity (P) and time-reversal (T) invariance induced by the MQM of the( 201) Hg nucleus in the HgH molecule, which has been proposed as a very promising candidate for the experimental search of the electric dipole moment of electron [M. G. Kozlov and A. Derevianko, Phys. Rev. Lett. 97, 063001 (2006)]. We report the precise value of the molecular parameter, W-M, associated with the P, T-odd nuclear MQM-electron interaction in (HgH)-Hg-201 using the four-component relativistic coupled-cluster method. This parameter is required to interpret the experimental P, T-odd frequency shift in terms of the MQM of nuclei. Furthermore, the magnetic hyperfine structure (HFS) constants of the molecule are computed at the same level of theory. We also study the role of core-correlating functions and the virtual energy functions in the calculations of the HFS constant and W-M. The most reliable value of W(M )in HgH is obtained as 3.22 x 10 (33) Hz/e cm (2) with an uncertainty of around 6\%.

}, issn = {2469-9926}, doi = {10.1103/PhysRevA.99.032503}, author = {Talukdar, Kaushik and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article {45527, title = {Operando X-ray absorption spectroscopy study of the Fischer-Tropsch reaction with a Co catalyst}, journal = {Journal of Synchrotron Radiation}, volume = {26}, year = {2019}, month = {JAN}, pages = {137-144}, type = {Article}, abstract = {

This article describes the setting up of a facility on the energy-scanning EXAFS beamline (BL-09) at RRCAT, Indore, India, for operando studies of structure-activity correlation during a catalytic reaction. The setup was tested by operando X-ray absorption spectroscopy (XAS) studies performed on a Co-based catalyst during the Fischer-Tropsch reaction to obtain information regarding structural changes in the catalyst during the reaction. Simultaneous gas chromatography (GC) measurements during the reaction facilitate monitoring of the product gases, which in turn gives information regarding the activity of the catalyst. The combination of XAS and GC techniques was used to correlate the structural changes with the activity of the catalyst at different reaction temperatures. The oxide catalyst was reduced to the metallic phase by heating at 400 degrees C for 5h under H-2 at ambient pressure and subsequently the catalytic reaction was studied at four different temperatures of 240, 260, 280 and 320 degrees C. The catalyst was studied for 10h at 320 degrees C and an attempt has been made to understand the process of its deactivation from the XANES and EXAFS results.

}, keywords = {catalysis, EXAFS, Fischer-Tropsch reaction, in situ studies, structure-activity correlation, XANES}, issn = {1600-5775}, doi = {10.1107/S1600577518015588}, author = {Nayak, Chandrani and Jain, Preeti and Vinod, C. P. and Jha, S. N. and Bhattacharyya, D.} } @article {46277, title = {Oxidative Olefination of Benzylamine with an Active Methylene Compound Mediated by Hypervalent Iodine (III)}, journal = {European Journal of Organic Chemistry}, year = {2019}, month = {SEP}, type = {Article}, abstract = {

Hypervalent iodine-mediated oxidative olefination of amines with an active methylene compound provides a rapid gateway towards the formation of electrophilic alkenes under mild reaction conditions in good to excellent yields. This is an efficient protocol for the preparation of substituted electrophilic alkenes.

}, doi = {10.1002/ejoc.201900970}, author = {Rupanawar, Bapurao D. and Veetil, Sruthi M. and Suryavanshi, Gurunath} } @article {45620, title = {Paintable room-temperature phosphorescent liquid formulations of alkylated bromonaphthalimide}, journal = {Angewandte Chemie - International Edition}, volume = {58}, year = {2019}, month = {FEB}, pages = {2284-2288}, type = {Article}, abstract = {Organic phosphors have been widely explored with an understanding that crystalline molecular ordering is a requisite for enhanced intersystem crossing. In this context, we explored the room-temperature phosphorescence features of a solvent-free organic liquid phosphor in air. While alkyl chain substitution varied the physical states of the bromonaphthalimides, the phosphorescence remained unaltered for the solvent-free liquid in air. As the first report, a solvent-free liquid of a long swallow-tailed bromonaphthalimide exhibits room-temperature phosphorescence in air. Doping of the phosphor with carbonyl guests resulted in enhanced phosphorescence, and hence a large-area paintable phosphorescent liquid composite with improved lifetime and quantum yield was developed.}, doi = {10.1002/anie.201811834}, author = {Goudappagouda and Manthanath, A. and Wakchaure, V. C. and Ranjeesh, K. C. and Das, T. and Vanka, K. and Nakanishi, T. and Babu, S. S.} } @article {46438, title = {Pathways to defense metabolites and evading fruit bitterness in genus Solanum evolved through 2-oxoglutarate-dependent dioxygenases}, journal = {Nature Communications}, volume = {10}, year = {2019}, month = {NOV}, pages = {5169}, type = {Article}, abstract = {

The genus Solanum comprises three food crops (potato, tomato, and eggplant), which are consumed on daily basis worldwide and also producers of notorious anti-nutritional steroidal glycoalkaloids (SGAs). Hydroxylated SGAs (i.e. leptinines) serve as precursors for leptines that act as defenses against Colorado Potato Beetle (Leptinotarsa decemlineata Say), an important pest of potato worldwide. However, SGA hydroxylating enzymes remain unknown. Here, we discover that 2-OXOGLUTARATE-DEPENDENT-DIOXYGENASE (2-ODD) enzymes catalyze SGA-hydroxylation across various Solanum species. In contrast to cultivated potato, Solanum chacoense, a widespread wild potato species, has evolved a 2-ODD enzyme leading to the formation of leptinines. Furthermore, we find a related 2-ODD in tomato that catalyzes the hydroxylation of the bitter a-tomatine to hydroxytomatine, the first committed step in the chemical shift towards downstream ripening-associated non-bitter SGAs (e.g. esculeoside A). This 2-ODD enzyme prevents bitterness in ripe tomato fruit consumed today which otherwise would remain unpleasant in taste and more toxic.

}, issn = {2041-1723}, doi = {10.1038/s41467-019-13211-4}, author = {Cardenas, Pablo D. and Sonawane, Prashant D. and Heinig, Uwe and Jozwiak, Adam and Panda, Sayantan and Abebie, Bekele and Kazachkova, Yana and Pliner, Margarita and Unger, Tamar and Wolf, Dalia and Ofner, Itai and Vilaprinyo, Ester and Meir, Sagit and Davydov, Olga and Gal-On, Amit and Burdman, Saul and Giri, Ashok and Zamir, Dani and Scherf, Tali and Szymanski, Jedrzej and Rogachev, Ilana and Aharoni, Asaph} } @article {47161, title = {Potent chitin-hydrolyzing enzyme from Myrothecium verrucaria affects growth and development of Helicoverpa armigera and plant fungal pathogens}, journal = {International Journal of Biological Macromolecules}, volume = {141}, year = {2019}, month = {DEC }, pages = {517-528}, type = {Article}, abstract = {

Chitin, a crucial structural and functional component of insects and fungi, serves as a target for pest management by utilizing novel chitinases. Here, we report the biocontrol potential of recombinant Myrothecium verrucaria endochitinase (rMvEChi) against insect pest and fungal pathogens. A complete ORF of MvEChi (1185 bp) was cloned and heterologously expressed in Escherichia coli. Structure based sequence alignment of MvEChi revealed the presence of conserved domains SXGG and DXXDXDXE specific for GH-18 family, involved in substrate binding and catalysis, respectively. rMvEChi (46.6 kDa) showed optimum pH and temperature as 7.0 and 30 degrees C, respectively. Furthermore, rMvEChi remained stable within the pH range of 6.0 to 8.0 and up to 40 degrees C. rMvEChi exhibited k(cat)/K-m values of 129.83 x 10(3) [(g/L)(-1) s(-1)] towards 4MU chitotrioside. Hydrolysis of chitooligosaccharides with various degrees of polymerization (DP) using rMvEChi indicated the release of DP2 as main end product with order of reaction as DP6 \> DP5 \> DP4 \> DP3. Bioassay of rMvEChi against Helicoverpa armigera displayed potent anti-feedant activity and induced mortality. In vitro antifungal activity against plant pathogenic fungi (Ustilago maydis and Bipolaris sorokiniana) exhibited significant inhibition of mycelium growth. These results suggest that MvEChi has significant potential in enzyme-based pest and pathogen management. (C) 2019 Elsevier B.V. All rights reserved.

}, keywords = {Biocontrol, endochitinase, Myrothecium verrucaria}, issn = {0141-8130}, doi = {10.1016/j.ijbiomac.2019.09.031}, author = {Vidhate, Ravindra P. and Bhide, Amey J. and Gaikwad, Sushama M. and Giri, Ashok P.} } @article {46209, title = {Probing the effect of selenium substitution in kesterite-Cu2ZnSnS4 nanocrystals prepared by hot injection method}, journal = {Journal of Materials Science-Materials in Electronics }, volume = {30}, year = {2019}, month = {AUG}, pages = {14781-14790}, type = {Article}, abstract = {

In this paper, we report the effect of sulfur (S) substitution with selenium (Se) in CZTS nanocrystals prepared by hot injection method. The formation of kesterite-copper zinc tin sulfide (Cu2ZnSnS4, CZTS) and copper zinc tin selenide (Cu2ZnSnSe4, CZTSe) nanocrystals is confirmed by X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy (TEM) analysis. The XRD, TEM and atomic force microscopy (AFM) analysis shows an overall increase in average crystallite size upon Se substitution. AFM images revealed an increase in root mean square surface roughness (S-q) and average surface roughness (S-a) when S in CZTS is replaced by Se. The substitution of S by Se in host CZTS narrows the optical band gap from 1.56 to 1.03 eV. The ultraviolet photoelectron spectroscopy (UPS) analysis shows shift in valence band and conduction band edge in CZTSe compared to CZTS. The photocurrent density measurement in synthesized CZTSe thin films is similar to 4 to 5 times higher than CZTS thin films. The obtained results show that CZTSe can be a promising candidate as absorber material in photovoltaic applications.

}, doi = {10.1007/s10854-019-01851-7}, author = {Pandharkar, Subhash and Rondiya, Sachin and Bhorde, Ajinkya and Nair, Shruthi and Aher, Rahul and Vairale, Priti and Waghmare, Ashish and Naik, Dhirsing and Waykar, Ravindra and Jadhav, Yogesh} } @article {46240, title = {Relativistic coupled-cluster investigation of parity (P) and time-reversal (T) symmetry violations in HgF}, journal = {Journal of Chemical Physics}, volume = {150}, year = {2019}, month = {FEB}, type = {Article}, abstract = {

We employ the Z-vector method in the four-component relativistic coupled-cluster framework to calculate the parity (P) and time-reversal (T) symmetry violating scalar-pseudoscalar nucleus-electron interaction constant (W-s), the effective electric field (E-eff) experienced by the unpaired electron, and the nuclear magnetic quadrupole moment-electron interaction constant (W-M) in the open-shell ground electronic state of HgF. The molecular frame dipole moment and the magnetic hyperfine structure (HFS) constant of the molecule are also calculated at the same level of theory. The outcome of our study is that HgF has a high value of E-eff (115.9 GV/cm), W-s (266.4 kHz), and W-M (3.59 x 10(33) Hz/e cm(2)), which shows that it can be a possible candidate for the search of new physics beyond the standard model. Our results are in good agreement with the available literature values. Furthermore, we investigate the effect of the basis set and the virtual energy functions on the computed properties. The role of the high-energy virtual spinors is found to be significant in the calculation of the HFS constant and the P,T-odd interaction coefficients. Published under license by AIP Publishing.

}, doi = {10.1063/1.5083000}, author = {Talukdar, Kaushik and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article {45628, title = {Role of Li+ and Fe3+ in modified ZnO: Structural, vibrational, opto-electronic, mechanical and magnetic properties}, journal = {Ceramics International}, volume = {45}, year = {2019}, month = {JAN}, pages = {7232-7243}, type = {Article}, abstract = {When Fe is doped in ZnO, a situation of charge imbalance is created due to the higher charge of Fe3+. A charge balance may be obtained by co-doping Li+0.5Fe3+0.5 combinations. A solid solution of Zn1-x(Fe0.5Li0.5)xO (0 <= x <= 0.03125) is synthesized with this viewpoint. The crystallites belong to a wurtzite P63mc space group, with lattice parameters a, b and c increasing nominally for x = 0.0156 and thereafter remaining invariant. The size varies in the range ~ 60{\textendash}142 nm. Interstitials of Li and Zn ions are formed. Along with Fe3+ substitution these defects are reasons for O interstitials. These oxygen interstitials increase the red emission while reduction of oxygen vacancies reduces the green emission. These point defects create structural distortion and strain which can generate Zn vacancies. Bandgap reduces due to shallow defects. Mid-bandgap states due to oxygen interstitials and Fe 3d-O 2p hybridization result in NIR emission. On the other hand the crystal surface deforms due to Li addition which hardens the materials. A weak ferromagnetism appears at very low temperature which is enhanced by Li+ addition. Long range exchange mechanism between Fe3+ ions appears in the samples, mediated by magnetic polarons due to point defects.}, keywords = {hardness, NIR emission, Shallow and deep level defects, Weak ferromagnetism, ZnO}, issn = {0272-8842}, doi = {10.1016/j.ceramint.2019.01.004}, author = {Bajpai, G. and Moirangthem, I. and Sarkar, S. and Barman, S. R. and Vinod, C. P. and Bajpai, S. and Riyajuddin, S. and Ghosh, K. and Basaula, D. R. and Khan, M. and Liu, S. -W. and Biring, S. and Sen, S.} } @article {46169, title = {Role of structural distortion in stabilizing electrosynthesized blue emitting phosphorene quantum dots}, journal = {Journal of Physical Chemistry Letters}, volume = {10}, year = {2019}, month = {MAR }, pages = {973-980}, type = {Article}, abstract = {

Luminescent phosphorene quantum dots (PQDs) have emerged as fascinating nanomaterials for potential applications in optoelectronics, catalysis, and sensing. Herein, we investigate the structural distortion of black phosphorus (BP) under an applied electric field to yield blue luminescent PQDs [average diameter 8 +/- 1.5 nm (N = 60)]. The electrosynthesized PQDs exhibit photoluminescence emission independent of excitation wavelength with 84\% quantum efficiency. Structural distortion that occurred during the transformation of BP to PQDs is confirmed by results obtained during transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Further, using first-principles-based density functional theory, calculations on oxygenated and nonoxygenated PQDs augment the experimental observations that an optimum oxygen content maintains the structural integrity of PQDs, above which the structural robustness of PQDs is drastically diminished.

}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.8b03600}, author = {Valappil, Manila Ozhukil and Joshi, Krati and John, Lisa and Krishnamurthy, Sailaja and Jana, Bikash and Patra, Amitava and Pillai, Vijayamohanan K. and Alwarappan, Subbiah} } @article {46159, title = {Silylene induced cooperative B-H bond activation and unprecedented aldehyde C-H bond splitting with amidinate ring expansion}, journal = {Chemical Communications}, volume = {55}, year = {2019}, month = {MAR }, pages = {3536-3539}, type = {Article}, abstract = {

The addition of HBpin to PhC(NtBu)(2)SiN(SiMe3)(2) (1) results in the cleavage of the B-H bond in a cooperative fashion across the Si and amidinate-C sites. The reaction of 1 with benzaldehyde led to C-H bond activation with amidinate ring expansion leading to a five-membered heterocycle. In case of 4-fluorobenzaldehyde, a C-C bond coupling takes place leading to a dioxasilolane derivative as the major product.

}, issn = {1359-7345}, doi = {10.1039/c9cc00296k}, author = {Swamy, V. S. V. S. N. and Raj, K. Vipin and Vanka, Kumar and Sen, Sakya S. and Roesky, Herbert W.} } @article {46097, title = {Solvothermal growth of PbBi2Se4 nano-flowers: a material for humidity sensor and photodetector applications}, journal = {Physica Status Solidi A-Applications and Materials Science}, volume = {216}, year = {2019}, month = {JUN}, pages = {1900065}, type = {Article}, abstract = {

In the present work, lead bismuth selenide (PbBi2Se4) nano-flowers are synthesized by using a simple solvothermal method. Humidity sensor and photodetector based on PbBi2Se4 nano-flowers are fabricated on indium tin oxide (ITO) substrates and their sensing properties are investigated. Formation of PbBi2Se4 is confirmed by XRD, EDS, and XPS whereas formation of nano-flowers is confirmed by SEM and TEM analysis. XRD analysis reveals the hexagonal crystal structure of PbBi2Se4 phase with a = b = 4.22 angstrom, and c= 17.42 angstrom. The surface morphology of PbBi2Se4 clearly shows the formation of well-organized flower-like nanostructures which closely resembles the shape of Dahlia. The elemental mapping of chemical constituents obtained from SEM-EDS analysis shows uniform distribution of chemical constituents for the Pb, Bi, and Se in PbBi2Se4 nano-flowers. The PbBi2Se4 nano-flowers based humidity sensor has a typical response time of approximate to 65s and recovery time of approximate to 75 s. In case of PbBi2Se4 nano-flowers-based photodetector, the response and recovery time are observed approximate to 121 and approximate to 123 s, respectively, under visible light illumination with photoresponsivity (5 x 10(-6)), photosensitivity (2.16\%), and quantum efficiency (1.5 x 10(4)). The obtained results demonstrate the potential applications of solvothermally grown PbBi2Se4 nano-flowers-based devices for humidity sensors and photodetectors. The ease of the present work is to develop novel material to obtain device quality humidity sensors and photodetectors.

}, keywords = {humidity sensor, PbBi2Se4, photodetector, XPS, XRD}, issn = {1862-6300}, doi = {10.1002/pssa.201900065}, author = {Aher, Rahul and Bhorde, Ajinkya and Nair, Shruthi and Borate, Haribhau and Pandharkar, Subhash and Naik, Dhirsing and Vairale, Priti and Karpe, Smita and Late, Dattatray and Prasad, Mohit and Jadkar, Sandesh} } @article {46002, title = {Stealth emulsion based on natural rubber latex, core-shell ferrofluid/carbon black in the S and X bands}, journal = {Nanotechnology}, volume = {30}, year = {2019}, month = {AUG }, pages = {315703}, type = {Article}, abstract = {

A lossy dielectric with an appropriate magnetic property is one of the requirements of a stealth material. The thickness of the absorber and the corresponding bandwidth of absorption are also other deciding factors that determine the choice of the material as microwave absorbers. A stable emulsion, which is lossy as well as magnetic, is promising, since it can be coated on surfaces with required thickness in the desired band. A magnetic nanofluidic emulsion serves the purpose. A microwave absorbing emulsion based on natural rubber latex with core-shell magnetic nanoparticles, based on superparamagnetic iron oxide nanoparticles (SPIONs), was developed. The effect of additives like carbon black on the bandwidth of absorption was also studied as a function of weight percentage of carbon black. The complex dielectric permittivity and magnetic permeability were evaluated using a vector network analyser in the S and X bands. Furthermore, these results were modelled using surface impedance equations. These investigations revealed that the incorporation of carbon black enhances the bandwidth of absorption and an emulsion with the required dielectric permittivity and magnetic permeability can be tailored for stealth applications.

}, keywords = {carbon black, core-shell nanoparticles, ferrofluid, microwave absorbing paint, natural rubber latex}, issn = {0957-4484}, doi = {10.1088/1361-6528/ab1194}, author = {Vinayasree, S. and Nair, Ajalesh Balachandran and Mani, Manoj and Archana, V. N. and Joseph, Rani and Mohanan, P. and Joy, P. A. and Anantharaman, M. R.} } @article {46267, title = {Structural insight into a membrane intrinsic Acyltransferase from Chlorobium tepidum }, journal = {Current Microbiology}, volume = {76}, year = {2019}, month = {NOV}, pages = {1290-1297}, type = {Article}, abstract = {

The Lipid A component of the outer membrane of Gram-negative bacteria is an integral part of the permeability barrier known as LPS, which actively prevents the uptake of bactericidal compounds. It is clinically very significant, as it is known to elicit a strong immune response in the humans, through the TLR4 complex. The Lipid A species are synthesized through a highly conserved multistep biosynthetic pathway. The final step is catalyzed by acyltransferases of the HtrB/MsbB family, which are members of a superfamily of enzymes, present in all domains of life with important roles to play in various biological processes. The investigation of a putative dual functioning enzyme which can add both laurate and myristate residues to the (Kdo)(2)-lipid IVA (precursor of Lipid A) would give a snapshot into the versatility of substrates that these enzymes catalyze. In this study we have cloned and purified to homogeneity, such a putative dual functional acyltransferase from Chlorobium tepidum, and attempted to study the enzyme in more details in terms of its sequence and structural aspects, as it lacks conserved residues with other enzymes of the same family.

}, doi = {10.1007/s00284-019-01743-3}, author = {Boral, Debjyoti and Vankudoth, Koteswara Rao and Ramasamy, Sureshkumar} } @article {46288, title = {Studies on the use of sodium polyacrylate (SPA) for low-salt animal skin preservation}, journal = {Environmental Science and Pollution Research}, volume = {26}, year = {2019}, month = {SEP}, pages = { 27100-27111}, type = {Article}, abstract = {

Salt-based preservation is practiced for decades in the leather industry because of its versatility, cost-effectiveness, and availability. The salt removed from the soaking process causes significant pollution including organic and elevated total dissolved solids (TDS). Hence, a low-salt skin preservation method using commercial sodium polyacrylate with a reduced quantity of sodium chloride aiming to retain leather properties and pollution reduction was the principal focus of the study. Commercial sodium polyacrylate initially characterized for water absorption capacity along with structural and functional properties is confirmed by NMR and IR spectroscopic techniques. In preliminary experiments, the process parameters attained optimized conditions of sodium polyacrylate (SPA) quantity (5\%), a minimal amount of salt (15\%), and contact time (4 h) required for skin preservation. Besides, reusability studies after SPA recovery (95\%) were applied to skins with an optimized quantity of SPA and salt subsequently stored for 15 days along with control (40\% salt). The results revealed that SPA with low salt aided an adequate curing efficiency with a substantial reduction (\> 65\%) of TDS and comparable physical and organoleptic properties on par with the conventional method. Overall, SPA supported low-salt skin preservation reduces pollutant load (TDS) caused due to using of 40\% sodium chloride in the conventional curing process.

}, doi = {10.1007/s11356-019-05871-y}, author = {Balasubramanian, Venkatakrishnan and Velappan, Brindha and Vijayan, Sandhya Kurvilla and Jabamani, Hepzibah and Nagarajan, Vedaraman and Victor, John Sundar and Ranganath, Suresha P. and Badiger, Manohar V. and Chinnaraj, Velappan kandukalpatti and Chellappa, Muralidharan} } @article {46143, title = {Surfactant free synthesis of Au@Ni core-shell nanochains in aqueous medium as efficient transfer hydrogenation catalyst}, journal = {Applied Catalysis A-General}, volume = {575}, year = {2019}, month = {APR }, pages = {93-100}, type = {Article}, abstract = {

A surfactant free aqueous phase synthesis method is reported for the generation of highly lattice mismatched Au@Ni core-shell nanochains without using any expensive and hazardous organic ligands. As synthesised Au@Ni nanochain structures showed high thermal stability and bulk oxidation resistance up to 300 degrees C. In situ near ambient pressure XPS (NAPXPS) analysis has been done for the bare Au@Ni nanochain surfaces under oxygen atmosphere and at different temperatures which showed evidence for the surface oxidation resistance of naked Au@Ni nanochains up to 200 degrees C. Ligand or capping agent free Au@Ni nanochain surfaces are found to be highly active for transfer hydrogenation of acetophenone to 1-phenyl ethanol an important commodity in perfumery industry.

}, keywords = {Au@Ni nanochains, core-shell, NAPXPS, Surfactant free, synergistic effects, transfer hydrogenation}, issn = {0926-860X}, doi = {10.1016/j.apcata.2019.01.017}, author = {Vysakh, A. B. and Shebin, K. J. and Jain, Ruchi and Sumanta, P. and Gopinath, Chinnakonda S. and Vinod, C. P.} } @article {46248, title = { Synthesis and reactivity of a hypersilylsilylene }, journal = {Inorganic chemistry}, volume = {58}, year = {2019}, month = {AUG}, pages = {10536-10542}, type = {Article}, abstract = {

Stabilization of an amidinatosilylene with a bulky tris(trimethylsilyl)silyl substituent was realized with the preparation of PhC(NtBu)(2)Si{Si(SiMe3)(3)} (1) from PhC(NtBu)(2)SiHCl2 with K{Si(SiMe3)(3)} in more than 90\% yield. The highly deshielded Si-29 NMR resonance (delta = 76.91 ppm) can be attributed to the absence of a pi-donating substituent. The molecular structure of 1 shows a trigonal-planar geometry around the Si-II center with a Si-II-Si-IV bond length of 2.4339(13) angstrom. A series of reactions of 1 with Me3NO, S, Se, and Te were performed. While siloxane derivatives (2 and 3) are obtained from reactions with Me3NO, silachalcogenones (4-6) are formed with other chalcogens. The presence of Si=E (E = S, Se, and Te) bonds in 4-6 have been confirmed by single crystal X-ray studies. Silaoxirane (7) formation was observed when 1 was treated with acetone, demonstrating the importance of the tris(trimethylsilyl)silyl group to kinetically and thermodynamically protect the silaoxirane derivative with less bulky substituents on the C atom.

}, doi = {10.1021/acs.inorgchem.9b00418}, author = {Bisai, Milan Kumar and Swamy, V. S. V. S. N. and Das, Tamal and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {46223, title = {Synthesis, biological evaluation and molecular modeling studies of novel chromone/Aza-Chromone fused alpha-aminophosphonates as src kinase inhibitors}, journal = {Journal of Scientific \& Industrial Research}, volume = {78}, year = {2019}, month = {FEB}, pages = {111-117}, type = {Article}, abstract = {

A series of novel chromone/aza-chromone fused alpha-aminophosphonate derivatives were synthesized in good yields using silica chloride as the catalyst. All the synthesized compounds were tested for their c-Src kinase inhibitory activity. Aza-chromone compound showed Src kinase inhibition with an IC50 value of 15.8 mu M. The compounds were subjected to molecular docking and dynamics simulations to study the atomic level interactions with an unphosphorylated proto-oncogenic tyrosine protein kinase Src (PDB code 1Y57) as well as phosphorylated tyrosine protein kinase Src (PDB code 2H8H). Docking and molecular dynamic results revealed phosphorylated Src tyrosine kinase protein better results than unphosphorylated tyrosine Src kinase protein. Chemoinformatics study revealed the compounds had lead like properties. Machine learning (SVR) models were built to study the structure activity correlations. A CC of 0.835 was obtained when the SVR model was applied to the 17 synthesized compounds. It is envisaged that the work will provide guidelines for future drug design efforts for Src kinase inhibitors.

}, author = {Bapat, S. and Viswanadh, N. and Mujahid, M. and Shirazi, A. N. and Tiwari, R. K. and Parang, K. and Karthikeyan, M. and Muthukrishnan, M. and Vyas, Renu} } @article {47493, title = {Synthesis, biological evaluation and molecular modeling studies of novel chromone/Aza-chromone fused α-aminophosphonates as Src kinase inhibitors}, journal = {Journal of Scientific and Industrial Research}, volume = {78}, year = {2019}, month = {FEB}, pages = {111-117}, type = {Article}, abstract = {A series of novel chromone/aza-chromone fused α-aminophosphonate derivatives were synthesized in good yields using silica chloride as the catalyst. All the synthesized compounds were tested for their c-Src kinase inhibitory activity. Aza-chromone compound showed Src kinase inhibition with an IC50 value of 15.8 {\textmu}M. The compounds were subjected to molecular docking and dynamics simulations to study the atomic level interactions with an unphosphorylated proto-oncogenic tyrosine protein kinase Src (PDB code 1Y57) as well as phosphorylated tyrosine protein kinase Src (PDB code 2H8H). Docking and molecular dynamic results revealed phosphorylated Src tyrosine kinase protein better results than unphosphorylated tyrosine Src kinase protein. Chemoinformatics study revealed the compounds had lead like properties. Machine learning (SVR) models were built to study the structure activity correlations. A CC of 0.835 was obtained when the SVR model was applied to the 17 synthesized compounds. It is envisaged that the work will provide guidelines for future drug design efforts for Src kinase inhibitors.}, author = {Bapat, Sanket and Viswanadh, N. and Mujahid, M. and Shirazi, Amir Nasrolahi and Tiwari, Rakesh and Parang, Keykavous and Karthikeyan, Muthukumarasamy and Muthukrishnan, M. and Vyas, Renu} } @article {46116, title = {Taxonomic insights into the phylogeny of Bacillus badius and proposal for its reclassification to the genus Pseudobacillus as Pseudobacillus badius comb. nov. and reclassification of Bacillus wudalianchiensis Liu et al.}, journal = {Systematic and Applied Microbiology}, volume = {42}, year = {2019}, month = {MAY}, pages = {360-372}, type = {Article}, abstract = {

The species Bacillus badius is one of the oldest members of the genus Bacillus isolated from faeces of children and was classified based on its ability to form endospores [8]. In 16S rRNA gene sequence and phylogenetic analysis, Bacillus badius DSM 23(T) shared low similarity (93.0\%) and distant relationship with B. subtilis, the type species of the genus Bacillus indicating that it does not belong to this genus. Additional strains of the species, B. badius DSM 5610, DSM 30822 and B. encimensis SGD-V-25 (which has been recently reclassified as a member of this species) were included in the study to consider intraspecies diversity. Detailed molecular phylogenetic and comparative genome analysis clearly showed that the strains of B. badius were consistently retrieved outside the cluster of Bacillus sensu stricto and also distantly related to the genera Domibacillus and Quasibacillus. Further, the data from biochemical reactions (inability to ferment most carbohydrates), polar lipids profile (presence of diphosphatidylglycerol, phosphatidylglycerol, phosphatidylethanolamine and an aminophosphoglycolipid) and fatty acids supported the molecular analysis. Thus the four B. badius strains; DSM 23(T), DSM 5610, DSM 30822 and SGD-V-25 displayed sufficient demarcating phenotypic characteristics that warrant their classification as members of a novel genus and single species, for which the name Pseudobacillus badius gen. nov. comb. nov. is proposed with Pseudobacillus badius DSM 23(T) (= ATCC 14574(T)) as the type strain. Additionally, based on our findings from phenotypic, chemotaxonomic and genotypic parameters, Bacillus wudalianchiensis DSM 100757(T) was reclassified as Pseudobacillus wudalianchiensis comb. nov. (C) 2019 Elsevier GmbH. All rights reserved.

}, keywords = {16S rRNA, Bacillus, Bacillus wudalianchiensis, Fatty acids, polar lipids, Pseudobacillus}, issn = {0723-2020}, doi = {10.1016/j.syapm.2019.03.003}, author = {Verma, Ashish and Pal, Yash and Ojha, Anup Kumar and Kumari, Munesh and Khatri, Indu and Rameshkumar, N. and Schumann, Peter and Dastager, Syed G. and Mayilraj, Shanmugam and Subramanian, Srikrishna and Krishnamurthi, Srinivasan} } @article {46244, title = { Temperature-dependent phonon dynamics of supported and suspended monolayer tungsten diselenide }, journal = {AIP Advances}, volume = {9}, year = {2019}, month = {AUG}, type = {Article}, abstract = {

Two-dimensional materials exhibit great potential for high-performance electronics applications and the knowledge of their thermal properties is extremely necessary, since they are closely related to efficient heat dissipation and electron-phonon interactions. In this study we report the temperature-dependence of the out-of-plane A(1g) Raman mode of suspended and supported CVD-grown single-crystalline tungsten diselenide (WSe2) monolayer. The A(1g) phonon wavenumber is linearly red-shifted for temperature ranging from 98 to 513 K, with first-order temperature coefficients beta of -0.0044 and -0.0064 cm(-1)/K for suspended and supported monolayer WSe2, respectively. The higher beta module value for supported sample is attributed to the increase of the phonon anharmonicity due to the phonon scattering with the surface roughness of the substrate. Our analysis of the temperature-dependent phonon dynamics reveal the influence of the substrate on thermal properties of monolayer WSe2 and provide fundamental information for developing of atomically-thin 2D materials devices. (C) 2019 Author(s).

}, doi = {10.1063/1.5118004}, author = {Carvalho, Thais C. V. and Araujo, Francisco D. V. and dos Santos, Clenilton Costa and Alencar, Luciana M. R. and Ribeiro-Soares, Jenaina and Late, Dattatray J. and Lobo, Anderson Oliveira and Souza Filho, Antonio Gomes and Alencar, Rafael S. and Viana, Bartolomeu C.} } @article {45482, title = {Thermally crosslinkable and chemically modifiable aromatic polyesters possessing pendant propargyloxy groups}, journal = {Journal of Polymer Science Part A-Polymer Chemistry}, volume = {57}, year = {2019}, month = {MAR}, pages = {588-597}, type = {Article}, abstract = {

New aromatic (co)polyesters containing pendant propargyloxy groups were synthesized by phase transfer-catalyzed interfacial polycondensation of 5-(propargyloxy)isophthaloyl chloride (P-IPC) and various compositions of P-IPC and isophthaloyl chloride with bisphenol A. FTIR and NMR spectroscopic data, respectively, revealed successful incorporation of pendant propargyloxy groups into (co)polyesters and formation of (co)polyesters with desired compositions. (Co)polyesters exhibited good solubility in common organic solvents such as chloroform, dichloromethane, and tetrahydrofuran and could be cast into transparent, flexible, and tough films from chloroform solution. Inherent viscosities and number average molecular weights of (co)polyesters were in the range 0.77-1.33 dL/g and 43,600-118,000 g/mol, respectively, indicating the achievement of reasonably high-molecular weights. The 10\% weight loss temperatures of (co)polyesters were in the range 390-420 degrees C, demonstrating their good thermal stability. (Co)polyesters exhibited T-g in the range 146-170 degrees C and T-g values decreased with increase in mol \% incorporation of P-IPC. The study of non-isothermal curing by DSC indicated thermal crosslinking of (co)polyesters via propargyloxy groups. The utility of pendant propargyloxy group was demonstrated by post-modification of the selected copolyester with 1-(4-azidobutyl)pyrene, 9-(azidomethyl)anthracene, and azido-terminated poly(ethyleneglycol) monomethyl ether via copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction. FTIR and H-1 NMR spectra confirmed that click reaction was quantitative. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 588-597

}, keywords = {Click chemistry, crosslinking, modification, polyesters, propargyloxy, step-growth polymerization}, issn = {0887-624X}, doi = {10.1002/pola.29297}, author = {Verma, Savita and Maher, Deepak M. and Nagane, Samadhan S. and Tawade, Bhausaheb V. and Wadgaonkar, Prakash P.} } @article {46340, title = {Water-promoted surface basicity in FeO(OH) for the synthesis of pseudoionones (PS) and their analogues}, journal = {Journal of Catalysis}, volume = {378}, year = {2019}, month = {OCT}, pages = {80-89}, type = {Article}, abstract = {

Use of Iron oxyhydroxide (gamma-FeO(OH)) as a robust catalyst for the synthesis of important intermediates like pseudoionones and their analogues through the C-C bond formation reactions like knoevenagel and aldol condensation is explored. These motifs are the building blocks for the construction of the sesquiterpenes as well as the diterpenes such as retinoic acid, Vitamin A etc. Iron oxyhydroxide (gamma-FeO(OH)) was synthesized and well characterized using XRD, FT-IR, TEM, XPS and adsorption studies to establish the catalytic activity. A thorough investigation on the nature of basic sites and the role of water as a promoter was explored based on dye adsorption, in situ methanol dissociation and CO2 adsorption studies. The catalyst also showed a wide range of substrate scope with active methylene groups involving various functional groups such as cyanides, esters and acetophenones along with its stability and reproducibility. (C) 2019 Elsevier Inc. All rights reserved.

}, keywords = {Bronsted basicity, Iron (III) oxyhydroxide, Knoevenagel condensation, Pseudoionones, Surface hydroxyl groups}, issn = {0021-9517}, doi = {10.1016/j.jcat.2019.08.026}, author = {Vernekar, Dnyanesh and Sakate, Sachin S. and Rode, Chandrashekhar V. and Jagadeesan, Dinesh} } @article {46231, title = {Weak intermolecular interactions in covalent organic framework-carbon nanofiber based crystalline yet flexible devices}, journal = {ACS Applied Materials \& Interfaces}, volume = {11}, year = {2019}, month = {AUG}, type = {Article}, abstract = {

The redox-active and porous structural backbone of covalent organic frameworks (COFs) can facilitate high-performance electrochemical energy storage devices. However, the utilities of such 2D materials as supercapacitor electrodes in advanced self-charging power-pack systems have been obstructed due to the poor electrical conductivity and subsequent indigent performance. Herein, we report an effective strategy to enhance the electrical conductivity of COF thin sheets through the in situ solid-state inclusion of carbon nanofibers (CNF) into the COF precursor matrix. The obtained COF-CNF hybrids possess a significant intermolecular π{\textperiodcentered}{\textperiodcentered}{\textperiodcentered}π interaction between COF and the graphene layers of the CNF. As a result, these COF-CNF hybrids (DqTp-CNF and DqDaTp-CNF) exhibit good electrical conductivity (0.25 {\texttimes} 10{\textendash}3\ S cm{\textendash}1), as well as high performance in electrochemical energy storage (DqTp-CNF: 464 mF cm{\textendash}2\ at 0.25 mA cm{\textendash}2). Also, the fabricated, mechanically strong quasi-solid-state supercapacitor (DqDaTp-CNF SC) delivered an ultrahigh device capacitance of 167 mF cm{\textendash}2\ at 0.5 mA cm{\textendash}2. Furthermore, we integrated a monolithic photovoltaic self-charging power pack by assembling DqDaTp-CNF SC with a perovskite solar cell. The fabricated self-charging power pack delivered excellent performance in the areal capacitance (42 mF cm{\textendash}2) at 0.25 mA cm{\textendash}2\ after photocharging for 300 s.

}, doi = {10.1021/acsami.9b08625}, author = {Mohammed, Abdul Khayum and Vijayakumar, Vidyanand and Halder, Arjun and Ghosh, Meena and Addicoat, Matthew and Bansode, Umesh and Kurungot, Sreekumar and Banerjee, Rahul} } @article {46233, title = {Zinc ion interactions in a two-dimensional covalent organic framework based aqueous zinc ion battery}, journal = {Chemical Science}, year = {2019}, month = {AUG}, type = {Article}, abstract = {

The two-dimensional structural features of covalent organic frameworks (COFs) can promote the electrochemical storage of cations like H+, Li+, and Na+\ through both faradaic and non-faradaic processes. However, the electrochemical storage of cations like Zn2+\ ion is still unexplored although it bears a promising divalent charge. Herein, for the first time, we have utilized hydroquinone linked β-ketoenamine COF acting as a Zn2+\ anchor in an aqueous rechargeable zinc ion battery. The charge-storage mechanism comprises of an efficient reversible interlayer interaction of Zn2+\ ions with the functional moieties in the adjacent layers of COF (-182.0 kcal mol-1). Notably, due to the well-defined nanopores and structural organization, a constructed full cell, displays a discharge capacity as high as 276 mA h g-1\ at a current rate of 125 mA g-1.

}, doi = {10.1039/C9SC03052B}, author = {Mohammed, Abdul Khayum and Ghosh, Meena and Vijayakumar, Vidyanand and Halder, Arjun and Nurhuda, Maryam and Kumar, Sushil and Addicoat, Matthew and Kurungot, Sreekumar and Banerjee, Rahul} } @article {46680, title = {Access to diverse germylenes and a six-membered dialane with a flexible beta-diketiminate}, journal = {Chemical Communications}, volume = {56}, year = {2020}, month = {OCT}, pages = {11871-11874}, type = {Article}, abstract = {

A nacnac-based tridentate ligand containing a picolyl group (L) was employed to isolate chlorogermylene (1). The reaction of1with another equivalent of GeCl2 center dot dioxane surprisingly gave pyridylpyrrolide-based chlorogermylene (2)viaC-N bond cleavage and C-C coupling, while with AlCl3, it afforded a transmetalated product,4. The reaction of L with AlH3 center dot NMe2Et led to an unusual cyclohexane type six-membered dialane heterocycle (5).

}, issn = {1359-7345}, doi = {10.1039/d0cc05202g}, author = {Pahar, Sanjukta and Swamy, V. S. V. S. N. and Das, Tamal and Gonnade, Rajesh G. and Vanka, Kumar and Sen, Sakya S.} } @article {46716, title = {Amidinato germylene-zinc complexes: synthesis, bonding, and reactivity}, journal = {Chemistry-An Asian Journal}, volume = {15}, year = {2020}, month = {OCT }, pages = {3116-3121}, type = {Article}, abstract = {

Despite the explosive growth of germylene compounds as ligands in transition metal complexes, there is a modicum of precedence for the germylene zinc complexes. In this work, the synthesis and characterization of new germylene zinc complexes [PhC(NtBu)(2)Ge{N(SiMe3)(2)}-\> ZnX2](2)(X= Br (2) and I (3)) supported by (benz)-amidinato germylene ligands are reported. The solid-state structures of2and3have been validated by single-crystal X-ray diffraction studies, which revealed the dimeric nature of the complexes, with distorted tetrahedral geometries around the Ge and Zn center. DFT calculations reveal that the Ge-Zn bonds in2and3are dative in nature. The reaction of2with elemental sulfur resulted in the first structurally characterized germathione stabilized ZnBr(2)complexes PhC(NtBu)(2)Ge(=S){N(SiMe3)(2)}-\> ZnBr2(5). Therefore, the Ge=S in5is in-between Ge-S single and Ge=S double bond length, owing to the coordination of a sulfur lone pair of electrons to ZnBr2.

}, keywords = {DFT, Germathione, Germylene, X-ray Structure, zinc}, issn = {1861-4728}, doi = {10.1002/asia.202000807, Early Access Date = SEP 2020}, author = {Yadav, Sandeep and Kumar, Rohit and Raj, K. Vipin and Yadav, Prashant and Vanka, Kumar and Sen, Sakya S.} } @article {46752, title = {Antibacterial properties of glycosylated surfaces: variation of the glucosidal moiety and fatty acid conformation of grafted microbial glycolipids}, journal = {Molecular Systems Design \& Engineering}, volume = {5}, year = {2020}, month = {AUG}, pages = {1307-1316}, type = {Article}, abstract = {

Glycosylated surfaces can display antimicrobial properties. It has been shown that sophorolipids can be used to develop biocidal coatings against Gram-positive and Gram-negative bacteria, but with a limited efficiency so far. Therefore, it appears necessary to further investigate the surface antibacterial activity of a broader set of structurally related glycolipids. The present work explores the influence of the glucosidic moiety (gluco-, sophoro-, cellobio-) and the fatty acid backbone (saturated,cisortransmonounsaturated). We show that the fatty acid backbone plays an important role:cisderivative of sophorolipids (SL) grafted onto model gold surfaces has better biocidal properties than saturated (SL0) andtransmonounsaturated (SLt) molecules, which appear to be inefficient. The number of glucose units is also a key factor: a one-third decrease in antibacterial activity is observed when having one glucose unit (GL) compared to two (SL). Sugar acetylation (SLa) does not seem to have an impact on the biocidal properties of surfaces. These results are not limited to sophorolipids, with cellobioselipids (CL) leading to similar antibacterial observations.

}, issn = {2058-9689}, doi = {10.1039/d0me00059k}, author = {Valotteau, Claire and Roelants, Sophie L. K. V. and Dhasaiyan, Prabhu and Zibek, Susanne and Guenther, Michael and Soetaert, Wim and Everaert, Bernd and Pradier, Claire-Marie and Babonneau, Florence and Baccile, Niki and Humblot, Vincent} } @article {47014, title = {Antidiabetic activity of dihydropyrimidine scaffolds and structural insight by single crystal x-ray studies}, journal = {Medicinal Chemistry}, volume = {16}, year = {2020}, month = {JAN}, pages = {996-1003}, type = {Article}, abstract = {

Background: This research project is designed to identify the anti-diabetic effects of the newly synthesized compounds to conclude the perspective of consuming one or more of these new synthetic compounds for diabetes management. Introduction: A series of dihydropyrimidine (DHPM) derivative bearing electron releasing and electron-withdrawing substituent{\textquoteright}s on phenyl ring (a-j) were synthesized and screened for antihyperglycemic(anti-diabetic) activity on streptozotocin (STZ) induced diabetic rat model. The newly synthesized compounds were characterized by using FT-IR, melting point, H-1 and C-13 NMR analysis. The crystal structure and supramolecular features were analyzed through single-crystal X-ray study. Anti-diabetic activity testing of newly prepared DHPM scaffolds was mainly based on their relative substituent on the phenyl ring along with urea and thiourea. Among the synthesized DHPM scaffold, the test compound c having chlorine group on phenyl ring at the ortho position to the hydropyrimidine ring with urea and methyl acetoacetate derivative shows moderate lowering of glucose level. However, the title compounds methyl 4-(4-hydroxy-3-methoxyphenyl)-6-methyl-2-thioxo-1,2,3,4-tetrahydropyrimi dine-5-carboxylate(g) and ethyl 4-(3-ethoxy-4-hydroxyphenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydroprimidine- 5-carboxylate(h) having methoxy and ethoxy substituents on phenyl ring show significant hypoglycemic activity compared to the remaining compounds from the Scheme 1. Methods: The experimental rat models for the study were divided into 13 groups (n = 10); group 1 animals were treated with 0.5\% CMC (0.5mL) (vehicle); group 2 were considered the streptozotocin (STZ)/nicotinamide diabetic control group (DC) and untreated, group 3 diabetic animals were administered with gliclazide 50 mg/kg and act as a reference drug group. The remaining groups of the diabetic animals were administered with the newly synthesized dihydropyrimidine compounds in a single dose of 50 mg/kg orally using the oral gavage, daily for 7 days continuously. The blood glucose level was measured before and 72 hrs after nicotinamide-STZ injection, for confirmation of hyperglycemia and type 2 diabetes development. Results: Blood glucose levels were significantly (p\<0.05) reduced after treatment with these derivatives. The mean percentage reduction for gliclazide was 50\%, while that of synthesized compounds were approximately 36\%. Conclusion: Our result suggests that the synthesized new DEEM derivative containing alkoxy group on the phenyl ring shows a significant lowering of glucose level compared to other derivatives.

}, keywords = {anti-Diabetic, blood glucose levels, dihydropyrimidine, hypoglycemic activity, Streptozotocin, type 2 diabetes mellitus}, issn = {1573-4064}, doi = {10.2174/1573406416666191227123048}, author = {Bairagi, Keshab M. and Younis, Nancy S. and Emeka, Promise M. and Sangtani, Ekta and Gonnade, Rajesh G. and Venugopala, Katharigatta N. and Alwassil, I. Osama and Khalil, Hany E. and Nayak, Susanta K.} } @article {46614, title = {Bacterial biofilm formation using PCL/curcumin electrospun fibers and its potential use for biotechnological applications}, journal = {Materials}, volume = {13}, year = {2020}, month = {DEC}, pages = {5556}, type = {Article}, abstract = {

Electrospun nanofibers are used for many applications due to their large surface area, mechanical properties, and bioactivity. Bacterial biofilms are the cause of numerous problems in biomedical devices and in the food industry. On the other hand, these bacterial biofilms can produce interesting metabolites. Hence, the objective of this study is to evaluate the efficiency of poly (x190;- caprolactone)/Curcumin (PCL/CUR) nanofibers to promote bacterial biofilm formation. These scaffolds were characterized by scanning electron microscopy (SEM), which showed homogeneous fibers with diameters between 441-557 nm; thermogravimetric analysis and differential scanning calorimetry (TGA and DSC) demonstrated high temperature resilience with degradation temperatures over \>350 degrees C; FTIR and H-1-NMR serve as evidence of CUR incorporation in the PCL fibers. PCL/CUR scaffolds successfully promoted the formation of Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa biofilms. These results will be valuable in the study of controlled harvesting of pathogenic biofilms as well as in metabolites production for biotechnological purposes.

}, keywords = {Bacteria, curcumin, electrospinning, Escherichia coli, Pseudomona aeruginosa, Staphylococcus aureus}, doi = {10.3390/ma13235556}, author = {Pompa-Monroy, Daniella Alejandra and Figueroa-Marchant, Paulina Guadalupe and Dastager, Syed G. and Thorat, Meghana Namdeo and Iglesias, Ana Leticia and Miranda-Soto, Valentin and Perez-Gonzalez, Graciela Lizeth and Villarreal-Gomez, Luis Jesus} } @article {47319, title = {Boron nitride and oxide supported on dendritic fibrous nanosilica for catalytic oxidative dehydrogenation of propane}, journal = {ACS Sustainable Chemistry \& Engineering}, volume = {8}, year = {2020}, month = {NOV }, pages = {16124-16135}, type = {Article}, abstract = {

In this work, we were able to significantly increase the activity of boron nitride (BN) catalysts used for the oxidative dehydrogenation (ODH) of propane by designing and synthesizing BN supported on dendritic fibrous nanosilica (DFNS). DFNS/BN showed a markedly increased catalytic efficiency, accompanied by exceptional stability and selectivity. Textural characterization, together with solid-state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopic analyses, indicates the presence of a combination of unique fibrous morphology of DFNS and various boron sites connected to silica to be the reason for this increase in the catalytic performance. Notably, DFNS/B2O3 also showed catalytic activity, although with more moderate selectivity compared to that of DFNS/BN. Solid-state NMR spectra indicate that the higher selectivity of DFNS/BN might stem from a larger amount of hydrogen-bonded hydroxyl groups attached to B atoms. This study indicates that both boron nitride and oxide are active catalysts and by using high surface area support (DFNS), conversion from propane to propene as well as productivity of olefins was significantly increased.

}, keywords = {Electron microscopy, heterogeneous catalysis, Nanostructures, NMR spectroscopy, propane dehydrogenation, X-ray diffraction, X-ray photoelectron spectroscopy}, issn = {2168-0485}, doi = {10.1021/acssuschemeng.0c04148}, author = {Belgamwar, Rajesh and Rankin, Andrew G. M. and Maity, Ayan and Mishra, Amit Kumar and Gomez, Jennifer S. and Trebosc, Julien and Vinod, Chathakudath P. and Lafon, Olivier and Polshettiwar, Vivek} } @article {46776, title = {Catalytic reductive deoxygenation of esters to ethers driven by hydrosilane activation through non-covalent interactions with a fluorinated borate salt}, journal = {Catalysis Science \& Technology}, volume = {10}, year = {2020}, month = {JUL}, pages = {4586-4592}, type = {Article}, abstract = {

We report the catalytic and transition metal-free reductive deoxygenation of esters to ethers through the use of a hydrosilane and a fluorinated borate BArF salt as a catalyst. Experimental and theoretical studies support the role of noncovalent interactions between the fluorinated catalyst, the hydrosilane and the ester substrate in the reaction mechanism.

}, issn = {2044-4753}, doi = {10.1039/d0cy00775g}, author = {Rysak, Vincent and Dixit, Ruchi and Trivelli, Xavier and Merle, Nicolas and Agbossou-Niedercorn, Francine and Vanka, Kumar and Michon, Christophe} } @article {46688, title = {CO2 hydrogenation to formate by palladium nanoparticles supported on N-incorporated periodic mesoporous organosilica}, journal = {ACS Sustainable Chemistry \& Engineering}, volume = {8}, year = {2020}, month = {OCT }, pages = {14765-14774}, type = {Article}, abstract = {

Development of a heterogeneous catalyst capable of selective transformation of CO2 to valuable products still remains a challenge. In this article, we account for the surfactant-directed synthesis of a new framework-incorporated nitrogen-containing periodic mesoporous organosilica nanosphere (NPMO). A thoroughly characterized N-incorporated hybrid PMO was utilized as a platform for stabilizing well-dispersed and easily accessible Pd nanoparticles (Pd-NPMO) without using any stabilizing agents or expensive dendrimers. Further, this bifunctional hybrid catalyst has been demonstrated to heterogeneously catalyze aqueous phase CO2 hydrogenation (CO2/H-2 ratio 1:3) for the direct synthesis of formate under 4 MPa pressure and at 100 degrees C. To validate the superior performance of the Pd-NPMO catalyst, we compared the activity with Pd-SBA-15 catalysts, and the results showed a 10-fold increase in turnover frequency of 108 h(-1) using Pd on NPMO which envisaged the crucial role of nitrogen sites in this catalyst to boost the CO2 valorization to formate.

}, keywords = {CO2 hydrogenation, Formic acid synthesis, Hybrid silica, Pd nanoparticles, PMO}, issn = {2168-0485}, doi = {10.1021/acssuschemeng.0c03860}, author = {Betsy, K. J. and Lazar, Anish and Pavithran, Anjuna and Vinod, C. P.} } @article {47013, title = {Design of novel drug-like molecules using informatics rich secondary metabolites analysis of Indian medicinal and aromatic plants}, journal = {Combinatorial Chemistry \& High Throughput Screening}, volume = {23}, year = {2020}, month = {JAN}, pages = {1113-1131}, type = {Article}, abstract = {

Background: Several medicinal plants are being used in Indian medicine systems from ancient times. However, in most cases, the specific molecules or the active ingredients responsible for the medicinal or therapeutic properties are not yet known. Objective: This study aimed to report a computational protocol as well as a tool for generating novel potential drug candidates from the bioactive molecules of Indian medicinal and aromatic plants through the chemoinformatics approach. Methods: We built a database of the Indian medicinal and aromatic plants coupled with associated information (plant families, plant parts used for the medicinal purpose, structural information, therapeutic properties, etc.) We also developed a Java-based chemoinformatics open-source tool called DoMINE (Database of Medicinally Important Natural products from plantaE) for the generation of virtual library and screening of novel molecules from known medicinal plant molecules. We employed chemoinformatics approaches to in-silico screened metabolites from 104 Indian medicinal and aromatic plants and designed novel drug-like bioactive molecules. For this purpose, 1665 ring containing molecules were identified by text mining of literature related to the medicinal plant species, which were later used to extract 209 molecular scaffolds. Different scaffolds were further used to build a focused virtual library. Virtual screening was performed with cluster analysis to predict drug-like and lead-like molecules from these plant molecules in the context of drug discovery. The predicted drug-like and lead-like molecules were evaluated using chemoinformatics approaches and statistical parameters, and only the most significant molecules were proposed as the candidate molecules to develop new drugs. Results and Conclusion: The supra network of molecules and scaffolds identifies the relationship between the plant molecules and drugs. Cluster analysis of virtual library molecules showed that novel molecules had more pharmacophoric properties than toxicophoric and chemophoric properties. We also developed the DoMINE toolkit for the advancement of natural product-based drug discovery through chemoinformatics approaches. This study will be useful in developing new drug molecules from the known medicinal plant molecules. Hence, this work will encourage experimental organic chemists to synthesize these molecules based on the predicted values. These synthesized molecules need to be subjected to biological screening to identify potential molecules for drug discovery research.

}, keywords = {Drugs, medicinal plants, Metabolites, scaffolds, text mining, virtual libraries, virtual screening}, issn = {1386-2073}, doi = {10.2174/1386207323666200606211342}, author = {Karade, Divya and Vijayasarathi, Durairaj and Kadoo, Narendra and Vyas, Renu and Ingle, P. K. and Karthikeyan, Muthukumarasamy} } @article {47006, title = {Dioxolanone-anchored poly(allyl ether)-based cross-linked dual-salt polymer electrolytes for high-voltage lithium metal batteries}, journal = {ACS Applied Materials \& Interfaces}, volume = {12}, year = {2020}, month = {JAN }, pages = {567-579}, type = {Article}, abstract = {

Novel cross-linked polymer electrolytes (XPEs) are synthesized by free-radical copolymerization induced by ultraviolet (UV)-light irradiation of a reactive solution, which is composed of a difunctional poly(ethylene glycol) diallyl ether oligomer (PEGDAE), a monofunctional reactive diluent 4-vinyl-1,3-dioxolan-2-one (VEC), and a stock solution containing lithium salt (lithium bis(trifluoromethanesulfonyl)imide, LiTFSI) in a carbonate-free nonvolatile plasticizer, poly(ethylene glycol) dimethyl ether (PEGDME). The resulting polymer matrix can be represented as a linear polyethylene chain functionalized with cyclic carbonate (dioxolanone) moieties and cross-linked by ethylene oxide units. A series of XPEs are prepared by varying the [O]/[Li] ratio (24 to 3) of the stock solution and thoroughly characterized using physicochemical (thermogravimetric analysis-mass spectrometry, differential scanning calorimetry, NMR, etc.) and electrochemical techniques. In addition, quantum chemical calculations are performed to elucidate the correlation between the electrochemical oxidation potential and the lithium ion-ethylene oxide coordination in the stock solution. Later, lithium bis(fluorosulfonyl)imide (LiFSI) salt is incorporated into the electrolyte system to produce a dual-salt XPE that exhibits improved electrochemical performance, a stable interface against lithium metal, and enhanced physical and chemical characteristics to be employed against high-voltage cathodes. The XPE membranes demonstrated excellent resistance against lithium dendrite growth even after reversibly plating and stripping lithium ions for more than 1000 h with a total capacity of 0.5 mAh cm(-2). Finally, the XPE films are assembled in a lab-scale lithium metal battery configuration by using carbon-coated LiFePO4 (LFP) or LiNi0.8Co0.15Al0.05O2 (NCA) as a cathode and galvanostatically cycled at 20, 40, and 60 degrees C. Remarkably, at 20 degrees C, the NCA-based lithium metal cells displayed excellent cycling stability and good capacity retention (\>50\%) even after 1000 cycles.

}, keywords = {cross-linked polymer electrolyte, dual-salt electrolyte, high-voltage cathode, lithium metal battery, solvent-free photopolymerization}, issn = {1944-8244}, doi = {10.1021/acsami.9b16348}, author = {Vijayakumar, Vidyanand and Diddens, Diddo and Heuer, Andreas and Kurungot, Sreekumar and Winter, Martin and Nair, Jijeesh Ravi} } @article {46830, title = {Distinct metabolic states of a cell guide alternate fates of mutational buffering through altered proteostasis}, journal = {Nature Communications}, volume = {11}, year = {2020}, month = {JUN}, pages = {2926}, type = {Article}, abstract = {

Metabolic changes alter the cellular milieu; can this also change intracellular protein folding? Since proteostasis can modulate mutational buffering, if change in metabolism has the ability to change protein folding, arguably, it should also alter mutational buffering. Here we find that altered cellular metabolic states in E. coli buffer distinct mutations on model proteins. Buffered-mutants have folding problems in vivo and are differently chaperoned in different metabolic states. Notably, this assistance is dependent upon the metabolites and not on the increase in canonical chaperone machineries. Being able to reconstitute the folding assistance afforded by metabolites in vitro, we propose that changes in metabolite concentrations have the potential to alter protein folding capacity. Collectively, we unravel that the metabolite pools are bona fide members of proteostasis and aid in mutational buffering. Given the plasticity in cellular metabolism, we posit that metabolic alterations may play an important role in cellular proteostasis.

}, issn = {2041-1723}, doi = {10.1038/s41467-020-16804-6}, author = {Verma, Kanika and Saxena, Kanika and Donaka, Rajashekar and Chaphalkar, Aseem and Rai, Manish Kumar and Shukla, Anurag and Zaidi, Zainab and Dandage, Rohan and Shanmugam, Dhanasekaran and Chakraborty, Kausik} } @article {46923, title = {Dynamics in amine-functionalized mesoporous hybrid materials probed through deuterium magic angle spinning NMR and molecular dynamic simulations}, journal = {Journal of Physical Chemistry C}, volume = {124}, year = {2020}, month = {MAR}, pages = {6154-6170}, type = {Article}, abstract = {

We present a deuterium magic angle spinning (MAS) NMR study on two widely used hybrid materials (3-glycidyloxy propyl)trimethoxysilane (3-GPTMS) and 3-(trimethoxysilyl)propyl methacrylate (3-MATMS) grafted on SBA-15. Methylene-deuterated diamine as a pendent group is anchored to GPTMS (O3Si-CH2-CH2-CH2-O-CH2-CH(OH)- CH2-NH-CD2-CD2-NH2) and MATMS (O3Si-CH2-CH2-CH2-O-C(N-CD2-CD2-NH2)-C(CH3)=-CH2) postgrafting. Proton and deuterium solid state NMR experiments under MAS were performed at two hydration levels and temperatures ranging from 253 to 315 K. Deuterium spectra were deconvoluted into three A Dr, components with different average quadrupolar parameters: a relatively rigid component arising from local or librational motion of C-H-2(2) corresponding to {\textquoteleft}{\textquoteleft}small angle{\textquoteright}{\textquoteright} jumps, an intermediate dynamic component, and a large amplitude dynamic component. Population ratios of rigid versus dynamic components show that diamine-MATMS is more rigid when compared with diamine-GPTMS at high hydration. The role of the length of the linkers, steric hindrance, grafting concentration, etc. in defining mobility is investigated. Finally, by correlating proton and deuterium MAS NMR spectral analysis, the role of a few water molecules in inducing dynamics of the linkers was investigated. Molecular dynamic (MD) simulations support the experimental analysis. MD simulations indicate different types of mobility arising from the same molecular binding configuration of diamine-MATMS. Dynamics induced by a few hydroxyls on the pore surface accessible to the linker, various molecular conformations, and stabilization of the linker through hydrogen bonding with the surface, derived from MD simulations, are discussed.

}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.9b11948}, author = {Veena, V. S. and Kavya, I and Lazar, A. and Vinod, C. P. and Ajithkumar, T. G. and Jayanthi, S.} } @article {46740, title = {Effect of bio-filler on hybrid sisal-banana-kenaf-flax based epoxy composites: a statistical correlation on flexural strength}, journal = {Journal of Bionic Engineering}, volume = {17}, year = {2020}, month = {NOV}, pages = {1263-1271}, type = {Article}, abstract = {

This work deals with the investigation of the synergistic effect of bagasse ash with sisal-banana-kenaf-flax fibers reinforced epoxy composite for their flexural behavior. The composites with three combinations of hybrid fibers viz. sisal/kenaf (HSK), banana/kenaf (HBK), and banana/flax (HBF) with bagasse ash (BGA) as filler material are fabricated using vacuum bag assisted resin transfer molding. Experiments were conducted based on L27 orthogonal array to understand the influence of control factor viz. fiber volume, alkali concentration \& BGA over output response.X-ray micro computed tomography analysis was conducted over the developed sample to infer the uniform dispersion of fiber and filler material. The experimental results reveal that the addition of fiber up to 30 vol\% depicts better strength and further addition results in a negative impact. Increasing in order of BGA decreases the flexural strength of the developed composites.

}, keywords = {bagasse ash, flexural strength, natural fiber, vacuum bag assisted resin transfer molding, X-ray micro computed tomography}, issn = {1672-6529}, doi = {10.1007/s42235-020-0083-7, Early Access Date = AUG 2020}, author = {Vivek, Somasundaram and Kanthavel, Karuppusamy and Torris, Arun and Kavimani, Vijayananth} } @article {46690, title = {Effect of solvent-substrate noncovalent interactions on the diastereoselectivity in the intramolecular carbonyl-ene and the staudinger [2+2] cycloaddition reactions}, journal = {Journal of Physical Chemistry A}, volume = {124}, year = {2020}, month = {OCT }, pages = {8019-8028}, type = {Article}, abstract = {

Noncovalent interactions (NCIs) have been identified as important contributing factors for determining selectivity in organic transformations. However, cases where NCIs between solvents and substrates are responsible for a major extent for determining selectivity are rare. The current computational study with density functional theory identifies two important transformations where this is the case: the intramolecular carbonyl-ene reaction and the Staudinger [2 + 2] cycloaddition reaction. In both cases, the role of explicit solvent molecules interacting non-covalently with the substrate has been taken into account. Calculations indicate that the diastereomeric ratio would be 95.0:5.0 for the formation of tricyclic tetrahydrofuran diastereomers via the intramolecular carbonyl-ene reaction and 94.0:6.0 for the formation of the triflone diastereomers via the Staudinger [2 + 2] cycloaddition reaction, which corroborates with the experiment. Interestingly, in both the cases, the calculations indicate that noninclusion of explicit solvent molecules would lead to only a small difference between the competing transition states, which leads to the conclusion that solvent-substrate NCIs are the major cause for diastereoselectivity in both the cases considered.

}, issn = {1089-5639}, doi = {10.1021/acs.jpca.0c05738}, author = {Jain, Shailja and Vanka, Kumar} } @article {46641, title = {Electronic structure parameter of nuclear magnetic quadrupole moment interaction in metal monofluorides}, journal = {Journal of Chemical Physics}, volume = {153}, year = {2020}, month = {NOV}, pages = {184306}, type = {Article}, abstract = {

The electronic structure parameter (W-M) of the nuclear magnetic quadrupole moment (MQM) interaction in numerous open-shell metal monofluorides (viz., MgF, CaF, SrF, BaF, RaF, and PbF) is computed in the fully relativistic coupled-cluster framework. The electron-correlation effects are found to be very important for the precise calculation of W-M in the studied molecular systems. The molecular MQM interaction parameter scales nearly as Z(2) in the alkaline earth metal monofluorides, where Z is the nuclear charge of metal. Our study identifies (RaF)-Ra-223 as a good candidate for the experimental search of the nuclear MQM, which can help unravel the physics beyond the standard model in the hadron sector of matter.

}, issn = {0021-9606}, doi = {10.1063/5.0028669}, author = {Talukdar, Kaushik and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article {46900, title = {Electrospun fibers and sorbents as a possible basis for effective composite wound dressings}, journal = {Micromachines}, volume = {11}, year = {2020}, month = {APR}, pages = {441}, type = {Article}, abstract = {

Skin burns and ulcers are considered hard-to-heal wounds due to their high infection risk. For this reason, designing new options for wound dressings is a growing need. The objective of this work is to investigate the properties of poly (epsilon-caprolactone)/poly (vinyl-pyrrolidone) (PCL/PVP) microfibers produced via electrospinning along with sorbents loaded with Argovit (TM) silver nanoparticles (Ag-Si/Al2O3) as constituent components for composite wound dressings. The physicochemical properties of the fibers and sorbents were characterized using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and inductively coupled plasma optical emission spectroscopy (ICP-OES). The mechanical properties of the fibers were also evaluated. The results of this work showed that the tested fibrous scaffolds have melting temperatures suitable for wound dressings design (58-60 degrees C). In addition, they demonstrated to be stable even after seven days in physiological solution, showing no macroscopic damage due to PVP release at the microscopic scale. Pelletized sorbents with the higher particle size demonstrated to have the best water uptake capabilities. Both, fibers and sorbents showed antimicrobial activity against Gram-negative bacteria Pseudomona aeruginosa and Escherichia coli, Gram-positive Staphylococcus aureus and the fungus Candida albicans. The best physicochemical properties were obtained with a scaffold produced with a PCL/PVP ratio of 85:15, this polymeric scaffold demonstrated the most antimicrobial activity without affecting the cell viability of human fibroblast. Pelletized Ag/Si-Al2O3-3 sorbent possessed the best water uptake capability and the higher antimicrobial activity, over time between all the sorbents tested. The combination of PCL/PVP 85:15 microfibers with the chosen Ag/Si-Al2O3-3 sorbent will be used in the following work for creation of wound dressings possessing exudate retention, biocompatibility and antimicrobial activity.

}, keywords = {electrospinning, poly (epsilon-caprolactone), poly (vinyl pyrrolidone), silver sorbents, wound dressings}, doi = {10.3390/mi11040441}, author = {Saul Alvarez-Suarez, Alan and Dastager, Syed G. and Bogdanchikova, Nina and Grande, Daniel and Pestryakov, Alexey and Carlos Garcia-Ramos, Juan and Lizeth Perez-Gonzalez, Graciela and Juarez-Moreno, Karla and Toledano-Magana, Yanis and Smolentseva, Elena and Antonio Paz-Gonzalez, Juan and Popova, Tatiana and Rachkovskaya, Lyubov and Nimaev, Vadim and Kotlyarova, Anastasia and Korolev, Maksim and Letyagin, Andrey and Jesus Villarreal-Gomez, Luis} } @article {46837, title = {Engineering pore morphology using silica template route over mesoporous cobalt oxide and its implications in atmospheric pressure carbon dioxide hydrogenation to olefins}, volume = {19}, year = {2020}, month = {JUN}, pages = {100586}, type = {Article}, abstract = {

Highly ordered mesoporous cobalt oxides (denoted as m-Co-KIT-6 and m-Co-SBA-15) with three dimensional and two dimensional pore morphology respectively have been synthesized using 3D KIT-6, and 2D SBA-15 as silica template via nanocasting route. CO2 hydrogenation activity was evaluated for these mesoporous materials under atmospheric pressure conditions. In comparison to nanoparticles of cobalt oxide (Co3O4-nano), mesoporous catalysts showed excellent activity for CO2 hydrogenation due to their higher number of exposed active sites and lower mass diffusion limitations. The ordered mesoporous structure of Co3O4 catalysts favored the chain growth of carbon atoms for the production of C2+ hydrocarbons while Co3O4 nanoparticles showed strong selectivity toward CH4. High selectivity for C2+ (similar to 25\%) was obtained for both m-Co-KIT-6 and m-Co-SBA-15 catalysts at 320 degrees C. In addition, the 3D pore structure of m-Co-KIT-6 catalyst exclusively formed more olefins (54.9\%) fraction. (C) 2020 Published by Elsevier Ltd.

}, keywords = {CO2 hydrogenation, Mesoporous CO3O4, Olefin fraction, Pore morphology, Silica hard template}, issn = {2352-9407}, doi = {10.1016/j.apmt.2020.100586}, author = {Gupta, Sharad and Ciotonea, Carmen and Royer, Sebastien and Dacquin, Jean-Philippe and Vinod, C. P.} } @article {46971, title = {Enhancing thermomechanical and chemical stability of polymer electrolyte membranes using polydopamine coated nanocellulose}, journal = {ACS Applied Energy Materials}, volume = {3}, year = {2020}, month = {FEB}, pages = {1988-1999}, type = {Article}, abstract = {

We report here an approach to enhance the chemical and thermomechanical stability of polymer electrolyte membranes without compromising proton conductivity. Multifunctional polydopamine coated nanocellulose (PNC) was prepared by oxidative polymerization of dopamine on nano cellulose fibers and subsequently incorporated in Nafion by solution blending. PNC had a very significant effect on the thermomechanical properties of Nafion showing up to 200\% improvement in the storage modulus at 90 degrees C. The PNC network also enhanced the dimensional stability of Nafion under constant stress. The 3 wt \% PNC composite membrane showed a drastic reduction in creep compliance of about 39.9\% and 46.5\% in J(max) at 30 degrees and 60 degrees C, respectively. Free radical scavenging properties of polydopamine also helped to significantly enhance the chemical stability of Nafion, which was ascertained by accelerated degradation tests conducted in Fenton{\textquoteright}s reagent at 70 degrees C over 40 days. F-19 CP MAS solid state NMR, FTIR, and tensile tests on the membranes show higher chemical stability of the 3 wt \% PNC composite membrane. The proton conductivity of the 3 wt \% PNC composite membrane at 90 degrees C and 100\% RH (similar to 125 mS/cm) was slightly higher than the Nafion membrane (similar to 94 mS/cm) at similar conditions. The retention of proton conductivity even with lower water uptake could be ascribed to proton hopping through polydopamine coated nanocellulose. Performance of the composite membrane was also evaluated in a single stack fuel cell and found to be better than recast Nafion. The benefits derived by this approach are not restricted to Nafion alone and shall broadly apply to many other polymer membranes.

}, keywords = {cellulose nanofibers, chemical stability, dimensional stability, fuel cell, polydopamine, polymer electrolyte membrane}, issn = {2574-0962}, doi = {10.1021/acsaem.9b02417}, author = {Ram, Farsa and Velayutham, Parthiban and Sahu, Akhila Kumar and Lele, Ashish K. and Shanmuganathan, Kadhiravan} } @article {46989, title = {Enzymatic and non-enzymatic detoxification of reactive carbonyl compounds improves the oxidative stress tolerance in cucumber, tobacco and rice seedlings}, journal = {Journal of Plant Growth Regulation}, volume = {39}, year = {2020}, month = {SEP}, pages = {1359-1372}, type = {Article}, abstract = {

Detoxification of reactive carbonyl compounds (RCC) is crucial to sustain cellular activity to improve plant growth and development. Seedling growth is highly affected by accumulation of RCC under stress. We report non-enzymatic, enzymatic mechanisms of detoxification of RCC in the cucumber, tobacco and rice seedling systems exposed to glucose, NaCl, methyl viologen (MV) induced oxidative stress. The cucumber seedlings exposed to carbonyl stress had higher levels of malondialdehyde (MDA), protein carbonyls (PCs) and advanced glycation end-product N-carboxymethyl-lysine (AGE-CML) that negatively affected the seedling growth. The overexpression of enzyme encoding aldo-keto reductase-1 (AKR1) in tobacco and rice showed detoxification of RCC, MDA and methylglyoxal (MG) with improved seedling growth under glucose, NaCl and MV-induced oxidative stress. Further, small molecules like acetylsalicylic acid (ASA), aminoguanidine (AG), carnosine (Car), curcumin (Cur) and pyridoxamine (PM) showed detoxification of RCC non-enzymatically and rescued the cucumber seedling growth from glucose, NaCl and MV-stress. In autotrophically grown rice seedlings these molecules substantially improved seedling growth under MV-induced oxidative stress. Seedlings treated with the small molecules sustained higher guaiacol peroxidase (GPX) enzyme activity signifying the role of small molecules in reducing carbonyl stress-induced protein inactivation and AGE-CML protein modifications. The results showed that besides enzymatic detoxification of RCC, the small molecules also could reduce cytotoxic effect of RCC under stress. The study demonstrates that small molecules are attractive compounds to improve the seedling growth under stress conditions.

}, keywords = {Oxidative stress, plant growth, Reactive carbonyl scavengers, Seed germination, small molecules}, issn = {0721-7595}, doi = {10.1007/s00344-020-10072-w, Early Access Date = JAN 2020}, author = {Nareshkumar, Ambekar and Subbarao, Sindhu and Vennapusa, Amarnatha Reddy and Ashwin, Vargheese and Banarjee, Reema and Kulkarni, Mahesh J. and Ramu, Vemanna S. and Udayakumar, Makarla} } @article {46765, title = {Evaluation of biomolecular interactions and cytotoxic activity of organometallic binuclear Ru(II) complexes of ferrocenyl thiosemicarbazones}, journal = {Journal of Biomolecular Structure \& Dynamics}, year = {2020}, month = {JUL}, type = {Article; Early Access}, abstract = {

{Four new ferrocenyl substituted thiosemicarbazone ligands (L1-L4) and their corresponding binuclear ruthenium(II) arene complexes of the general type [(eta(6)-pcym)(L)Ru(mu-im)Ru(L)(eta(6)-p-cym)]Cl (C1-C4) and [(eta(6)-pcym)(L)Ru(mu-azpy)Ru(L)(eta(6)-p-cym)]Cl-2(C5-C8) (cym = cymene

}, keywords = {binuclear ruthenium(II) complexes, BSA binding interactions, DNA, Ferrocenyl thiosemicarbazone, HeLa human cervical carcinoma}, issn = {0739-1102}, doi = {10.1080/07391102.2020.1798284}, author = {Khanvilkar, Priyanka and Dash, Soumya R. and Vohra, Alisagar and Devkar, Ranjitsinh and Chakraborty, Debjani} } @article {47325, title = {Evaluation of uttroside B, a saponin from Solanum nigrum Linn, as a promising chemotherapeutic agent against hepatocellular carcinoma (vol 6, 36318, 2016)}, journal = {Scientific Reports}, volume = {10}, year = {2020}, month = {NOV}, pages = {20431}, type = {Correction}, abstract = {

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

}, issn = {2045-2322}, doi = {10.1038/s41598-020-77440-0}, author = {Nath, Lekshmi R. and Gorantla, Jaggaiah N. and Thulasidasan, Arun Kumar T. and Vijayakurup, Vinod and Shah, Shabna and Anwer, Shabna and Joseph, Sophia M. and Antony, Jayesh and Veena, Kollery Suresh and Sundaram, Sankar and Marelli, Udaya K. and Lankalapalli, Ravi S. and Anto, Ruby John} } @article {47331, title = {Examining the compatibility of energetic plasticizer DNDA-5 with energetic binders}, journal = {Journal of Macromolecular Science Part A-Pure and Applied Chemistry}, volume = {57}, year = {2020}, month = {JAN 2}, pages = {46-54}, type = {Article}, abstract = {

The requirement of developing energetic binders with suitable energetic plasticizers is to enhance the mechanical properties and to reduce glass transition temperature of propellant and explosive formulations. Compatibility of energetic plasticizer 2,4-dinitro-2,4-diazapentane (DNDA-5) with four different energetic binders viz. poly glycidyl nitrate (PGN), poly(3-nitratomethyl-3-methyloxetane) (PLN), glycidyl azide polymer (GAP) and tetra functional glycidyl azide polymer (t-GAP) was studied by using differential scanning calorimeter (DSC) and density functional theory (DFT) methods. Results obtained for the pure binder was compared with the results obtained for binder/plasticizer blend in the parameters of decomposition temperature and the format of the peak which indicated the compatibility or incompatibility of DNDA-5 with the studied binders. Glass transition temperatures of all these blends were determined by low temperature DSC and showed desirable lowering of glass transition temperature with single peak in the case of PLN. The proposed energetic plasticizer DNDA-5 has displayed its compatibility with three binders PGN, PLN and GAP employing thermal techniques. DNDA-5 has been found as incompatible when it is mixed with t-GAP. The predicted relative trend of interaction energies between plasticizer and binder has provided concurrence to results drawn from thermal studies.

}, keywords = {Computational study, DNDA-5, Glass transition temperature, plasticizing effect, thermal}, issn = {1060-1325}, doi = {10.1080/10601325.2019.1669458}, author = {Vijayalakshmi, R. and Agawane, N. T. and Talawar, M. B. and Khan, Md Abdul Shafeeuulla} } @article {46689, title = {Five concomitant polymorphs of a green fluorescent protein chromophore (GFPc) analogue: understanding variations in photoluminescence with pi-stacking interactions}, journal = {Acta Crystallographica Section B-Structural Science Crystal Engineering and Materials}, volume = {76}, year = {2020}, month = {OCT}, pages = {850-864}, type = {Article}, abstract = {

The synthetically modified green fluorescent protein chromophore analogue 3,4,5-trimethoxybenzylidene imidazolinone (1) yielded five polymorphs (I, II, III, IV, V) concomitantly irrespective of the solvent used for crystallization. The pentamorphic modification of 1 is solely due to the interplay of iso-energetic weak intermolecular interactions in molecular associations as well as the conformational flexibility offered by a C-C single bond, which connects the electron-deficient moiety imidazolinone with the electron-rich trimethoxybenzylidene group. A common structural feature observed in all the polymorphs is the formation of a {\textquoteleft}zero-dimensional{\textquoteright} centrosymmetric dimeric unit through a short and linear C-H center dot center dot center dot O hydrogen bond engaging phenyl C-H and imidazolinone carbonyl oxygen. However, the networking of these dimeric units showed a subtle difference in all the polymorphs. The 2D isostructurality was observed between polymorphs I, II and III, while the other two polymorphs IV and V revealed only {\textquoteleft}zero-dimensional{\textquoteright} isostructurality. The different fluorescence emissions of Form I (blue) and Forms II to V (yellow) were attributed to the differences in pi-stacking interactions. It shows that one can modulate the photophysical properties of these smart materials by slightly altering their crystal structure. Such an approach will aid in developing new multi-colour organic fluorescent materials of varying crystal structures for live-cell imaging and fluorescent sensing applications.

}, keywords = {green fluorescent protein, hydrogen bonds, isostructurality, photoluminescence, pi-stacking, Polymorphs}, doi = {10.1107/S2052520620010343}, author = {Mali, Bhupendra P. and Dash, Soumya Ranjan and Nikam, Shrikant B. and Puthuvakkal, Anisha and Vanka, Kumar and Manoj, Kochunnoonny and Gonnade, Rajesh G.} } @article {46925, title = {Geometrical isomerism directed electrochemical sensing}, journal = {Analytical Chemistry}, volume = {92}, year = {2020}, month = {MAR}, pages = {4541-4547}, type = {Article}, abstract = {

We report the independent role of isomerism of secondary sphere substituents over their nature, a factor often overlooked in molecular electrocatalysis pertaining to electrochemical sensing, by establishing that isomerism redefines the electronic structure at the catalytic reaction center via geometrical factors. UV-vis spectroscopy and X-ray photoelectron spectroscopy suggest that a substituent{\textquoteright}s isomerism in molecular catalysts conjoins molecular planarity and catalytic activation through competing field effects and resonance effects. As a classical example, we demonstrate the influence of isomerism of the -NO2 substituents for the electrocatalytic multi electron oxidation of As(III), a potentially important electrochemical pathway for water remediation and arsenic detection. The isomerism dependent oxidative activation of catalytic center leads to a nonprecious molecular catalyst capable for direct As(III) oxidation with an experimental detection limit close to WHO guidelines. This work opens up an unusual approach in analytical chemistry for developing various sensing platforms for challenging chemical and electrochemical reactions.

}, issn = {0003-2700}, doi = {10.1021/acs.analchem.9b05753}, author = {Kottaichamy, Alagar Raja and Begum, Shabbah and Devendrachari, Mruthyunjayachar Chattanahalli and Bhat, Zahid Manzoor and Thimmappa, Ravikumar and Kotresh, Harish Makri Nimbegondi and Vinod, Chathakudath Prabhakaran and Thotiyl, Musthafa Ottakam} } @article {46834, title = {Highly efficient chemoselective N-tert butoxycarbonylation of aliphatic/aromatic/heterocyclic amines using diphenylglycoluril as organocatalyst}, journal = {Tetrahedron}, volume = {76}, year = {2020}, month = {JUN }, pages = {131223}, type = {Article}, abstract = {

An efficient approach for the Chemoselective N-tert-butoxycarbonylation of a variety of amines using diphenylglycoluril as organocatalyst has been described. For the first time, a plausible mechanism for the N-tert-butoxycarbonylation has been proposed using density functional theory (DFT) calculations supported by NMR studies. The reusability of the organocatalyst and observation of the desired N-Boc protected amines being formed without the formation of side products like urea, oxazolidinone, isocyanate, and N, N-di-Boc derivatives makes the present protocol desirable. (C) 2020 Elsevier Ltd. All rights reserved.

}, keywords = {DFT studies, Diphenylglycouril, N-tert butoxycarbonylation, organocatalyst, Proton shuttle mechanism}, issn = {0040-4020}, doi = {10.1016/j.tet.2020.131223}, author = {Awasthi, Amardeep and Mukherjee, Anagh and Singh, Mandeep and Rathee, Garima and Vanka, Kumar and Chandra, Ramesh} } @article {46930, title = {Highly sensitive label-free bio-interfacial colorimetric sensor based on silk fibroin-gold nanocomposite for facile detection of chlorpyrifos pesticide}, journal = {Scientific Reports}, volume = {10}, year = {2020}, month = {MAR}, pages = {4198}, type = {Article}, abstract = {

Herein, the preparation of gold nanoparticles-silk fibroin (SF-AuNPs) dispersion and its label-free colorimetric detection of the organophosphate pesticide, namely chlorpyrifos, at ppb level are reported. The silk fibroin solution was extracted from B. mori silk after performing degumming, dissolving and dialysis steps. This fibroin solution was used for synthesis of gold nanoparticles in-situ without using any external reducing and capping agent. X-ray Diffractometry (XRD), Field Emission Transmission Electron Microscopy (FETEM) along with Surface Plasmon Resonance based optical evaluation confirmed generation of gold nanoparticles within SF matrix. The resultant SF-AuNPs dispersion exhibited rapid and excellent colorimetric pesticide sensing response even at 10 ppb concentration. Effect of additional parameters viz. pH, ionic concentration and interference from other pesticide samples was also studied. Notably, SF-AuNPs dispersion exhibited selective colorimetric pesticide sensing response which can be calibrated. Furthermore, this method was extended to various simulated real life samples such as tap water, soil and agricultural products including plant residues to successfully detect the presence of chlorpyrifos pesticide. The proposed colorimetric sensor system is facile yet effective and can be employed by novice rural population and expert researchers alike. It can be exploited as preliminary tool for label-free colorimetric chlorpyrifos pesticide sensing in water and agricultural products.

}, issn = {2045-2322}, doi = {10.1038/s41598-020-61130-y}, author = {Mane, Pramod C. and Shinde, Manish D. and Varma, Sanjana and Chaudhari, Bhushan P. and Fatehmulla, Amanullah and Shahabuddin, M. and Amalnerkar, Dinesh P. and Aldhafiri, Abdullah M. and Chaudhari, Ravindra D.} } @article {46761, title = {In situ cross-linked nonaqueous polymer electrolyte for zinc-metal polymer batteries and hybrid supercapacitors}, journal = {Small}, volume = {16}, year = {2020}, month = {SEP}, pages = {2002528}, type = {Article}, abstract = {

This work reports the facile synthesis of nonaqueous zinc-ion conducting polymer electrolyte (ZIP) membranes using an ultraviolet (UV)-light-induced photopolymerization technique, with room temperature (RT) ionic conductivity values in the order of 10(-3)S cm(-1). The ZIP membranes demonstrate excellent physicochemical and electrochemical properties, including an electrochemical stability window of \>2.4 V versus Zn|Zn(2+)and dendrite-free plating/stripping processes in symmetric Zn||Zn cells. Besides, a UV-polymerization-assisted in situ process is developed to produce ZIP (abbreviated i-ZIP), which is adopted for the first time to fabricate a nonaqueous zinc-metal polymer battery (ZMPB; VOPO4|i-ZIP|Zn) and zinc-metal hybrid polymer supercapacitor (ZMPS; activated carbon|i-ZIP|Zn) cells. The VOPO(4)cathode employed in ZMPB possesses a layered morphology, exhibiting a high average operating voltage of approximate to 1.2 V. As compared to the conventional polymer cell assembling approach using the ex situ process, the in situ process is simple and it enhances the overall electrochemical performance, which enables the widespread intrusion of ZMPBs and ZMPSs into the application domain. Indeed, considering the promising aspects of the proposed ZIP and its easy processability, this work opens up a new direction for the emergence of the zinc-based energy storage technologies.

}, keywords = {nonaqueous electrolytes, polymer electrolytes, postlithium batteries, Supercapacitors, zinc-metal batteries}, issn = {1613-6810}, doi = {10.1002/smll.202002528, Early Access Date = JUL 2020}, author = {Vijayakumar, Vidyanand and Ghosh, Meena and Kurian, Maria and Torris, Arun and Dilwale, Swati and Badiger, V. Manohar and Winter, Martin and Nair, Jijeesh Ravi and Kurungot, Sreekumar} } @article {46798, title = {Iron-catalyzed C(sp(2))-H alkylation of indolines and benzo[h]quinoline with unactivated alkyl chlorides through chelation assistance}, journal = {ACS Catalysis}, volume = {10}, year = {2020}, month = {JUL }, pages = {7312-7321}, type = {Article}, abstract = {

Regioselective C-H bond alkylation of indolines and benzo[h]quinoline with a wide range of unactivated and highly demanded primary and secondary alkyl chlorides is accomplished using a low-cost iron catalyst. This reaction tolerates diverse functionalities, such as C(sp(2))-Cl, fluoro, alkenyl, silyl, ether, thioether, pyrrolyl, and carbazolyl groups including cyclic and acyclic alkyls as well as alkyl-bearing fatty-alcohol and polycyclic-steroid moieties. The demonstrated iron-catalyzed protocol proceeded via either a five-membered or a six-membered metallacycle. Intriguingly, the C-7-alkylated indolines can be readily functionalized into free-NH indolines/indoles and tryptamine derivatives. A detailed mechanistic investigation highlights the participation of an active Fe(I) catalyst and the involvement of a halogen-atom transfer process via a single-electron-based mechanism. Deuterium labeling and kinetics analysis indicate that the C-H metalation of indoline is the probable turnover-limiting step. Overall, the experimental and theoretical studies supported an Fe(I)/Fe(III) pathway for the alkylation reaction comprising the two-step, one-electron oxidative addition of alkyl chloride.

}, keywords = {alkyl chlorides, Alkylation, C-H activation, chelation assistance, indolines, iron}, issn = {2155-5435}, doi = {10.1021/acscatal.0c02030}, author = {Jagtap, Rahul A. and Samal, Pragnya Paramita and Vinod, C. P. and Krishnamurty, Sailaja and Punji, Benudhar} } @article {47024, title = {Magnetic and luminescent multifunctional nanohybrid: Fe3O4@CaF2:Tb3+: a facile synthesis and characterization}, journal = {Indian Journal of Pure \& Applied Physics}, volume = {58}, year = {2020}, month = {JAN}, pages = {31-35}, type = {Article}, abstract = {

In the present study, bi-functional hybrid nanomaterial has been synthesized and characterized via facile method and characterized. The synthesized nanomaterial shows both magnetic and luminescent properties which are confirmed by VSM (vibrating sample magnetometer), UV-Vis spectra and the photoluminescence emission spectra. For the magnetic phase, i.e., nanocrystalline magnetite, Fe3O4 is used as the core which is then functionalized using polyethylene glycol (PEG) and for the luminescent phase, polyethylenimine (PEI) functionalized CaF2 doped with Tb3+ is used as the emitter. Wherein, both PEG and PEI serve the dual purpose of functionalization as well as stabilization by steric repulsion. The structure and morphology of the synthesized bifunctional hybrid nanomaterial are studied with the help of scanning electron microscopy (SEM) and X-ray powder diffraction.

}, keywords = {Biocompatible, CaF2, Co-precipitation, Fe3O4, Luminescent nanoparticle, Magnetic nanoparticles, Nanohybrid, Tb3+ doping}, issn = {0019-5596}, author = {Vats, Monika and Kumar, Rakesh and Sharma, Jyotsna and Luwang, Meitram Niraj} } @article {46999, title = {Methoxymethyl threofuranosyl thymidine (4 {\textquoteleft}-MOM-TNA-T) at the T7 position of the thrombin-binding aptamer boosts anticoagulation activity, thermal stability, and nuclease resistance}, journal = {ACS Omega}, volume = {5}, year = {2020}, month = {JAN }, pages = {498-506}, type = {Article}, abstract = {

The synthesis of 4{\textquoteright}-methoxymethyl threofuranosyl (4{\textquoteright}-MOM-TNA) thymidine and derived oligomers of the G-rich thrombin-binding aptameric (TBA) sequence is reported. The G-quadruplex stability, anticoagulation activity, and the enzymatic stability of these oligomers bearing the 2{\textquoteright}-3{\textquoteright}-phosphodiester backbone as single substitutions in the loop regions are studied. Amongst all the oligomers, TBA-7T bearing the 4{\textquoteright}-MOM-TNA unit at the T7 position formed a quadruplex with the highest thermal stability. It also resulted in enhanced anticlotting activity that allowed a one-third reduction in the dose, relative to TBA. Further, TBA-7T exhibited enhanced nuclease resistance properties to both endo- and exonucleases.

}, issn = {2470-1343}, doi = {10.1021/acsomega.9b03042}, author = {Varada, Manojkumar and Aher, Manisha and Erande, Namrata and Kumar, Vaijayanti A. and Fernandes, Moneesha} } @article {46818, title = {MnBr2-catalyzed direct and site-selective alkylation of indoles and benzo[h]quinoline}, journal = {Organic Letters}, volume = {22}, year = {2020}, month = {JUN}, pages = {4643-4647}, type = {Article}, abstract = {

Manganese-catalyzed regioselective C-H alkylation of indoles and benzo[h]quinoline with a variety of unactivated alkyl iodides is reported. Unlike other Mn-catalyzed C-H functionalization, this protocol does not require a Grignard reagent base and employs a simple and inexpensive MnBr2 as a catalyst. This method tolerates diverse functionalities, including fluoro, chloro, bromo, iodo, alkenyl, alkynyl, pyrrolyl, and carbazolyl groups. The alkylation proceeds through a single-electron transfer pathway comprising reversible C-H manganesation and involving an alkyl radical intermediate.

}, issn = {1523-7060}, doi = {10.1021/acs.orglett.0c01398}, author = {Jagtap, Rahul A. and Verma, Suryadev K. and Punji, Benudhar} } @article {46637, title = {Molecular investigation of coleopteran specific alpha-amylase inhibitors from amaranthaceae members}, journal = {International Journal of Biological Macromolecules}, volume = {163}, year = {2020}, month = {NOV}, pages = {1444-1450}, type = {Article}, abstract = {

alpha-Amylase inhibitors (alpha-AIs) target alpha-amylases and interfere with the carbohydrate digestion of insects. Among different classes of alpha-AIs, a knottin-type inhibitor from Amaranthus hypochondriacus (AhAI) was found to be specific against coleopteran storage pests. In this report, we have characterized three previously unidentified knottin-type alpha-AIs from various Amaranthaceae plants namely, Amaranthus hypochondriacus (AhAI2), Alternanthera sessilis (AsAI) and Chenopodium quinoa (CqAI). They contain a signal peptide, pro-peptide, and mature peptide. The mature peptides of the new alpha-AIs shared 68 to 78\% identity with AhAI and have highly variable pro-peptide regions. Along with the cystine-knot fold, they showed conservation of reactive site residues. All recombinant alpha-AIs were successfully expressed in their active form and native state using an oxidative cytoplasmic environment. Inhibition studies against various amylases revealed that these inhibitors showed selective inhibition of coleopteran recombinant insect alpha-amylases viz., Tribolium castaneum, and Callosobruchus chinensis. Tribolium castaneum alpha-amylase inhibition potency was highest for AhAI2 (Ki similar to 15 mu M) followed by AsAI (Ki similar to 43 mu M) and CqAI (Ki similar to 61 mu M). Interaction analysis of these inhibitors illustrated that the reactive site of inhibitors make several non-covalent interactions with the substrate-binding pocket of coleopteran alpha-amylases. The selectivity of these inhibitors against coleopteran a-amylases highlights their potential in storage grain pest control. (C) 2020 Elsevier B.V. All rights reserved.

}, keywords = {alpha-amylase, alpha-amylase inhibitor, Amaranthaceae, Coleoptera, Knottin-type}, issn = {0141-8130}, doi = {10.1016/j.ijbiomac.2020.07.219}, author = {Rane, Ashwini S. and Venkatesh, Varun and Joshi, Rakesh S. and Giri, Ashok P.} } @article {46922, title = {Molecular networking and whole-genome analysis aid discovery of an angucycline that inactivates mTORC1/C2 and induces programmed cell death}, journal = {ACS Chemical Biology}, volume = {15}, year = {2020}, month = {MAR}, pages = {780-788}, type = {Article}, abstract = {

Rediscovery of known compounds and time consumed in identification, especially high molecular weight compounds with complex structure, have let down interest in drug discovery. In this study, whole-genome analysis of microbe and Global Natural Products Social (GNPS) molecular networking helped in initial understanding of possible compounds produced by the microbe. Genome data revealed 10 biosythethic gene clusters that encode for secondary metabolites with anticancer potential. NMR analysis of the pure compound revealed the presence of a four-ringed benz[a]anthracene, thus confirming angucycline; molecular networking further confirmed production of this class of compounds. The type II polyketide synthase gene identified in the microbial genome was matched with the urdamycin duster by BLAST analysis. This information led to ease in identification of urdamycin E and a novel natural derivative, urdamycin V, purified from Streptomyces sp. OA293. Urdamycin E (Urd E) induced apoptosis and autophagy in cancer cell lines. Urd E exerted anticancer action through inactivation of the mTOR complex by preventing phosphorylation at Ser 2448 and Ser 2481 of mTORC1 and mTORC2, respectively. Significant reduction in phosphorylation of the major downstream regulators of both mTORC1 (p70s6k and 4e-bp1) and mTORC2 (Akt) were observed, thus further confirming complete inhibition of the mTOR pathway. Urd E presents itself as a novel mTOR inhibitor that employs a novel mechanism in mTOR pathway inhibition.

}, issn = {1554-8929}, doi = {10.1021/acschembio.0c00026}, author = {Dan, Vipin Mohan and Vinodh, J. S. and Sandesh, C. J. and Sanawar, Rahul and Lekshmi, Asha and Kumar, R. Ajay and Kumar, T. R. Santhosh and Marelli, Uday Kiran and Dastager, Syed G. and Pillai, M. Radhakrishna} } @article {46898, title = {Nafion lonomer-based single component electrolytes for aqueous Zn/MnO2 batteries with long cycle life}, journal = {ACS Sustainable Chemistry \& Engineering}, volume = {8}, year = {2020}, month = {APR }, pages = {5040-5049}, type = {Article}, abstract = {

Recently, aqueous rechargeable Zn/MnO2 batteries are emerging as promising energy storage aids owing to their improved safety, low cost of fabrication, and high energy density. However, the rapid decay of capacity during extended charge- discharge cycles hinders the prospect of this technology beyond lab-scale. In the conventional Zn/MnO2 cell, additives such as Mn2+ have been used to tackle the stability issue. Here, we demonstrate that cycling performance of the Zn/MnO2 cell can be improved substantially by using Nafion ionomer as the separator in combination with zinc-ion conducting electrolytes. The Nafion ionomer-based Zn/MnO2 cells do not require any Mn{\textquoteright} additive in the electrolyte and hence termed as {\textquoteleft}{\textquoteleft}single component{\textquoteright}{\textquoteright} electrolytes. The postmortem study of the post-cycled electrodes reveals that the structural evolution of both the anode and cathode in various electrolytes (1 M Zn(CF3SO3)(2), 1 M ZnSO4 center dot 7H(2)O, and 3 M ZnSO4 center dot 7H(2)O) during prolonged cycling significantly influences the cycle life of the respective cells. Optimizing the Nafion ionomer membrane with a suitable electrolyte could render the desired combination of high capacity and high cycle life for a Zn/MnO2 cell.

}, keywords = {aqueous Zn-ion batteries, Cycling stability, dendrite suppression, Electrodeposition, MnO2, Nafion ionomer separator, single component electrolyte}, issn = {2168-0485}, doi = {10.1021/acssuschemeng.9b06798}, author = {Ghosh, Meena and Vijayakumar, Vidyanand and Anothumakkool, Bihag and Kurungot, Sreekumar} } @article {46789, title = {Nanocellulose reinforced flexible composite nanogenerators with enhanced vibrational energy harvesting and sensing properties}, volume = {2}, year = {2020}, month = {JUL}, pages = {2550-2562}, type = {Article}, abstract = {

We report here enhanced vibration and pressure sensing properties of nanocellulose reinforced flexible composite piezoelectric nanogenerators (PENGs). Surface fluorinated nanocellulose crystals (FNC) were incorporated into poly(vinylidene fluoride) (PVDF) and electrospun into composite nanofibers. Incorporation of only 2 wt \% FNC in PVDF resulted in a significant enhancement in pressure sensitivity with a very low detectable pressure limit of 10 Pa and a sensitivity of up to 18 mV/kPa. The composite PENGs also demonstrated very high sensitivity for forced continuous vibrations. 2FNC/PVDF composites resulted in an order of magnitude higher voltage response over neat PVDF for a given strain. When PENGs were mounted on a vacuum pump for transduction of mechanical vibrations into electrical energy, 2FNC/PVDF composite devices manifested similar to 3.8 times enhanced voltage output over neat PVDF and faster charging of a capacitor. The enhanced piezoelectric properties of PVDF/FNC nanocomposites could be attributed to the tailored interface between PVDF and nanocellulose and enhanced polarizability.

}, keywords = {Composite, Nanofiber, piezoelectric, pressure, Sensor, vibration}, issn = {2637-6105}, doi = {10.1021/acsapm.0c00158}, author = {Ram, Farsa and Gudadhe, Aniket and Vijayakanth, Thangavel and Aherrao, Swapnil and Borkar, Vivek and Boomishankar, Ramamoorthy and Shanmuganathan, Kadhiravan} } @article {46802, title = {Nanocrystalline Ag3PO4 for sunlight- and ambient air-driven oxidation of amines: high photocatalytic efficiency and a facile catalyst regeneration strategy}, journal = {ACS Applied Materials \& Interfaces}, volume = {12}, year = {2020}, month = {JUL}, pages = {29324-29334}, type = {Article}, abstract = {

Selective oxidation of amines to imines using sunlight as clean and renewable energy source is an important but challenging chemical transformation because of high reactivity of the generated imines and lack of visible light-responsive materials with high conversion rates. In addition, oxygen gas has to be purged in the reaction mixture in order to increase the reaction efficiency which, in itself, is an energy-consuming process. Herein, we report, for the first time, the use of Ag3PO4 as an excellent photocatalyst for the oxidative coupling of benzyl amines induced by ambient air in the absence of any external source of molecular oxygen at room temperature. The conversion efficiency for the selective oxidation of benzyl amine was found to be greater than 95\% with a selectivity of \>99\% after 40 min of light irradiation indicating an exceptionally high conversion efficiency with a rate constant of 0.002 min(-1), a turnover frequency of 57 h(-1), and a quantum yield of 19\%, considering all of the absorbed photons. Ag3PO4, however, is known for its poor photostability owing to a positive conduction band position and a favorable reduction potential to metallic silver. Therefore, we further employed a simple catalyst regeneration strategy and showed that the catalyst can be recycled with negligible loss of activity and selectivity.

}, keywords = {amine oxidation, energy harvesting, nanocrystalline Ag3PO4, Photocatalysis, regeneration strategy}, issn = {1944-8244}, doi = {10.1021/acsami.0c05961}, author = {Garg, Reeya and Mondal, Sanjit and Sahoo, Lipipuspa and Vinod, C. P. and Gautam, Ujjal K.} } @article {47318, title = {Nanoporous covalent organic framework embedded with Fe/Fe3O4 nanoparticles as air-stable low-density nanomagnets}, journal = {ACS Applied Nano Materials}, volume = {3}, year = {2020}, month = {SEP }, pages = {9088-9096}, type = {Article}, abstract = {

Covalent organic frameworks (COFs) made of light atoms such as H, C, N, and O with a significant void-to-framework ratio are excellent low-density supports for nanoparticles (nPs). Their framework can be precoded with heteroatoms to ensure binding with metallic nanoclusters. With these advantages, if controlled amounts of magnetic nPs are anchored to them, they can yield low-density organic-inorganic nanomagnets. Their organic nature facilitates fusion with bulk materials such as paper/textile to enable bulk composites with well-dispersed low-density magnets, which have potential for defense and next-generation aviation applications. Herein, we have grown small Fe/Fe3O4 nPs (5-18 wt \%) inside a COF. Interestingly, 300 mg of this organic-inorganic framework material (containing 50 mg of nPs) can lift a vial of similar to 15,000 mg (300 times heavier). Also, the hydrophobic COF wraps around the Fe/Fe3O4 nanocluster retaining its room-temperature magnetic character even after 1 year, while the naked nPs lose it within a few days because of air oxidation. Bulk composites with paper and polymers have been made using this low-density Fe-COF to demonstrate their processability.

}, keywords = {air-stable nanomagnets, Covalent organic framework, Fe/Fe3O4 nanoparticles, low-density nanomagnets, magnetic rayon, nanoporous COF}, issn = {2574-0970}, doi = {10.1021/acsanm.0c01762}, author = {Kushwaha, Rinku and Kaleeswaran, Dhananjayan and Haldar, Sattwick and Chakraborty, Debanjan and Mullangi, Dinesh and Borah, Aditya and Vinod, Chathakudath P. and Murugavel, Ramaswamy and Vaidhyanathan, Ramanathan} } @article {46600, title = {Negative ion resonance states: the fock-space coupled-cluster way}, journal = {Journal of Physical Chemistry A}, volume = {124}, year = {2020}, month = {DEC}, pages = {10407-10421}, type = {Article}, abstract = {

The negative ion resonance states, which are electron-molecule metastable compound states, play the most important role in free-electron controlled molecular reactions and low-energy free-electron-induced DNA damage. Their electronic structure is often only poorly described but crucial to an understanding of their reaction dynamics. One of the most important challenges to current electronic structure theory is the computation of negative ion resonance states. As a major step forward, coupled-cluster theories, which are well-known for their ability to produce the best approximate bound state electronic eigen solutions, are upgraded to offer the most accurate and effective approximations for negative ion resonance states. The existing Fock-space coupled-cluster (FSCC) and the equation-of-motion coupled-cluster (EOM-CC) approaches that compute bound states are redesigned for the direct and simultaneous determination of both the kinetic energy of the free electron at which the electron-molecule compound states are resonantly formed and the corresponding autodetachment decay rate of the electron from the metastable compound state. This Feature Article reviews the computation of negative ion resonances using the FSCC approach and, in passing, provides the highlights of the equivalent EOM-CC approach.

}, issn = {1089-5639}, doi = {10.1021/acs.jpca.0c09148}, author = {Basumallick, Suhita and Sajeev, Y. and Pal, Sourav and Vaval, Nayana} } @article {46854, title = {Novel synthesis of 3-((benzo[d]thiazol-2-ylamino)(phenyl)methyl)-4-hydroxy-1-methylquinol in-2(1H)-one via consecutive C-C and C-N bond formation in water}, journal = {Research on Chemical Intermediates}, volume = {46}, year = {2020}, month = {AUG}, pages = {3801-3815}, type = {Article}, abstract = {

A simple, efficient, and eco-friendly protocol has been developed for the synthesis of novel 3-((benzo[d]thiazol-2-ylamino)(4-methoxyphenyl)methyl)-4-hydroxy-1-met hylquinolin-2(1H)-one derivatives using a one-pot C-C and C-N bond forming strategy from the reaction of 4-hydroxy-1-methylquinolin-2(1H)-one, 2-aminobenzothiazole and aromatic aldehydes in aqueous solvent without using any metal catalyst. Several advantages of this protocol include its operational simplicity, short reaction time, mild reaction condition, efficient utilization of all the reactants, wide functional group tolerance, using water as an environmentally friendly solvent and non-chromatographic purification procedure. [GRAPHICS] .

}, keywords = {4-Hydroxy-1-methylquinolin-2(1H)-one, Green solvent, Multicomponent reactions (MCRs), Quinolines, Thiazole}, issn = {0922-6168}, doi = {10.1007/s11164-020-04173-0, Early Access Date = MAY 2020}, author = {Yadav, Maruti B. and Vagh, Sandip S. and Jeong, Yeon Tae} } @article {46966, title = {Para-selective copper-catalyzed C(sp(2))-H amidation/dimerization of anilides via a radical pathway}, journal = {Chemical Communications}, volume = {56}, year = {2020}, month = {FEB }, pages = {1565-1568}, type = {Article}, abstract = {

Copper-catalyzed amidation/dimerization of anilides via regioselective C(sp(2))-H functionalization is achieved. The para-selective amidation is accomplished on the anilide aromatic ring via a radical pathway leading to C-N bond formation in the presence of ammonium persulfate as a radical source/oxidant for the copper catalyst. The developed protocol tolerates a wide range of anilide substrates. The regioselectivity is confirmed by single-crystal X-ray studies.

}, issn = {1359-7345}, doi = {10.1039/c9cc09824k}, author = {Viveki, Amol B. and Garad, Dnyaneshwar N. and Gonnade, Rajesh G. and Mhaske, Santosh B.} } @proceedings {47332, title = {Photocatalytic hydrogen production from H2S using nanostructured CNT blended CdZnS/Fe2O3 thin film on glass substrate}, volume = {1495}, year = {2020}, month = {MAR}, publisher = {IOP Publishing Ltd}, abstract = {

A co-precipitation method was employed to prepare the CNT blended CdZnS/Fe2O3\ photocatalyst. Using the powder photocatalyst, the thin film of CNT blended CdZnS/Fe2O3\ photocatalyst over a glass substrate was prepared using the drop-casting method. The obtained thin film was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy-dispersive X-ray analysis (EDAX), photoluminescence (PL), and hydrogen production activity studies in order to obtain information on their structural, morphology, chemical composition, optical and hydrogen production efficiency. The hydrogen production activity of catalyst or effective conversion of H2S into hydrogen (H2) and sulfur (S) using thin-film photocatalyst was evaluated using a simulated sulfide solution. The results showed that 1 mg of CNT blended CdZnS/Fe2O3\ catalyst coated as thin film over glass substrate (4.69 cm2) showed the highest hydrogen production value of 3180 μmol h-1g-1; compared to that of 1 mg CNT blended CdZnS/Fe2O3\ powder of 2510 μmol h-1g-1. From the above results, it is concluded that the thin film form of photocatlyst produced more hydrogen than the powder form. This is attributed to the effective charge separation and increased specific surface area in thin film photocatalyst.

}, doi = {10.1088/1742-6596/1495/1/012035}, author = {Raja, M. Anthony and Vijayarengan, Preethi and Pal, Yash and Nalajala, Naresh and Gopinath, Chinnakonda} } @article {46893, title = {Piezoelectric energy harvesting from a ferroelectric hybrid salt [Ph3MeP](4)[Ni(NCS)(6)] embedded in a polymer matrix}, journal = {Angewandte Chemie-International Edition}, volume = {59}, year = {2020}, month = {JUN }, pages = {10368-10373}, type = {Article}, abstract = {

Organic-inorganic hybrid ferroelectrics are an exciting class of molecular materials with promising applications in the area of energy and electronics. The synthesis, ferroelectric and piezoelectric energy harvesting behavior of a 3d metal ion-containing A(4)BX(6) type organic-inorganic hybrid salt [Ph3MeP](4)[Ni(NCS)(6)] (1) is now presented. P-E hysteresis loop studies on 1 show a remnant ferroelectric polarization value of 18.71 mu C cm(-2), at room temperature. Composite thermoplastic polyurethane (TPU) devices with 5, 10, 15 and 20 wt \% compositions of 1 were prepared and employed for piezoelectric energy harvesting studies. A maximum output voltage of 19.29 V and a calculated power density value of 2.51 mW cm(-3) were observed for the 15 wt \% 1-TPU device. The capacitor charging experiments on the 15 wt \% 1-TPU composite device shows an excellent energy storage performance with the highest stored energies and measured charges of 198.8 mu J and 600 mu C, respectively.

}, keywords = {energy conversion, mechanical properties, non-covalent interactions, organic-inorganic hybrid composites, Phosphorus}, issn = {1433-7851}, doi = {10.1002/anie.202001250, Early Access Date = APR 2020}, author = {Vijayakanth, Thangavel and Ram, Farsa and Praveenkumar, Balu and Shanmuganathan, Kadhiravan and Boomishankar, Ramamoorthy} } @article {46955, title = {Plausible diagnostic value of urinary isomeric dimethylarginine ratio for diabetic nephropathy}, journal = {Scientific Reports}, volume = {10}, year = {2020}, month = {FEB}, pages = {2970}, type = {Article}, abstract = {

Altered circulatory asymmetric and symmetric dimethylarginines have been independently reported in patients with end-stage renal failure suggesting their potential role as mediators and early biomarkers of nephropathy. These alterations can also be reflected in urine. Herein, we aimed to evaluate urinary asymmetric to symmetric dimethylarginine ratio (ASR) for early prediction of diabetic nephropathy (DN). In this cross-sectional study, individuals with impaired glucose tolerance (IGT), newly diagnosed diabetes (NDD), diabetic microalbuminuria (MIC), macroalbuminuria (MAC), and normal glucose tolerance (NGT) were recruited from Dr. Mohans{\textquoteright} Diabetes Specialties centre, India. Urinary ASR was measured using a validated high-throughput MALDI-MS/MS method. Significantly lower ASR was observed in MIC (0.909) and MAC (0.741) in comparison to the NGT and NDD groups. On regression models, ASR was associated with MIC [OR: 0.256; 95\% CI: 0.158-0.491] and MAC [OR 0.146; 95\% CI: 0.071-0.292] controlled for all the available confounding factors. ROC analysis revealed ASR cut-point of 0.95 had C-statistic of 0.691 (95\% CI: 0.627-0.755) to discriminate MIC from NDD with 72\% sensitivity. Whereas, an ASR cut-point of 0.82 had C-statistic of 0.846 (95\% CI: 0.800 - 0.893) had 91\% sensitivity for identifying MAC. Our results suggest ASR as a potential early diagnostic biomarker for DN among the Asian Indians.

}, issn = {2045-2322}, doi = {10.1038/s41598-020-59897-1}, author = {Parmar, Dharmeshkumar and Bhattacharya, Nivedita and Kannan, Shanthini and Vadivel, Sangeetha and Pandey, Gautam Kumar and Ghanate, Avinash and Ragi, Nagarjuna Chary and Prabu, Paramasivam and Pramodkumar, Thyparambil Aravindakshan and Manickam, Nagaraj and Mohan, Viswanathan and Sripadi, Prabhakar and Kuppan, Gokulakrishnan and Panchagnula, Venkateswarlu} } @article {46612, title = {Preparation, spectroscopic characterization, theoretical investigations, and in vitro anticancer activity of Cd(II), Ni(II), Zn(II), and Cu(II) complexes of 4(3H)-quinazolinone-derived schiff base}, journal = {Molecules}, volume = {25}, year = {2020}, month = {DEC}, pages = {5973}, type = {Article}, abstract = {

Herein, we report the synthesis and characterization of a new Schiff base ligand 3-[[(E)-(3-hydroxyphenyl)-methylidene]amino]-2-methyl-quinazolin-4(3 H)-one (HAMQ) and its Cd(II), Ni(II), Zn(II), and Cu(II) complexes (C-1-C-4). The ligand HAMQ was synthesized by reacting 3-hydroxybenzaldehyde and 3-amino-2-methyl-4(3H)-quinazolinone in a 1:1 molar ratio. The structure of the ligand and its complexes (C-1-C-4) were evaluated using ultraviolet (UV)-visible (Vis) light spectroscopy, H-1-NMR, Fourier-transform infrared (FT-IR) spectroscopy, MS, elemental analysis, conductance data, and thermogravimetric analysis (TGA). The characterization results suggested that the bidentate ligand, HAMQ, coordinated to the metal center through the lactum oxygen and the azomethine nitrogen. Moreover, all the metal complexes were analyzed using powder X-ray diffraction studies, which revealed that all of them belong to a triclinic crystal system. The research was supplemented by density functional theory (DFT) studies on the IR and UV-Vis spectra, as well as the chemical reactivity of the HAMQ and its four metallic derivatives making use of conceptual density functional theory (CDFT) by means of KID (Koopmans in DFT) methodology. The synthesized complexes displayed significant in vitro anticancer activity against human cancer cell lines (HeLa and HCT-115).

}, keywords = {3-quinolin-4(3H)-one, chemical reactivity properties, conceptual DFT, Metal complexes, spectral studies}, doi = {10.3390/molecules25245973}, author = {Ashok, Ubale Panchsheela and Kollur, Shiva Prasad and Anil, Nishad and Arun, Bansode Prakash and Jadhav, Sanjay Namdev and Sarsamkar, Sanjay and Helavi, Vasant Baburao and Srinivasan, Asha and Kaulage, Sandeep and Veerapur, Ravindra and Al-Rashed, Sarah and Syed, Asad and Ortega-Castro, Joaquin and Frau, Juan and Flores-Holguin, Norma and Glossman-Mitnik, Daniel} } @article {46632, title = {Process development for 6-aminopenicillanic acid production using lentikats-encapsulated escherichia coli cells expressing penicillin V acylase}, journal = {ACS Omega}, volume = {5}, year = {2020}, month = {NOV }, pages = {28972-28976}, type = {Article}, abstract = {

Penicillin V acylase (PVA, EC 3.5.1.11) hydrolyzes the side chain of phenoxymethylpenicillin (Pen V) and finds application in the manufacture of the pharmaceutical intermediate 6-aminopenicillanic acid (6-APA). Here, we report the scale-up of cultivation of Escherichia coli whole cells expressing a highly active PVA from Pectobacterium atrosepticum and their encapsulation in polyvinyl alcohol-poly(ethylene glycol) Lentikats hydrogels. A biocatalytic process for the hydrolysis of 2\% (w/v) Pen V was set up in a 2 L reactor using the Lentikats-immobilized whole cells, with a customized setup to enable continuous downstream processing of the reaction products. The biocatalytic reaction afforded complete conversion of Pen V for 10 reaction cycles, with an overall 90\% conversion up to 50 cycles. The bioprocess was further scaled up to the pilot-scale at 10 L, enabling complete conversion of Pen V to 6-APA for 10 cycles. The 6-APA and phenoxy acetic acid products were recovered from downstream processing with isolated yields of 85-90 and 87-92\%, respectively. Immobilization in Lentikats beads improved the stability of the whole cells on storage, maintaining 90-100\% activity and similar conversion efficiency after 3 months at 4 degrees C. The robust PVA biocatalyst can be employed in a continuous process to provide a sustainable route for bulk 6-APA production from Pen V.

}, issn = {2470-1343}, doi = {10.1021/acsomega.0c02813}, author = {Sawant, Amol M. and Sunder, Avinash Vellore and Vamkudoth, Koteswara Rao and Ramasamy, Sureshkumar and Pundle, Archana} } @article {46788, title = {Relativistic coupled-cluster study of BaF in search of CP violation}, journal = {Journal of Physics B-Atomic Molecular and Optical Physics}, volume = {53}, year = {2020}, month = {JUL}, pages = {135102}, type = {Article}, abstract = {

BaF is one of the potential candidates for the experimental search of the electric dipole moment of the electron (eEDM). The NL-eEDM collaboration is building a new experimental set up to measure the eEDM using the BaF molecule (The NL-eEDM collaboration, 2018 Eur. Phys. J. D 72: 197). To analyze the results of such an experiment, one would require the accurate value of the molecular P, T-odd interaction parameters that cannot be measured from any experiment. In this work, we report the precise value of the P, T-odd interaction parameters of the BaF molecule obtained from the four-component relativistic coupled-cluster calculations. We also calculate the hyperfine structure (HFS) constants of the same molecule to assess the reliability of the reported molecular parameters. The calculated HFS constants show good agreement with the available experimental values. Further, the systematic effects of electron-correlation along with the roles of inner-core electrons and the virtual energy functions in the calculation of the studied properties of BaF are investigated.

}, keywords = {electric dipole moment of the electron, electron-correlation, Relativistic effects}, issn = {0953-4075}, doi = {10.1088/1361-6455/ab84c8}, author = {Talukdar, Kaushik and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article {46927, title = {Relativistic double-ionization equation-of-motion coupled-cluster method: application to low-lying doubly ionized states}, journal = {Journal of Chemical Physics}, volume = {152}, year = {2020}, month = {MAR}, pages = {104302}, type = {Article}, abstract = {

This article deals with the extension of the relativistic double-ionization equation-of-motion coupled-cluster (DI-EOMCC) method [H. Pathak et al. Phys. Rev. A 90, 010501(R) (2014)] for the molecular systems. The Dirac-Coulomb Hamiltonian with four-component spinors is considered to take care of the relativistic effects. The implemented method is employed to compute a few low-lying doubly ionized states of noble gas atoms (Ar, Kr, Xe, and Rn) and Cl-2, Br-2, HBr, and HI. Additionally, we presented results with two intermediate schemes in the four-component relativistic DI-EOMCC framework to understand the role of electron correlation. The computed double ionization spectra for the atomic systems are compared with the values from the non-relativistic DI-EOMCC method with spin-orbit coupling [Z. Wang et al. J. Chem. Phys. 142, 144109 (2015)] and the values from the National Institute of Science and Technology (NIST) database. Our atomic results are found to be in good agreement with the NIST values. Furthermore, the obtained results for the molecular systems agree well with the available experimental values.

}, issn = {0021-9606}, doi = {10.1063/1.5140988}, author = {Pathak, Himadri and Sasmal, Sudip and Talukdar, Kaushik and Nayak, Malaya K. and Veval, Nayana and Pal, Sourav} } @article {46777, title = {Role of B site ions in bifunctional oxygen electrocatalysis: a structure-property correlation study on doped Ca(2)Fe(2)O(5)brownmillerites}, journal = {Physical Chemistry Chemical Physics}, volume = {22}, year = {2020}, month = {JUL }, pages = {15520-15527}, type = {Article}, abstract = {

The role of B site doping with transition metals in brownmillerites, a perovskite related family of compounds, in bifunctional oxygen electrocatalysis,viz., simultaneous reduction and evolution reactions, is analysed. Ca2Fe1.9M0.1O5(M = Mn, Co, Ni, and Cu) is synthesised and structurally characterised by powder XRD and Rietveld refinement. Valence states of the surface B site ions are identified by X-ray photoelectron spectroscopy. Bifunctional oxygen electrochemistry is studied with the RDE and RRDE techniques and correlated with the structural and electronic parameters like oxygen non-stoichiometry and B site catalytic activity. Since the widely accepted electronic descriptors like e(g)filling may not be sufficient for explaining the bifunctional activity, B site electron donating capability as well as the extent of oxygen vacancies enhancing O(2)adsorption is also considered. Such structural parameters are also found to influence both the ORR and OER and based on this, Ni doping is proposed as advantageous for the bifunctional activity.

}, issn = {1463-9076}, doi = {10.1039/d0cp02391d}, author = {Thundiyil, Shibin and Vinod, C. P. and Kurungot, Sreekumar and Devi, R. Nandini} } @article {46932, title = {Role of electron correlation in the P, T-odd effects of CdH: a relativistic coupled-cluster investigation}, journal = {Physical Review A}, volume = {101}, year = {2020}, month = {MAR }, pages = {032505}, type = {Article}, abstract = {

We investigate the parity (P) and time-reversal (T) symmetry violating effects in the CdH molecule and perform the relativistic coupled-cluster calculation of the molecular parameters-E-eff, W-s, and W-M-related to the electric dipole moment of electron (eEDM) interaction, the scalar-pseudoscalar (S-PS) nucleus-electron neutral current coupling, and the nuclear magnetic quadrupole moment (MQM) interaction with electrons, respectively. We also compute the molecular dipole moment and the magnetic hyperfine structure coupling constant of CdH. The values of E-eff, W-s, and W-M obtained by us in the said molecule are 12.2 GV/cm, 14.0 kHz, and 0.82 x 10(33) Hz/e cm(2), respectively, within an uncertainty of 10\%. Furthermore, we study the trend of electron-correlation in the computed properties of CdH and that of the P, T-odd parameters in the group-12 monohydrides (i.e., ZnH, CdH, and HgH).

}, issn = {2469-9926}, doi = {10.1103/PhysRevA.101.032505}, author = {Talukdar, Kaushik and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article {47317, title = {Role of exposed crystal facets in the atmospheric pressure CO hydrogenation on Co3O4}, journal = {Nano-Structures \& Nano-Objects}, volume = {23}, year = {2020}, month = {JUL}, type = {Article}, abstract = {

Co3O4 nanostructures with different exposed planes are studied for atmospheric pressure CO hydrogenation. Existence of different facets is characterized by HR-TEM and found Co3O4 - NSP (nanospheres) expose (112) facet, NB (nanobelts) exhibit (110) plane and (100) is the dominant surface facet in NC (nanocubes). Different catalytic activity is demonstrated by the specific facet of Co3O4 catalysts. CO hydrogenation is facet dependent and the catalytic activity follows the order of Co3O4-NB \> Co3O4-NC \> Co3O4-NSP.

}, doi = {10.1016/j.nanoso.2020.100504}, author = {Jain, Preeti and Gupta, Sharad and Vinod, C. P.} } @article {46881, title = {Room temperature processed in-situ carbon-coated vanadium carbide (VC@C) as a high capacity robust Li/Na battery anode material}, journal = {Carbon}, volume = {161}, year = {2020}, month = {MAY}, pages = {108-116}, type = {Article}, abstract = {

3D carbide systems with their robust physical and mechanical properties have always attracted multiple application interests. In this report, we have synthesized a three-dimensional in-situ carbon coated cubic carbide, Vanadium Carbide (VC@C), by a very simple, scalable and cost-effective room temperature mechano-chemical ball-milling procedure and researched its promise as effective anode material for Li and Na ion batteries. We have demonstrated that VC@C shows an impressive initial discharge/lithiation capacity of 1165 mAh g(-1) with a high reversible capacity of 640 mAh g(-1) after 100 charge-discharge cycles at an applied current density of 0.1 A g(-1). We have also found that this material renders a very promising rate performance with significantly low capacity drop after exposing it to variable current densities ranging from 0.05 A g(-1) to 2 A g(-1) with an excellent stability up to 1000 cycles owing to its structural robustness, as verified by post-cycling characterizations. A Li-ion full cell study using LiCoO2 as cathode also showed excellent promise in terms of practical application demonstrating a reversible capacity of 95 mAh g(-1) after 100 cycles. Even for Na insertion/de-insertion VC@C shows a clear promise in terms of capacity, cyclic stability and rate performance. (C) 2020 Elsevier Ltd. All rights reserved.

}, keywords = {3D carbide, In-situ synthesis, Li-ion battery, Post cycling characterization, Room temperature ball milling, Williamson-Hall analysis}, issn = {0008-6223}, doi = {10.1016/j.carbon.2020.01.057}, author = {Mahajan, Mani and Roy, Kingshuk and Parmar, Swati and Singla, Gourav and Pandey, O. P. and Singh, K. and Vaidhyanathan, Ramanathan and Ogale, Satishchandra} } @article {46664, title = {Scalable synthesis of manganese-doped hydrated vanadium oxide as a cathode material for aqueous zinc-metal battery}, journal = {ACS Applied Materials \& Interfaces}, volume = {12}, year = {2020}, month = {OCT }, pages = {48542-48552}, type = {Article}, abstract = {

Rechargeable aqueous zinc-metal batteries (ZMBs) are considered as potential energy storage devices for stationary applications. Despite the significant developments in recent years, the performance of ZMBs is still limited due to the lack of advanced cathode materials delivering high capacity and long cycle life. In this work, we report a low-temperature and scalable synthesis method following a surfactant-assisted route for preparing manganese-doped hydrated vanadium oxide (MnHVO-30) and its application as the cathode material for ZMB. The as-prepared material possesses a porous architecture and expanded interlayer spacing. Therefore, the MnHVO-30 cathode offers fast and reversible insertion of Zn2+ ions during the charge/discharge process and delivers 341 mAh g(-1) capacity at 0.1 A g(-1). Moreover, the MnHVO-30 parallel to Zn cell retains 82\% of its initial capacity over 1200 stability cycles, which is higher compared to that of the undoped system. Besides, a quasi-solid-state home-made pouch cell with an area of 3.3 x 1.6 cm(2) and 3.6 mg cm(-2) loading is assembled, achieving 115 mAh g(-1) capacity over 100 stability cycles. Therefore, this work provides an easy and attractive way for preparing efficient cathode materials for aqueous ZMBs.

}, keywords = {anionic surfactant, hydrated vanadium pentoxide, Nafion ionomer membrane, post-lithium battery, quasi-solid-state battery}, issn = {1944-8244}, doi = {10.1021/acsami.0c13221}, author = {Ghosh, Meena and Dilwale, Swati and Vijayakumar, Vidyanand and Kurungot, Sreekumar} } @article {46959, title = {Shape resonance of sulphur dioxide anion excited states using the CAP-CIP-FSMRCCSD method}, journal = {Molecular Physics}, volume = {118}, year = {2020}, month = {AUG }, type = {Article}, abstract = {

We have studied the shape resonance of excited states of sulphur dioxide (SO2) anion by using the correlated independent particle Fock space multi-reference coupled cluster (CAP-CIP-FSMRCCSD) method augmented by complex absorption potential. These resonant states have been trapped experimentally in recent years by electron collision. In particular, we have investigated e(-)-SO2 scattering and computed the negative-ion resonance states of the anion responsible for the two resonances around 4.45 and 6.56 eV and compared the results with the existing experimental observations. From the computational results using the CAP-CIP-FSMRCCSD method, it has been observed that both the resonances near 4.45 and 6.56 eV result from A(1) symmetries. [GRAPHICS] .

}, keywords = {CAP augmented correlated independent particle (CAP-CIP-FSMRCCSD), complex absorption potential (CAP), coupled cluster, Fock space multireference coupled cluster (FSMRCCSD), shape resonance}, issn = {0026-8976}, doi = {10.1080/00268976.2020.1726521, Early Access Date = FEB 2020}, author = {Basumallick, Suhita and Bhattacharya, Sumantra and Jana, Irina and Vaval, Nayana and Pal, Sourav} } @article {46715, title = {Spectroscopic evidences for the size dependent generation of pd species responsible for the low temperature CO oxidation activity on Pd-SBA-15 nanocatalyst}, journal = {Applied Catalysis B-Environmental}, volume = {272}, year = {2020}, month = {SEP }, pages = {118934}, type = {Article}, abstract = {

A comprehensive size dependent CO oxidation activity has been demonstrated for Pd-SBA-15 catalysts with Pd NPs of varying sizes such as 1-2, 4-6 and 7-10 nm. Pd-SBA-15 catalyst with smallest sized NPs (Pd-S-N) has been synthesized by modified deposition precipitation method recently developed in our lab. Pd-S-N catalyst (reduced at 400 degrees C) demonstrated CO oxidation activity with lower light off temperature (50 degrees C), clearly one of the best reported for a Pd-silica system. A detailed XPS and in-situ DRIFTS analyses further supported by XAS and DFT calculations reveal the presence of easily decomposable highvalent Pd-oxide on co-ordinatively unsaturated Pd sites (Pdcus). Weak binding of CO on Pdcus sites in small Pd NPs leaving sites for oxygen activation is attributed to the low temperature activity of Pd-S-N for CO oxidation.

}, keywords = {CO oxidation, high-valent Pd species, Pd nanoparticles, SBA-15, under coordinated Pd atoms}, issn = {0926-3373}, doi = {10.1016/j.apcatb.2020.118934}, author = {Soni, Yogita and Pradhan, Sumanta and Bamnia, Mahesh K. and Yadav, A. K. and Jha, S. N. and Bhattacharyya, D. and Khan, Tuhin Suvra and Haider, M. A. and Vinod, C. P.} } @article {46969, title = {Stress-induced electronic structure modulation of manganese-incorporated Ni2P leading to enhanced activity for water splitting}, journal = {ACS Applied Energy Materials}, volume = {3}, year = {2020}, month = {FEB}, pages = {1271-1278}, type = {Article}, abstract = {

The cornerstone of the emerging hydrogen economy is hydrogen production by water electrolysis with concomitant oxygen generation. Incorporating a third element in metal phosphides can tune the crystalline and electronic structure, hence improving the electrocatalytic properties. In this work, Mn-doped Ni2P with varying ratios of Mn and Ni has been explored as excellent catalysts for water splitting. A complete cell made of the best catalyst Ni1.5Mn0.5P electrodes showed low voltage of 1.75 V at a current density of 10 mA cm(-2) due to enhanced electrical conductivity, induction of tensile stress, enhanced electrochemical surface area, and increased electric dipole upon Mn incorporation.

}, keywords = {Electronic Structure, hydrogen evolution reaction, Oxygen Evolution Reaction, phosphides, water splitting}, issn = {2574-0962}, doi = {10.1021/acsaem.9b02097}, author = {Sarkar, Shreya and Dheer, Lakshay and Vinod, C. P. and Thapa, Ranjit and Waghmare, V. Umesh and Peter, Sebastian C.} } @article {47312, title = {Synthesis, crystal structure and Hirshfeld surface analysis of the hydrated form of N{\textquoteright}, N-(1,4-phenylenebis(methanylylidene) di(iso-nicotinic hydrazide)}, journal = {Chemical Data Collections}, volume = {28}, year = {2020}, month = {AUG}, type = {Article}, abstract = {

The title compound, C20H16N6O2\ was synthesized by reflux with isonicotinic hydrazide and terephthaldehyde in ethanol solvent with the acidic condition. The single-crystal X-ray structure determination of the title compound,\ N, N-(1,4-phenylene bis (methanylylidene) di(iso-nicotinic hydrazide), reveals that the molecule crystallizes in center of symmetry with water molecules (Dihydrated form, C20H16N6O2.2H2O) through N-H...O and C-H...O hydrogen bondings. Further, the crystal structure is stabilized by O-H...O and weak C-H...N hydrogen bondings with the formation of infinite chain and dimer. Further, surface analysis and fingerprint plot reveal that the significant hydrogen bonding such as H{\textbullet}{\textbullet}{\textbullet}O (15.9\%) and N{\textbullet}{\textbullet}{\textbullet}H (11.4\%) interactions play the most crucial role for its molecular packing.

}, doi = {10.1016/j.cdc.2020.100401}, author = {Ingle, Kapil S. and Mohurle, Smital A. and Bairagi, Keshab M. and Shaikh, Tabrez R. and Venugopala, Katharigatta N. and Chandrashekharappa, Sandeep and Gonnade, Rajesh G. and Nayak, Susanta K.} } @article {46820, title = {Synthesis of alpha-ketoamides using potassium superoxide (KO2) as an oxidizing agent}, journal = {Tetrahedron}, volume = {76}, year = {2020}, month = {JUN }, pages = {131262}, type = {Article}, abstract = {

A simple and convenient method for the synthesis of alpha-ketoamides by the oxidation of aryl acetamides using potassium superoxide (KO2) as an oxidizing agent is disclosed here. The scope of the developed method is successfully tested with fifteen substrates. In addition, the utility of method has been demonstrated by synthesizing an orexin receptor antagonist, a medicinally interesting compound. (C) 2020 Published by Elsevier Ltd.

}, keywords = {alpha-Ketoamide, Orexin receptor, Oxidation, Potassium superoxide (KO2)}, issn = {0040-4020}, doi = {10.1016/j.tet.2020.131262}, author = {Vasudevan, N. and Routholla, Ganesh and Illa, Giri Teja and Reddy, D. Srinivasa} } @article {46790, title = {Synthesis of diverse nitrogen fused polycyclic dihydroisoquinoline (DHIQ) derivatives via GBB-based cyclic iminium induced double-annulation cascade}, journal = {Tetrahedron Letters}, volume = {61}, year = {2020}, month = {JUL}, pages = {152101}, type = {Article}, abstract = {

A highly efficient and distinct Bronsted acid-mediated unprecedented cyclic iminium induced double annulation cascade (DAC) protocol for the synthesis of novel dihydroindazolo[30,20:2,3]imidazo[5,1-a]isoquinolinamines has been achieved through the three-component Groebke-Blackburn-Bienayme reaction. The transformation is based on sequential cascade processes involving imine formation followed by an intramolecular nucleophilic substitution to generate a highly reactive cyclic iminium species, which would undergo a rapid [4 + 1] formal cycloaddition steps in one-pot fashion. This strategy provides novel skeletally diverse complex nitrogen fused polycyclic DHIQ derivatives by employing readily available substrates and a simple procedure, which would render this method potentially useful in organic synthesis. (C) 2020 Elsevier Ltd. All rights reserved.

}, keywords = {diversity-oriented synthesis, Excellent yields, GBB-based approach, Novel polycyclic N-fused architecture, Scalable}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2020.152101}, author = {Balwe, Sandip Gangadhar and Vagh, Sandip S. and Jeong, Yeon Tae} } @article {46956, title = {Tale of biphenyl and terphenyl substituents for structurally diverse ketiminato magnesium, calcium and germanium complexes}, journal = {Chemistry-An Asian Journal}, volume = {15}, year = {2020}, month = {MAR}, pages = {820-827}, type = {Article}, abstract = {

In this paper, we have used two N,O-ketiminato ligands (L1 and L2) with biphenyl and terphenyl substituent on the nitrogen atom. Deprotonation of L1 with KN(SiMe3)(2) and subsequent reaction with MgI2 led to a homoleptic dinuclear magnesium complex (1) with a Mg2O2 four-membered ring. Deprotonation with nBuLi and subsequent reaction with MgI2 afforded a unusual dinuclear magnesium complex (2) with a Mg2O2 ring. Extension of the ligand for calcium resulted in a trinuclear calcium complex (3) with six four-membered Ca2O2 rings. We could not isolate any chelating complex when L2 was used as a ligand, and only oxygen bound magnesium (4) and calcium (5) adducts were isolated. DFT studies were performed to understand this dissimilar behavior. More diverse results were obtained when lithiated L1 and L2 were treated with germanium dichloride. We were able to stabilize a monomeric germylene monochloride (7) with L1. However, with L2, an unusual ligand scrambling, and a C-C coupling take place, leading to the formation of a secondary carbocation with GeCl3- as a counter-anion (8). Besides, a germanium dichloride adduct (9) bound to the oxygen center of the ligand was obtained as the minor product.

}, keywords = {calcium, Germylene, ligand, Magnesium, X-ray Structure}, issn = {1861-4728}, doi = {10.1002/asia.201901801, Early Access Date = FEB 2020}, author = {Kumar, Rohit and Yadav, Sandeep and Gour, Kritika and Sangtani, Ekta and Ranjan Dash, Soumya and Raja, Abhishekram and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {47004, title = {TDR Targets 6: driving drug discovery for human pathogens through intensive chemogenomic data integration}, journal = {Nucleic Acids Research}, volume = {48}, year = {2020}, month = {JAN }, pages = {D992-D1005}, type = {Article}, abstract = {

The volume of biological, chemical and functional data deposited in the public domain is growing rapidly, thanks to next generation sequencing and highly-automated screening technologies. These datasets represent invaluable resources for drug discovery, particularly for less studied neglected disease pathogens. To leverage these datasets, smart and intensive data integration is required to guide computational inferences across diverse organisms. The TDR Targets chemogenomics resource integrates genomic data from human pathogens and model organisms along with information on bioactive compounds and their annotated activities. This report highlights the latest updates on the available data and functionality in TDR Targets 6. Based on chemogenomic network models providing links between inhibitors and targets, the database now incorporates network-driven target prioritizations, and novel visualizations of network subgraphs displaying chemical- and target-similarity neighborhoods along with associated target-compound bioactivity links. Available data can be browsed and queried through a new user interface, that allow users to perform prioritizations of protein targets and chemical inhibitors. As such, TDR Targets now facilitates the investigation of drug repurposing against pathogen targets, which can potentially help in identifying candidate targets for bioactive compounds with previously unknown targets. TDR Targets is available at https://tdrtargets.org.

}, issn = {0305-1048}, doi = {10.1093/nar/gkz999}, author = {Landaburu, Lionel Uran and Berenstein, Ariel J. and Videla, Santiago and Maru, Parag and Shanmugam, Dhanasekaran and Chernomoretz, Ariel and Aguero, Fernan} } @article {46793, title = {TIAs pathway genes and associated miRNA identification in Vinca minor: supporting aspidosperma and eburnamine alkaloids linkage via transcriptomic analysis}, journal = {Physiology and Molecular Biology of Plants}, volume = {26}, year = {2020}, month = {AUG}, pages = {1695-1711}, type = {Article}, abstract = {

V. minorcontains monomeric eburnamine-type of indole alkaloids having utilization as a neuro-medicinal plant. The biosynthetic pathway studies using miRNAs has been the focal point for plant genomic research in recent years and this technique is utilized to get an insight into a possible pathway level study inV. minoras understanding of genes in this prized medicinal plant is meagrely understood. The de novo transcriptomic analysis using Illumina Next gen sequencing has been performed in glasshouse shifted plant and transformed roots to elucidate the possible non confirmed steps of terpenoid indole alkaloids (TIAs) pathway inV. minor. A putative TIA pathway is elucidated in the study including twelve possible TIAs biosynthetic genes. The specific miRNA associated with TIAs pathway were identified and their roles were discussed for the first time inV. minor. The comparative analysis of transcriptomic data of glasshouse shifted plant and transformed roots showed that the raw reads of transformed roots were higher (83,740,316) compared to glasshouse shifted plant (67,733,538). The EST-SSR prediction showed the maximum common repeats among glasshouse shifted plant and transformed roots, although small variation was found in trinucleotide repeats restricted to glasshouse shifted plant. The study reveals overall 37 miRNAs which were observed to be true and can have a role in pathway as they can regulate the growth and alkaloid production. The identification of putative pathway genes plays an important role in establishing linkage between Aspidosperma and Eburnamine alkaloids.

}, keywords = {de novo transcriptomic analysis, EST-SSR, miRNA, Terpenoid indole alkaloids, Vinca minor}, issn = {0971-5894}, doi = {10.1007/s12298-020-00842-x, Early Access Date = JUL 2020}, author = {Verma, Priyanka and Singh, Noopur and Khan, Shamshad Ahmad and Mathur, Ajay Kumar and Sharma, Ashok and Jamal, Farrukh} } @article {46910, title = {Transmetallation vs adduct: diverse reactivity of N,O-ketiminato germylene with [Cp*MCl2](2) (M = Rh or Ir; Cp* = eta(5)-C5Me5) and MCl5 (M = Nb and Ta)}, journal = {Journal of Organometallic Chemistry}, volume = {911}, year = {2020}, month = {APR }, pages = {121142}, type = {Article}, abstract = {

The reactions of the germylenes, [(Dipp)NCMeCHCORGeCl] (1a: R = Me, 1b: R = Ph) with [Ir2Cl2(mu-Cl)(2)(eta(5)-Cp*)(2)] led to the formation of the adducts [(Dipp)NCMeCHCORGeClIrCl2Cp*] (3a: R = Me and 3b: R = Ph). On the other hand, [Rh2Cl2(mu-Cl)(2)(eta(5)-Cp*)(2)] does not react with the germylenes (1a and 1b). When the reactions of 1a and 1b are carried out with [Cp*TaCl4], the reaction led to decomposition. The reaction of 1a or 1b with TaCl5 yielded the transmetallated products [(Dipp)NCMeCHCORTaCl4] (4a: R = Me, 4b: R = Ph) with the extrusion of GeCl2. Our theoretical studies show that for, the insertion of TaCl5 to 1a and the formation of 4a with concomitant elimination of GeCl2 is energetically favourable. Extrusion of SnCl2 is also observed when the corresponding stannylene, [(Dipp)NCMeCHCOMeSnCl] was reacted with TaCl5. All these compounds have been characterized by H-1 and C-13 NMR spectroscopy, elemental analysis and the constitution of compounds 1b, 3b, and 4a were confirmed by single-crystal X-ray crystallography. (C) 2020 Elsevier B.V. All rights reserved.

}, keywords = {Adduct formation, Germylenes, Iridium, Ketoiminate, Tantalum, Transmetallation}, issn = {0022-328X}, doi = {10.1016/j.jorganchem.2020.121142}, author = {Raghavendra, Beesam and Bakthavachalam, K. and Das, Tamal and Roisnel, Thierry and Sen, Sakya S. and Vanka, Kumar and Ghosh, Sundargopal} } @article {46982, title = {Tris-heteroleptic ruthenium(II) polypyridyl complexes: Synthesis, structural characterization, photophysical, electrochemistry and biological properties}, journal = {Journal of Inorganic Biochemistry}, volume = {203}, year = {2020}, month = {FEB}, pages = {110903}, type = {Article}, abstract = {

{Three water-soluble tris-heteroleptic ruthenium(II) polypyridyl complexes [Ru(bpy)(phen)(bpg)](2+) (1), [Ru (bpy)(dppz)(bpg)]2+ (2), and [Ru(phen)(dppz)(bpg)]2+ (3) (where bpy = 2,2{\textquoteright}-bipyridine

}, keywords = {Circular dichroism, Cytotoxicity, fluorescence, Polypyridyl, ruthenium}, issn = {0162-0134}, doi = {10.1016/j.jinorgbio.2019.110903}, author = {Bhat, Satish S. and Kumbhar, Avinash S. and Purandare, Neeraja and Khan, Ayesha and Grampp, Gunter and Loennecke, Peter and Hey-Hawkins, Evamarie and Dixit, Ruchi and Vanka, Kumar} } @article {46771, title = {Tweaking palladium electronic structure to attain oxygen reduction activity superior to platinum/C}, journal = {ACS Applied Energy Materials}, volume = {3}, year = {2020}, month = {JUL}, pages = {6127-6132}, type = {Article}, abstract = {

Enhancing oxygen reduction (ORR) activity through alloying is crucial to improve the performance of a fuel-cell catalysts. In this work, we have studied the alloying effects of 4f rare-earth (RE) metals with palladium. The modified catalyst exhibits better activity (E-onset = 1 V and E-1/2 = 0.88 V) and higher selectivity toward H2O (similar to 97\%) compared to the state-of-the-art catalysts due to complete dissociation of O-2. Hirshfeld charge analysis and 2D-electron localization function reveal improved adsorbate-adsorbent interaction on the catalyst surface. This work paves a strategy to design highly selective non-Pt-based catalysts for the ORR by controlling electronic structures and surface oxide formation.

}, keywords = {d-band center, DFT calculation, durability, EuPd, oxygen reduction reaction, YbPd}, issn = {2574-0962}, doi = {10.1021/acsaem.0c01241}, author = {Sarma, Saurav Ch. and Kaja, Sai Manoj and Mishra, Vidyanshu and Vinod, Chathakudath Prabhakaran and Peter, Sebastian C.} } @article {47011, title = {Unprecedented isomerism-activity relation in molecular electrocatalysis}, journal = {Journal of Physical Chemistry Letters}, volume = {11}, year = {2020}, month = {JAN }, pages = {263-271}, type = {Article}, abstract = {

The role of electrocatalysts in energy storage/conversion, biomedical and environmental sectors, green chemistry, and much more has generated enormous interest in comprehending their structure-activity relations. While targeting the surface-to-volume ratio, exposing reactive crystal planes and interfacial modifications are time-tested considerations for activating metallic catalysts; it is primarily by substitution in molecular electrocatalysts. This account draws the distinction between a substituent{\textquoteright}s chemical identity and isomerism, when regioisomerism of the -NO2 substituent is conferred at the {\textquoteleft}{\textquoteleft}alpha{\textquoteright}{\textquoteright} and {\textquoteleft}{\textquoteleft}beta{\textquoteright}{\textquoteright} positions on the macrocycle of cobalt phthalocyanines. Spectroscopic analysis and theoretical calculations establish that the beta isomer accumulates catalytically active intermediates via a cumulative influence of inductive and resonance effects. However, the field effect in the alpha isomer restricts this activation due to a vanishing resonance effect. The demonstration of the distinct role of isomerism in substituted molecular electrocatalysts for reactions ranging from energy conversion to biosensing highlights that isomerism of the substituents makes an independent contribution to electrocatalysis over its chemical identity.

}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.9b02689}, author = {Kottaichamy, Alagar Raja and Begum, Shabbah and Nazrulla, Mohammed Azeezulla and Dargily, Neethu Christudas and Devendrachari, Mruthyunjayachari Chattanahalli and Bhat, Zahid Manzoor and Thimmappa, Ravikumar and Kotresh, Harish Makri Nimbegondi and Vinod, Chathakudath Prabhakaran and Thotiyl, Musthafa Ottakam} } @article {46691, title = {Unraveling the hidden role of the counteranion in {\textquoteleft}{\textquoteleft}cation in a cage{\textquoteright}{\textquoteright} systems}, journal = {Journal of Physical Chemistry A}, volume = {124}, year = {2020}, month = {OCT }, pages = {8040-8049}, type = {Article}, abstract = {

The current work showcases general principles at play in systems consisting of cations present inside molecular cages. Such systems, relevant to chemistry and biology, have been carefully investigated by computational methods. The important Ge(II)-encapsulating cage systems have been studied first. The very fact that such compounds exist appears highly unlikely, given the highly reactive nature of the Ge(II) dication. Our studies reveal what really occurs in solution when such complexes are formed: the Ge(II) dications are actually present as [Ge-X](+) (where X is the {\textquoteleft}{\textquoteleft}non-coordinating{\textquoteright}{\textquoteright} counterion employed in such systems) during entry and subsequent existence at the center of the cage. Hence, what is actually present is a {\textquoteleft}{\textquoteleft}pseudomonocation{\textquoteright}{\textquoteright}. Interestingly, such pseudomonocation-encapsulated cages are seen to be equally relevant in systems of biological importance, such as for dicationic s block-based ionophores. In explaining such cases, the concept of {\textquoteleft}{\textquoteleft}isoionicity{\textquoteright}{\textquoteright} is introduced, demonstrating that the counterion-coordinated dications are isoionic with a monocation, such as Li(I), isolated in the same ionophore.

}, issn = {1089-5639}, doi = {10.1021/acs.jpca.0c06995}, author = {Mukherjee, Anagh and Ghule, Siddharth and Tiwari, Mrityunjay K. and Vanka, Kumar} } @article {46718, title = {Vinylogous michael addition of 3-alkylidene-2-oxindoles to beta,gamma-unsaturated alpha-keto esters by bifunctional cinchona alkaloids}, journal = {European Journal of Organic Chemistry}, volume = {2020}, year = {2020}, month = {SEP }, pages = {5690-5694}, type = {Article}, abstract = {

A highly enantioselective vinylogous Michael addition of 3-alkylidene-2-oxindoles with beta,gamma-unsaturated alpha-keto esters using a bifunctional tertiary-amine thiourea catalyst is demontsrated. The challenging Michael reaction with the beta,gamma-unsaturated alpha-keto esters has been accomplished due to the synchronized H-bond guided dual activation of vinylogous nucleophile and electrophile by catalyst. The reaction afforded product in high yield while resulting in excellent stereocontrol (\> 19:1E/Zand upto 99 \%ee).

}, keywords = {3-Alkylidene-2-oxindoles, Asymmetric synthesis, beta, gamma-Unsaturated alpha-keto esters, Michael adduct, Vinylogous Michael addition}, issn = {1434-193X}, doi = {10.1002/ejoc.202000835, Early Access Date = SEP 2020}, author = {Jaiswal, Manish K. and Kumar, Rajesh and Singh, Sanjay and Jain, Shailija and Vanka, Kumar and Singh, Ravi P.} } @article {46670, title = {Wavelength dependent luminescence decay kinetics in {\textquoteleft}quantum-confined{\textquoteright} g-C(3)N(4)nanosheets exhibiting high photocatalytic efficiency upon plasmonic coupling}, journal = {Journal of Materials Chemistry A}, volume = {8}, year = {2020}, month = {OCT }, pages = {20581-20592}, type = {Article}, abstract = {

Serendipitous observations offer newer insights into materials properties. Here we describe g-C(3)N(4)nanosheets exhibiting remarkably blue-shifted photoluminescence within the 390-580 nm range centred at 425 nm which matches more closely with its {\textquoteleft}quantum-dots{\textquoteright}, and yet is excitation-wavelength independent. Moreover, surprisingly, the luminescence decay becomes increasingly slow at higher emission wavelengths, by up to 10 times. The nanosheets absorb only a fraction of visible-light. To improve this, when we designed a nanocomposite of g-C(3)N(4)and Au nanoparticles (NPs), it retained the PL characteristics and also exhibited excellent light-harvesting and photocatalytic efficiency for benzylamine (BA) oxidation. The surface plasmon resonance of the Au NPs is responsible for the high visible-light response and assisting the reaction by the {\textquoteleft}hot-electron{\textquoteright} injection mechanism, while an uncharacteristic, pronounced co-catalytic effect by them further improves the efficiency. The conversion is 98\% with \>99\% selectivity over 1.5 h of natural sunlight and open-air, probably the highest efficiency for BA photo-oxidation reactions. Even though such a dual role by plasmonic NPs has remained unscrutinized, we argue that the charge-transfer processes for the {\textquoteleft}hot-carrier{\textquoteright} injection and co-catalytic events are well-separated in time due to a much slower photon incident frequency on a catalyst particle, enabling both to occur simultaneously in the same particle.

}, issn = {2050-7488}, doi = {10.1039/d0ta08001b}, author = {Mondal, Sanjit and Sahoo, Lipipuspa and Vaishnav, Yuvraj and Mishra, Samita and Roy, Raj Sekhar and Vinod, C. P. and De, Arijit K. and Gautam, Ujjal K.} } @article {47079, title = {[1,3]-Claisen rearrangement via removable functional group mediated radical stabilization}, journal = {Organic Letters}, volume = {23}, year = {2021}, month = {FEB }, pages = {890-895}, type = {Article}, abstract = {

A thermal O-to-C [1,3]-rearrangement of alpha-hydroxy acid derived enol ethers was achieved under mild conditions. The 2-aminothiophenol protection of carboxylic acids facilitates formation of the [1,3] precursor and its thermal rearrangement via stabilization of a radical intermediate. Experimental and theoretical evidence for dissociative radical pair formation, its captodative stability via aminothiophenol, and a unique solvent effect are presented. The aminothiophenol was deprotected from rearrangement products as well as after derivatization to useful synthons.

}, issn = {1523-7060}, doi = {10.1021/acs.orglett.0c04109}, author = {Alam, Md Nirshad and Dash, Soumya Ranjan and Mukherjee, Anirban and Pandole, Satish and Marelli, Udaya Kiran and Vanka, Kumar and Maity, Pradip} } @article {47398, title = {Advances in transition-metal-catalyzed C-H bond oxygenation of amides}, journal = {Synthesis-Stuttgart}, year = {2021}, month = {APR }, type = {Article; Early Access}, abstract = {

C-O bond formation represents a fundamental chemical transformation in organic synthesis to develop valuably oxygenated (hetero)arenes. Particularly, the direct and regioselective C-H bond oxygenation of privileged amides, using a transition metal catalyst and a mild oxygenating source, is a step-economy and attractive approach. During the last decade, considerable progress has been realized in the direct C-H oxygenation of primary, secondary, and tertiary amides. This Short Review compiles the advances in transition-metal-catalyzed oxygenation of C(sp(2))-H and C(sp(3))-H bonds on various amides with diverse oxygenation sources. The review is categorized into two different major sections: (i) C(sp(2))-H oxygenation and (ii) C(sp(3))-H oxygenation. Each section is discussed based on the directing group (monodentate and bidentate) attached to the amide derivatives.

}, keywords = {Amides, C-H activation, directing group, Oxygenation, Transition Metal}, issn = {0039-7881}, doi = {10.1055/a-1481-2584, Early Access Date = APR 2021}, author = {Vijaykumar, Muniyappa and Punji, Benudhar} } @article {47651, title = {Annulation of enals with carbamoylpropiolates via NHC-catalyzed enolate pathway: access to functionalized maleimides/iso-maleimides and synthesis of aspergillus FH-X-213}, journal = {Journal of Organic Chemistry}, volume = {86}, year = {2021}, month = {JUL }, pages = {9466-9477}, type = {Article}, abstract = {Herein we report the N-heterocyclic carbene (NHC)-catalyzed [3 + 2] annulation of alpha,beta-unsaturated aldehydes with carbamoylpropiolates via an unusual enolate pathway leading to the construction of highly functionalized maleimides or isomaleimides. The electronic effect imposed by the alkyl/aryl group present on the amide nitrogen of carbamoylpropiolates plays a crucial role in the selective formation of these important five-membered heterocyclic building blocks. The developed protocol is mild and tolerates a wide range of substituents on both substrates. The application of this protocol in the synthesis of the antibacterial natural product Aspergillus FH-X-213 has also been demonstrated.}, issn = {0022-3263}, doi = {10.1021/acs.joc.1c00782}, author = {Viveki, Amol B. and Pol, Mahesh D. and Halder, Priyanka and Sonavane, Sameer R. and Mhaske, Santosh B.} } @article {47362, title = {Antiviral drugs prioritization for COVID-19 management based on rational selection}, journal = {Current Science}, volume = {120}, year = {2021}, month = {MAY }, pages = {1464-1470}, type = {Article}, abstract = {

The SARS-CoV-2 infection has resulted in COVID-19 pandemic worldwide. It has infected around 0.1 billion individuals and caused 2 million fatalities across the globe till mid-January 2021. Drug repurposing has been utilized as the most preferred therapeutic intervention for COVID-19 mitigation due to its necessity and feasibility. To prioritize therapeutic regime against COVID-19, we used 61 antiviral drugs and their combinations. Selected molecules were subjected to virtual screening against: (i) human angiotensin-converting enzyme 2 receptor binding domain (hACE-2) which serves as an anchor for virus attachment and entry, (ii) SARS-CoV-2 RNA dependent RNA polymerase (RdRp) responsible for viral RNA replication, and (iii) SARS-CoV-2 main protease (M-Pro) needed for viral polyprotein slab proteolytic processing. Based on docking score, pharmacodynamic and pharmacokinetic parameters, combinations of Daclatasvir, Elbasvir, Indinavir, Ledipasvir, Paritaprevir and Rilpivirine were analysed further. Our analysis suggested Sofosbuvir in combination with Ledipasvir and Daclatasvir as potential therapeutic agents for SARS-CoV-2. The combined score suggests that these combinations have superior anti-SARS-CoV-2 potential than Remdesivir and other investigational drugs. The present work provides a rationale-based approach to select drugs with possible anti-SARS-CoV-2 activity for further clinical evaluation.

}, keywords = {Drug repurposing, hACE-2, main protease, RNA dependent RNA polymerase, SARS-CoV-2}, issn = {0011-3891}, doi = {10.18520/cs/v120/i9/1464-1470}, author = {Joshi, Rakesh S. and Giri, Ashok P. and Kulkarni, Mahesh J. and Gupta, Mahesh and Verma, Savita and Chaudhry, Dhruva and Deshmukh, Narendra and Chugh, Anita} } @article {47452, title = {Aspergillus derived mycotoxins in food and the environment: prevalence, detection, and toxicity}, journal = {Toxicology Reports }, volume = {8}, year = {2021}, month = {JAN}, pages = {1008-1030}, type = {Article}, abstract = {

Aspergillus\ species are the paramount ubiquitous fungi that contaminate various food substrates and produce biochemicals known as mycotoxins. Aflatoxins (AFTs), ochratoxin A (OTA), patulin (PAT), citrinin (CIT), aflatrem (AT), secalonic acids (SA), cyclopiazonic acid (CPA), terrein (TR), sterigmatocystin (ST) and gliotoxin (GT), and other toxins produced by species of\ Aspergillus\ plays a major role in food and human health. Mycotoxins exhibited wide range of toxicity to the humans and animal models even at nanomolar (nM) concentration. Consumption of detrimental mycotoxins adulterated foodstuffs affects human and animal health even trace amounts. Bioaerosols consisting of spores and hyphal fragments are active elicitors of bronchial irritation and allergy, and challenging to the public health.\ Aspergillus\ is the furthermost predominant environmental contaminant unswervingly defile lives with a 40{\textendash}90 \% mortality risk in patients with conceded immunity. Genomics, proteomics, transcriptomics, and metabolomics approaches useful for mycotoxins{\textquoteright} detection which are expensive. Antibody based detection of toxins chemotypes may result in cross-reactivity and uncertainty. Aptamers (APT) are single stranded DNA (ssDNA/RNA), are specifically binds to the target molecules can be generated by systematic evolution of ligands through exponential enrichment (SELEX). APT are fast, sensitive, simple, in-expensive, and field-deployable rapid point of care (POC) detection of toxins, and a better alternative to antibodies.

}, doi = {10.1016/j.toxrep.2021.04.013}, author = {Navale, Vishwambar and Vamkudoth, Koteswara Rao and Ajmera, Shanthipriya and Dhuri, Vaibhavi} } @article {47438, title = {Autophagy and unique aerial oxygen harvesting properties exhibited by highly photocatalytic carbon quantum dots}, journal = {Carbon}, volume = {181}, year = {2021}, month = {AUG}, pages = {16-27}, type = {Article}, abstract = {

Plastic pollution is a serious threat to the environment as they are not bio-degradable. Herein using waste-polyethylene, we report two inter-related important findings. First that they can be converted economically and completely into highly photocatalytic carbon quantum-dots (CQDs) using H2O2\ as a residue-free oxidant in an acid medium, and they have the ability to enrich a reaction medium with an extraordinary amount of molecular oxygen harvested from the air so that no separate oxygen source is needed while carrying out facile photocatalytic\ oxidation reactions. Second, when they are not performing any photocatalytic reaction, they exhibit self-sensitized photo-oxidation to convert themselves completely to CO2\ in the presence of sunlight, a phenomenon that we term as {\textquoteleft}CQD-autophagy{\textquoteright} by drawing parallels to the death of useless-cells in the body. Such extinction from the reaction media is unique as no other material is known to do so and advantageous because the removal of carbon-dots from a solution is rather inefficient from an industry-viewpoint due to their high solubility. Instead, the inexpensive CQDs can be discarded casually with the notion that they will gradually get eliminated from the environment.

}, keywords = {Carbon dots, Oxygen-enrichment, Photocatalytic oxidation, Self-sensitized photo-oxidation}, issn = {0008-6223}, doi = {10.1016/j.carbon.2021.04.054}, author = {Mondal, Sanjit and Vinod, C. P. and Gautam, Ujjal K.} } @article {46671, title = {Biological process of lysine-tRNA charging is therapeutically targetable in liver cancer}, journal = {Liver International}, volume = {41}, year = {2021}, month = {JAN }, pages = {206-219}, type = {Article }, abstract = {

Background \& Aims Mature transfer RNAs (tRNA) charged with amino acids decode mRNA to synthesize proteins. Dysregulation of translational machineries has a fundamental impact on cancer biology. This study aims to map the tRNAome landscape in liver cancer patients and to explore potential therapeutic targets at the interface of charging amino acid with tRNA. Methods Resected tumour and paired tumour-free (TFL) tissues from hepatocellular carcinoma (HCC) patients (n = 69), and healthy liver tissues from organ transplant donors (n = 21), HCC cell lines, and cholangiocarcinoma (CC) patient-derived tumour organoids were used. Results The expression levels of different mature tRNAs were highly correlated and closely clustered within individual tissues, suggesting that different members of the tRNAome function cooperatively in protein translation. Interestingly, high expression of tRNA-Lys-CUU in HCC tumours was associated with more tumour recurrence (HR 1.1;P = .022) and worse patient survival (HR 1.1;P = .0037). The expression of Lysyl-tRNA Synthetase (KARS), the enzyme catalysing the charge of lysine to tRNA-Lys-CUU, was significantly upregulated in HCC tumour tissues compared to tumour-free liver tissues. In HCC cell lines, lysine deprivation, KARS knockdown or treatment with the KARS inhibitor cladosporin effectively inhibited overall cell growth, single cell-based colony formation and cell migration. This was mechanistically mediated by cell cycling arrest and induction of apoptosis. Finally, these inhibitory effects were confirmed in 3D cultured patient-derived CC organoids. Conclusions The biological process of charging tRNA-Lys-CUU with lysine sustains liver cancer cell growth and migration, and is clinically relevant in HCC patients. This process can be therapeutically targeted and represents an unexplored territory for developing novel treatment strategies against liver cancer.

}, keywords = {Cladosporin, liver cancer, lysine, Lysyl-tRNA Synthetase, tRNA-Lys-CUU, tRNAome}, issn = {1478-3223}, doi = {10.1111/liv.14692}, author = {Zhang, Ruyi and Noordam, Lisanne and Ou, Xumin and Ma, Buyun and Li, Yunlong and Das, Pronay and Shi, Shaojun and Liu, Jiaye and Wang, Ling and Li, Pengfei and Verstegen, Monique M. A. and Reddy, D. Srinivasa and van Der Laan, Luc J. W. and Peppelenbosch, Maikel P. and Kwekkeboom, Jaap and Smits, Ron and Pan, Qiuwei} } @article {47084, title = {Can we identify the salt-cocrystal continuum state using XPS?}, journal = {Crystal Growth \& Design}, volume = {21}, year = {2021}, month = {FEB }, pages = {735-747}, type = {Article}, abstract = {

X-ray photoelectron spectroscopy (XPS) is used to understand the nature of acid-base crystalline solids, to know whether the product is a salt (proton transfer, O-center dot center dot center dot H-N+) or a cocrystal (neutral adduct, O-H center dot center dot center dot N). The present study was carried out to explore if intermediate states of proton transfer from COOH to nitrogen (the proton resides between hydrogen bonded to O and N, O center dot center dot center dot H center dot center dot center dot N, quasi state) can be differentiated from a salt (complete proton transfer, N+-H center dot center dot center dot center dot O-) and cocrystal (no proton transfer, O-H center dot center dot center dot N) using N 1s XPS spectroscopy. The intermediate states of proton transfer arise when the pK(a) difference between the acid and the conjugate base is between -1 and 4, -1 \< Delta pK(a) \< 4, a situation common with COOH and pyridine functional groups present in drug molecules and pharmaceutically acceptable coformers. Complexes of pyridine N bases with aromatic COOH molecules in nine salts/cocrystals were cocrystallized, and their N 1s core binding energies in XPS spectra were measured. The proton state was analyzed by single-crystal X-ray diffraction for confirmation. Three new complexes were crystallized and analyzed by XPS spectra (without knowledge of their X-ray structures), to assess the predictive ability of XPS spectra in differentiating salt-cocrystal intermediate states against the extremities. The XPS results were subsequently confirmed by single-crystal X-ray data. Complexes of 3,5-dinitrobenzoic acid and isonicotinamide in 1:1 and 1:2 ratios exist as a salt and a salt-cocrystal continuum, respectively, as shown by the N 1s core binding energies. The proton states of the crystalline solids by XPS are in good agreement with the corresponding crystal structures. Other complexes, such as those of 3,5-dinitrobenzoic acid with 1,2-bis(4-pyridyl)ethylene, exhibit a salt-cocrystal continuum, maleic acids with 1,2-bis(4-pyridyl)ethylene and acridine are salts, 2-hydroxybenzoic acid and acridine is a salt, and the complex of 3,5-dinitrobenzoic acid and 3-hydroxypyridine is a salt and salt-cocrystal continuum, while fumaric acids with 1,2-bis(4-pyridyl)ethylene and acridine are cocrystals. Furthermore, three new acidbase complexes of 3,5-dinitrobenzoic acid with phenazine, 4-hydroxypyridine, and 4-cyanopyridine were studied initially by XPS and then confirmed by X-ray diffraction. In summary, since the N 1s binding energies cluster in a narrow range as cocrystals (398.7-398.9 eV) and salts (400.1-401.1 eV), it is clearly possible to differentiate between cocrystals and salts, but the saltcocrystal continuum values in XPS spectra are clustered in an intermediate range of cocrystals and salts but overlap with those of cocrystal or salt binding energies.

}, issn = {1528-7483}, doi = {10.1021/acs.cgd.0c00661}, author = {Tothadi, Srinu and Shaikh, Tabrez Rafique and Gupta, Sharad and Dandela, Rambabu and Vinod, Chathakudath P. and Nangia, Ashwini K.} } @article {47045, title = {Chemistry, anti-diabetic activity and structural analysis of substituted dihydropyrimidine analogues}, journal = {Journal of Molecular Structure}, volume = {1227}, year = {2021}, month = {MAR }, pages = {129412}, type = {Article}, abstract = {

In an effort to identify an anti-diabetic agent, a series of methyl/ethyl 4-(hydroxyphenyl)-6-methyl-2-oxo/thioxo-1,2,3,4 tetrahydropyrimidine-5-carboxylate analogues (4a-h) have been synthesized, purified, and characterized by using Fourier-Transform Infrared Spectroscopy (FT-IR) and NMR (H-1 and C-13). The synthesized compounds were screened for anti-hyperglycemic activity using Streptozotocin (STZ) induced diabetic rat model. The anti-hyperglycemic activity of dihydropyrimidine (DHPM) compound is mainly analyzed with the variation of substituents present on the phenyl ring and urea/thiourea group on pharmacophoric features. Further, the crystal structure and supramolecular characteristics of two compounds 4c and 4f were analyzed through a single-crystal X-ray method and the Hirshfeld Surface Analysis, which shows hydrogen bonding through N-H center dot center dot center dot O and N-H center dot center dot center dot S interactions with the formation of ring motif in the crystal structure. It is interesting to note that among the title compounds, the 4a, 4e, 4f, and 4g significantly displayed a better hypoglycemic effect in vivo rat model study. (C) 2020 Elsevier B.V. All rights reserved.

}, keywords = {Dihydropyrimidine (DHPM), Hypoglycemia, Streptozotocin (STZ), Type-2 diabetes mellitus (T2DM)}, issn = {0022-2860}, doi = {10.1016/j.molstruc.2020.129412}, author = {Bairagi, Keshab M. and Younis, Nancy Safwat and Emeka, Promise Madu and Venugopala, Katharigatta N. and Alwassil, I, Osama and Khalil, Hany Ezzat and Sangtani, Ekta and Gonnade, Rajesh G. and Mohanlall, Viresh and Nayak, Susanta K.} } @article {47373, title = {Chronic systemic exposure to IL6 leads to deregulation of glycolysis and fat accumulation in the zebrafish liver}, journal = {Biochimica ET Biophysica Acta-Molecular and Cell Biology of Lipids}, volume = {1866}, year = {2021}, month = {MAY}, pages = {158905}, type = {Article}, abstract = {

Inflammation is a constant in Non-Alcoholic Fatty Liver Disease (NAFLD), although their relationship is unclear. In a transgenic zebrafish system with chronic systemic overexpression of human IL6 (IL6-OE) we show that inflammation can cause intra-hepatic accumulation of triglycerides. Transcriptomics and proteomics analysis of the IL6-OE liver revealed a deregulation of glycolysis/gluconeogenesis pathway, especially a striking down regulation of the glycolytic enzyme aldolase b. Metabolomics analysis by mass spectrometry showed accumulation of hexose monophosphates and their derivatives, which can act as precursors for triglyceride synthesis. Our results suggest that IL6-driven repression of glycolysis/gluconeogenesis, specifically aldolase b, may be a novel mechanism for fatty liver. This mechanism may be relevant for NAFLD in lean individuals, an emerging class of NAFLD prevalent more in Asian Indian populations.

}, keywords = {Aldolase b, DHAP, Inflammation, Interleukin 6, Lean NAFLD, Non-alcoholic fatty liver}, issn = {1388-1981}, doi = {10.1016/j.bbalip.2021.158905}, author = {Singh, Manoj K. and Jayarajan, Rijith and Varshney, Swati and Upadrasta, Sindhuri and Singh, Archana and Yadav, Rajni and Scaria, Vinod and Sengupta, Shantanu and Shanmugam, Dhanasekaran and Shalimar and Sivasubbu, Sridhar and Gandotra, Sheetal and Sachidanandan, Chetana} } @article {47608, title = {Computational insights into the role of external and local electric fields in macrocyclic chemical and biological systems}, journal = {ChemPhysChem}, volume = {22}, year = {2021}, month = {DEC}, pages = {2484-2492}, type = {Article}, abstract = {The investigation of the role of the electric field in systems of widespread interest employing computational techniques is an emerging area of research. The outcome of applying an oriented external electric field (OEEF) on the geometric and electronic properties of the chemically unique pi-conjugated cyclic carbon ring compounds has been explored with density functional theory (DFT). Distinct changes in the structural and electronic features of such ring compounds are observed upon the application of OEEFs. Importantly, the calculations indicate that a mixed aliphatic-aromatic conjugated ring converts from a singlet to a triplet after the application of an OEEF, suggesting potential applications in optoelectronics for such molecules, without the need for photochemically induced change in the spin state. Furthermore, the influence of built-in local electric fields (LEFs) present in naturally occurring macrocyclic systems such as valinomycin has also been explored. Static and ab initio molecular dynamics (AIMD) calculations indicate that LEFs are the primary driving factor in determining the energetically favoured position of counter anions such as chloride (Cl-) in the potassium (K+) and sodium (Na+) coordinated valinomycin macrocycle structures: they exist inside the cage in the case of K+ sequestration by valinomycin and outside for Na+. This divergence has been proposed to be the determining factor for the selectivity of the valinomycin macrocycle for binding a K+ cation over Na+.}, keywords = {counter anions, Density functional calculations, electric field, ion selectivity, macrocyclic systems}, issn = {1439-4235}, doi = {10.1002/cphc.202100581}, author = {Mukherjee, Anagh and Ghule, Siddharth and Vanka, Kumar} } @article {47037, title = {Conductive interface promoted bifunctional oxygen reduction/evolution activity in an ultra-low precious metal based hybrid catalyst (vol 57, pg 1951, 2021)}, journal = {Chemical Communications}, volume = {57}, year = {2021}, month = {MAR }, pages = {2824}, type = {Correction}, issn = {1359-7345}, doi = {10.1039/d1cc90088a}, author = {Sarkar, Shreya and Varghese, Merin and Vinod, C. P. and Peter, Sebastian C.} } @article {47060, title = {Conductive interface promoted bifunctional oxygen reduction/evolution activity in an ultra-low precious metal based hybrid catalyst}, journal = {Chemical Communications}, volume = {57}, year = {2021}, month = {FEB}, pages = {1951-1954}, type = {Article}, abstract = {

Ultra low PtPd alloy deposited on Ni12P5 nanostructures (PtPd/Ni12P5) exhibited enhanced ORR activity (onset: 1.003 V and E-1/2:0.95 V) on par with commercial Pt/C and superior OER activity with 81\% reduction of the precious metal compared to the commercial catalyst.

}, issn = {1359-7345}, doi = {10.1039/d0cc08225b}, author = {Sarkar, Shreya and Varghese, Merin and Vinod, C. P. and Peter, Sebastian C.} } @article {47500, title = {Conserved RNA binding activity of phosphatidyl inositol 5-phosphate 4-kinase (PIP4K2A)}, journal = {Frontiers in Molecular Biosciences}, volume = {8}, year = {2021}, month = {MAY}, pages = {631281}, type = {Article}, abstract = {Plasmodium falciparum is a causative agent for malaria and has a complex life cycle in human and mosquito hosts. During its life cycle, the malarial parasite Plasmodium goes through different asexual and sexual stages, in humans and mosquitoes. Expression of stage-specific proteins is important for successful completion of its life cycle and requires tight gene regulation. In the case of Plasmodium, due to relative paucity of the transcription factors, it is postulated that posttranscriptional regulation plays an important role in stage-specific gene expression. Translation repression of specific set of mRNA has been reported in gametocyte stages of the parasite. A conserved element present in the 3 {\textquoteleft} UTR of some of these transcripts was identified. Phosphatidylinositol 5-phosphate 4-kinase (PIP4K2A) was identified as the protein that associates with these RNA. We now show that the RNA binding activity of PIP4K2A is independent of its kinase activity. We also observe that PIP4K2A is imported into the parasite from the host on Plasmodium berghei and Toxoplasma gondii. The RNA binding activity of PIP4K2A seems to be conserved across species from Drosophila and C. elegans to humans, suggesting that the RNA binding activity of PIP4K may be important, and there may be host transcripts that may be regulated by PIP4K2A. These results identify a novel RNA binding role for PIP4K2A that may not only play a role in Plasmodium propagation but may also function in regulating gene expression in multicellular organisms.}, keywords = {malaria, posttranscriptional gene regulation, RNA-protein interaction, translation regulation}, doi = {10.3389/fmolb.2021.631281}, author = {Behari, Jatin and Borkar, Pranita and Vindu, Arya and Dandewad, Vishal and Upadrasta, Sindhuri and Shanmugam, Dhanasekaran and Seshadri, Vasudevan} } @article {47746, title = {CuO as a reactive and reusable reagent for the hydrogenation of nitroarenes}, journal = {Applied Catalysis B-Environmental}, volume = {297}, year = {2021}, month = {NOV}, pages = {120417}, type = {Article}, abstract = {{Copper oxide (CuO) is used as a reusable solid reagent for hydrogenation of nitroarenes to aminoarenes. The use of CuO resulted in 100 \% conversion of 2.9 mmol of nitrobenzene to aniline in 45 s at room temperature using hydrazine hydrate as the reducing agent. During the reaction, CuO is converted to inactive metallic Cu which can be regenerated to active CuO by thermal oxidation. DFT simulations indicated facile formation of oxygen vacancies (EO}, keywords = {Copper vacancy, CuO, Hydrogenation, Nitroarene reduction, Oxygen defects, Reactive solids}, issn = {0926-3373}, doi = {10.1016/j.apcatb.2021.120417}, author = {Rajendran, K. and Pandurangan, N. and Vinod, C. P. and Khan, Tuhin S. and Gupta, Shelaka and Haider, M. Ali and Jagadeesan, D.} } @article {47381, title = {D-A-D based complementary unsymmetrical squaraine dyes for co-sensitized solar cells: enhanced photocurrent generation and suppressed charge recombination processes by controlled aggregation}, journal = {ACS Applied Energy Materials}, volume = {4}, year = {2021}, month = {APR}, pages = {3182-3193}, type = {Article}, abstract = {

A series of donor-acceptor-donor (D-A-D) based unsymmetrical squaraine dyes have been synthesized with indoline and aniline as donor units. The sp(3)-C, N atoms of the indoline and N atom of the aniline donors are appended with alkyl groups systematically to control the self-assembly of dyes on TiO2 and to passivate the photoanode that helps in improving the open circuit voltage (V-oc) of the dye-sensitized solar cell (DSSC) device. The resulting dyes, AK1-4, possess strong absorptions between 529 and 541 nm with extinction coefficients of 1.44-1.84 X 10(5) M-1 cm(-1). Photophysical and electrochemical studies revealed that the lowest unoccupied molecular orbital and highest occupied molecular orbital of the dyes are aligned with the conduction band of TiO2 and the redox function of the electrolyte for the efficient charge injection and dye regeneration processes, respectively. A DSSC device performance for AK4 of 7.93\% (V-oc of 815.88 mV and short circuit current density (J(sc)) of 12.4 mA/cm(2)) is obtained, with an incident photon to current conversion efficiency (IPCE) response of 92\% at 473 nm and 86\% at 566 nm without sensitizing with coadsorbent. IPCE studies revealed the equal contribution for the photocurrent generation from the H-aggregated structures. Further, such a high V-oc and DSSC efficiency have been observed first time for this class of zwitterionic dyes with the I-/I-3(-) electrolyte without sensitizing with coadsorbent. The importance of introducing the alkyl groups at the indoline as well as aniline donor units for the synergistic boosting of both V-oc, and J(sc) is compared with the model dye AK1. Complementary light absorbing dyes SQ1 and SQS4 possess absorption at 643 nm with extinction coefficients of 1.4 and 3.0 x 10(5) M-1 cm(-1), respectively. A cosensitized device performance of 9.36\% is obtained for the AK4:SQS4 (1:1) combination in the I-/I-3(-) electrolyte. The IPCE profile indicates a good response over 450-700 nm with 94\% at 621 nm. The importance of aggregated structures from both the dyes AK4 and SQS4 for photocurrent generation is realized.

}, keywords = {aggregation of dyes, co-sensitization, extension of conjugation, H-aggregate, squaraine dyes}, issn = {2574-0962}, doi = {10.1021/acsaem.0c02966}, author = {Singh, Ambarish Kumar and Veetil, Athulya Nellur and Nithyanandhan, Jayaraj} } @article {47701, title = {DART: deep learning enabled topological interaction model for energy prediction of metal clusters and its application in identifying unique low energy isomers}, journal = {Physical Chemistry Chemical Physics}, volume = {23}, year = {2021}, month = {OCT }, pages = {21995-22003}, type = {Article}, abstract = {Recently, machine learning (ML) has proven to yield fast and accurate predictions of chemical properties to accelerate the discovery of novel molecules and materials. The majority of the work is on organic molecules, and much more work needs to be done for inorganic molecules, especially clusters. In the present work, we introduce a simple topological atomic descriptor called TAD, which encodes chemical environment information of each atom in the cluster. TAD is a simple and interpretable descriptor where each value represents the atom count in three shells. We also introduce the DART deep learning enabled topological interaction model, which uses TAD as a feature vector to predict energies of metal clusters, in our case gallium clusters with sizes ranging from 31 to 70 atoms. The DART model is designed based on the principle that the energy is a function of atomic interactions and allows us to model these complex atomic interactions to predict the energy. We further introduce a new dataset called GNC_31-70, which comprises structures and DFT optimized energies of gallium clusters with sizes ranging from 31 to 70 atoms. We show how DART can be used to accelerate the process of identification of low energy structures without geometry optimization. Albeit using a topological descriptor, DART achieves a mean absolute error (MAE) of 3.59 kcal mol(-1) (0.15 eV) on the test set. We also show that our model can distinguish core and surface atoms in the Ga-70 cluster, which the model has never encountered earlier. Finally, we demonstrate the transferability of the DART model by predicting energies for about 6k unseen configurations picked up from molecular dynamics (MD) data for three cluster sizes (46, 57, and 60) within seconds. The DART model was able to reduce the load on DFT optimizations while identifying unique low energy structures from MD data.}, issn = {1463-9076}, doi = {10.1039/d1cp02956h}, author = {Modee, Rohit and Agarwal, Sheena and Verma, Ashwini and Joshi, Kavita and Priyakumar, U. Deva} } @article {47644, title = {Deoxygenative hydroboration of primary and secondary amides: a catalyst-free and solvent-free approach}, journal = {Chemical Communications}, volume = {57}, year = {2021}, month = {OCT }, pages = {10596-10599}, type = {Article}, abstract = {In contrast to the recent reports on catalytic hydroboration of amides to amines with pinacolborane (HBpin), a simple catalyst-free and solvent-free method for the hydroboration of a variety of amides has been realized. To get the mechanistic insights, DFT calculations have been performed.}, issn = {1359-7345}, doi = {10.1039/d1cc04148g}, author = {Kumar, Rohit and Bisai, Milan Kumar and Jain, Shailja and Vanka, Kumar and Sen, Sakya S.} } @article {47576, title = {Development of enhanced hypericin yielding transgenic plants and somaclones: high throughput direct organogenesis from leaf and callus explants of Hypericum perforatum (Retraction of Vol 111, Pg 544, 2018)}, journal = {Industrial Crops and Products}, volume = {171}, year = {2021}, month = {NOV }, pages = {113863}, type = {Retraction}, issn = {0926-6690}, doi = {10.1016/j.indcrop.2021.113863}, author = {Khan, A. Shamshad and Verma, Priyanka and Arbat, Akshata and Gaikwad, Sushma and Parasharami, A. Varsha} } @article {47756, title = {Direct oxidation of cyclohexane to adipic acid by a WFeCoO(OH) catalyst: role of bronsted acidity and oxygen vacancies}, journal = {ACS Catalysis}, volume = {11}, year = {2021}, month = {SEP }, pages = {10754-10766}, type = {Article}, abstract = {This work reports the catalytic activity of the trimetallic mixed-metal oxyhydroxide WFeCoO(OH) for the direct oxidation of cyclohexane to adipic acid (AA) without the use of concentrated HNO3. WFeCoO(OH) displayed a 40\% conversion of cyclohexane and a 67\% selectivity to AA under relatively milder conditions of temperature (90 degrees C) and pressure (1 atm). Experimental evidence confirmed the presence of acidic, basic, and redox sites on WFeCoO(OH). The detailed investigation revealed that doping W in the Co-FeO(OH) matrix increased the amount of surface lattice oxygen (OS-L) and caused a significant surge in acidity (5.1 mmol/g). The calculated deprotonation energy of WFeCoO(OH) was 1434 kJ/mol, and the trend in acidity was WCoO(OH) < WFeCoO(OH) < FeCoO(OH) similar to CoO(OH). Energy calculations showed that WFeCoO(OH) had a high propensity to generate oxygen vacancies by the loss of either a water molecule or an oxygen atom (-132.2 or -140.9 kJ/mol, respectively). Basicity was generated due to the presence of conjugate pairs of the surface hydroxyl groups. The combined action of the trifunctional acidic, basic, and redox-active metal centers along with the oxygen vacancies was responsible for the enhanced catalytic performance.}, keywords = {Adipic Acid, deprotonation energy, metal oxyhydroxides, multifunctional catalysts, oxygen vacancies}, issn = {2155-5435}, doi = {10.1021/acscatal.1c01464}, author = {Vernekar, Dnyanesh and Dayyan, Mohammad and Ratha, Satyajit and Rode, V, Chandrashekhar and Haider, M. Ali and Khan, Tuhin Suvra and Jagadeesan, Dinesh} } @article {47410, title = {Direct synthesis of mesoporous siliceous phosphotungstic acid and its superior catalytic activity on the cyclohexylation of phenol}, journal = {Journal of Physical Chemistry C }, volume = {125}, year = {2021}, month = {APR }, pages = {6723-6734}, type = {Article}, abstract = {

The synthesis of highly active and reusable mesoporous siliceous phosphotungstic acid materials (mPTA-Si) which are prepared through a simple self-assembly between phosphotungstic acid (PTA), the polymeric surfactant, and the silica precursor assisted by KCl for cyclohexylation of phenol is reported. The surface area and the acidity of these materials are tuned with a simple adjustment of PTA in the silica framework. The prepared samples exhibit mesoporous structure with a high surface area, but the structure is collapsed when the loading of PTA is high. It is established that the Keggin structure of PTA is retained on the final mPTA-Si. mPTA-Si with different loadings of PTA are employed as the catalysts for the cyclohexylation of phenol under liquid phase conditions. Among the catalysts studied, 10.0-mPTA-8.3Si calcined at 350 degrees C is found to be highly active, selective, and recyclable and offers 100\% conversion of phenol with the highest selectivity for p-cyclohexylphenol (96.8\%).

}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.1c01596}, author = {Ilbeygi, Hamid and Sawant, Dhanashri P. and Ruban, Sujanya M. and Reshma, Kokane S. and Umbarkar, Shubhangi B. and Halligudi, Shivappa B. and Vinu, Ajayan} } @article {47422, title = {Diverse reactivity of carbenes and silylenes towards fluoropyridines}, journal = {Chemical Communications}, volume = {57}, year = {2021}, month = {MAY }, pages = {4428-4431}, type = {Article}, abstract = {

The reaction of IDipp with C5F5N led to functionalization of all three carbon atoms of the imidazole ring with HF2- as the counter-anion (1). Reactivity with 2,3,5,6-tetrafluoropyridine gives only C-F bond activation leaving C-H bonds intact (5b). The reaction of SIDipp with C5F5N in the presence of BF3 afforded the ring cleavage product (3). Analogous reactions with silylene led to oxidative addition at the Si(II) center.

}, issn = {1359-7345}, doi = {10.1039/d1cc01401c, Early Access Date = MAR 2021}, author = {Kundu, Gargi and Ajithkumar, V. S. and Bisai, Milan Kumar and Tothadi, Srinu and Das, Tamal and Vanka, Kumar and Sen, Sakya S.} } @article {47086, title = {Diverse reactivity of hypersilylsilylene with boranes and threecomponent reactions with aldehyde and HBpin}, journal = {Inorganic Chemistry}, volume = {60}, year = {2021}, month = {FEB }, pages = {1654-1663}, type = {Article}, abstract = {

The recently reported hypersilylsilylene PhC-(NtBu)(2)SiSi(SiMe3)(3) (1) reacts with BH3, 9-BBN, and PhBCl2 to yield the respective Lewis acid base adducts 2-4, respectively. Compound 4 undergoes isomerization to form a ring expansion product 5. The same silylene was found to initially form an adduct with HBpin (6) and subsequently isomerized to 7 via the rupture of the B-H bond of HBpin (7), where the hydride was bound to the carbon atom of the amidinate ligand and the Bpin unit was attached to the silicon center. Surprisingly, the reaction of 1 with HBcat results in PhC(NtBu)(2)Bcat (8). Subsequently, we have shown that HBcat forms the same product when it reacts with related silylene PhC(NtBu)(2)SiN(SiMe3)(3) (1{\textquoteright}). With all of these reactions in hand, we ponder if silylene can activate two small molecules at one time. In this work, we delineate the three-component reactions of silylenes 1 and 1{\textquoteright} with 4-fluorobenzaldehyde and HBpin, which afforded unusual coupling products, 9 and 10, respectively. Note that 9 and 10 were prepared from the cleavage of the B-H and C=O bonds by silylene in a single reaction and are the first structurally attested Si-C-O-B coupled products.

}, issn = {0020-1669}, doi = {10.1021/acs.inorgchem.0c03137}, author = {Bisai, Milan Kumar and Swamy, V. S. V. S. N. and Raj, K. Vipin and Vanka, Kumar and Sen, Sakya S.} } @article {47388, title = {Easy and practical approach to access multifunctional cylcopentadiene- and cyclopentene-spirooxindoles via [3+2] annulation}, journal = {Organic \& Biomolecular Chemistry}, volume = {19}, year = {2021}, month = {MAY}, pages = {4338-4345}, type = {Article}, abstract = {

A highly regioselective [3 + 2] annulation of Morita-Baylis-Hillman (MBH) carbonates of isatin with aurone/thioaurone is developed. Spiroheterocycles such as spirooxindole cyclopentadiene and spirooxindole fused hydroxy cyclopentene derivatives are constructed in one pot by exploring the reactivity of Lewis bases. Combined experimental and density functional theory (DFT) calculations offered an insight into the reaction mechanism.

}, issn = {1477-0520}, doi = {10.1039/d1ob00514f, Early Access Date = APR 2021}, author = {Warghude, Prakash K. and Sabale, Abhijeet S. and Dixit, Ruchi and Vanka, Kumar and Bhat, Ramakrishna G.} } @article {47067, title = {Exceptional capacitance enhancement of a non-conducting COF through potential-driven chemical modulation by redox electrolyte}, journal = {Advanced Energy Materials}, volume = {11}, year = {2021}, month = {APR}, pages = {2003626}, type = {Article}, abstract = {

Capacitors are the most practical high-storage and rapid charge-release devices. The number of ions stored per unit area and their interaction strength with the electrode dictates capacitor-performance. Microporous materials provide a high storage surface and optimal interactions. Adsorbing electron-rich and easily polarizable molecules into microporous electrodes is expected to boost Faradaic pseudo-activity. If such electrode-electrolyte interactions can be made as a potential-driven reversible process, the resulting capacitors would be adaptable and device-friendly. A composite covalent organic framework (COF)-carbon electrode with redox-active KI is combined in an H2SO4 electrolyte for the first time. This composite electrode benefits from the redox-functionality of COF and electronic conductivity of carbon, leading to superior capacitative activity. Operando spectro-electrochemical measurements reveal the existence of multiple polyiodide species, although the I-3(-) is the predominantly electroactive species adsorbing on the microporous triazine-phenol COF electrode. A systematic fabrication of the flexible solid-state devices using the COF-redox-electrolyte reveals a high areal capacitance of 270 +/- 11 mF cm(-2) and gravimetric capacitance of 57 +/- 8 F g(-1). The inclusion of KI in H2SO4 (electrolyte) yields an approximately eight-fold enhancement in solid-state gravimetric specific capacitance. The imine-COF retains 89\% of its capacity even after 10 000 cycles.

}, keywords = {covalent organic frameworks, polyiodide, redox electrolytes, solid\&\#8208, state capacitors, Supercapacitors}, issn = {1614-6832}, doi = {10.1002/aenm.202003626, Early Access Date = FEB 2021}, author = {Kushwaha, Rinku and Haldar, Sattwick and Shekhar, Pragalbh and Krishnan, Akshara and Saha, Jayeeta and Hui, Pramiti and Vinod, Chathakudath Prabhakaran and Subramaniam, Chandramouli and Vaidhyanathan, Ramanathan} } @article {47028, title = {Facile transfer of excited electrons in Au/SnS2 nanosheets for efficient solar-driven selective organic transformations}, journal = {Applied Catalysis B-Environmental}, volume = {286}, year = {2021}, month = {JUN }, pages = {119927}, type = {Article}, abstract = {

Solar driven aerial oxidation processes have gained importance in organic transformations leading to the development of many nanocrystalline photocatalysts. Although such nanomaterials have many potential advantages, they often underperform due to poor visible light absorption and rapid recombination of excitons. Incorporation of plasmonic nanoparticles (NPs) on the catalyst surfaces can extend their response to visible light and improve photocatalytic efficiency by the {\textquoteleft}hot-electron{\textquoteright} injection mechanism. Nanostructures of SnS2 too absorb a part of the visible light to induce many photocatalytic reactions, though their ability to perform the selective and controlled organic transformations has not yet been observed. Herein, we demonstrate the first example of such transformation with the oxidative coupling of various benzylamine (BA) derivatives to imines under ambient conditions using SnS2 nanosheets (NSs). The reaction rate improves manifold and shows similar to 98 \% conversion (\>99 \% selectivity) in 2 h under direct sunlight and open-air when the NSs were decorated with 1.5 wt\% Au NPs on (Au/SnS2), making it one of the best catalysts for this reaction. We found that the large enhancement in activity upon Au loading is accompanied by a noticeable change in photo-induced charge accumulation behaviour in Au/SnS2 from the usual {\textquoteleft}{\textquoteleft}spike and overshoot{\textquoteright}{\textquoteright} one and contributed by facile transfer of excited electrons across the Au-SnS2 heterojunction in which Au NPs act as both sources and sinks for the photo-excited electrons. Finally, a detailed mechanism of the oxidation reaction has been proposed.

}, keywords = {Benzylamine oxidation, Hot-electron injection, Plasmonic nanoparticle, SnS2 nanosheet, Solar energy harvesting}, issn = {0926-3373}, doi = {10.1016/j.apcatb.2021.119927}, author = {Mondal, Sanjit and Sahoo, Lipipuspa and Vinod, C. P. and Gautam, Ujjal K.} } @article {47694, title = {FnCas9-based CRISPR diagnostic for rapid and accurate detection of major SARS-CoV-2 variants on a paper strip}, journal = {eLife}, volume = {10}, year = {2021}, month = {JUN }, pages = {e67130}, type = {Article}, abstract = {The COVID-19 pandemic originating in the Wuhan province of China in late 2019 has impacted global health, causing increased mortality among elderly patients and individuals with comorbid conditions. During the passage of the virus through affected populations, it has undergone mutations, some of which have recently been linked with increased viral load and prognostic complexities. Several of these variants are point mutations that are difficult to diagnose using the gold standard quantitative real-time PCR (qRT-PCR) method and necessitates widespread sequencing which is expensive, has long turn-around times, and requires high viral load for calling mutations accurately. Here, we repurpose the high specificity of Francisella novicida Cas9 (FnCas9) to identify mismatches in the target for developing a lateral flow assay that can be successfully adapted for the simultaneous detection of SARS-CoV-2 infection as well as for detecting point mutations in the sequence of the virus obtained from patient samples. We report the detection of the S gene mutation N501Y (present across multiple variant lineages of SARS-CoV-2) within an hour using lateral flow paper strip chemistry. The results were corroborated using deep sequencing on multiple wild-type (n = 37) and mutant (n = 22) virus infected patient samples with a sensitivity of 87\% and specificity of 97\%. The design principle can be rapidly adapted for other mutations (as shown also for E484K and T716I) highlighting the advantages of quick optimization and roll-out of CRISPR diagnostics (CRISPRDx) for disease surveillance even beyond COVID-19. This study was funded by Council for Scientific and Industrial Research, India.}, issn = {2050-084X}, doi = {10.7554/eLife.67130}, author = {Kumar, Manoj and Gulati, Sneha and Ansari, Asgar H. and Phutela, Rhythm and Acharya, Sundaram and Azhar, Mohd and Murthy, Jayaram and Kathpalia, Poorti and Kanakan, Akshay and Maurya, Ranjeet and Vasudevan, Janani Srinivasa and Aparna, S. and Pandey, Rajesh and Maiti, Souvik and Chakraborty, Debojyoti} } @article {47653, title = {Glycerol-triazole conjugated rhodamine as colorimetric and fluorimetric sensor for Cu2+}, journal = {ChemistrySelect}, volume = {6}, year = {2021}, month = {SEP}, pages = {9288-9292}, type = {Article}, abstract = {{A glycerol-triazole tethered rhodamine based colorimetric and fluorimetric sensor 3 {\textquoteleft},6 {\textquoteleft}-bis(diethylamino)-2-(((1-(1,3-dihydroxypropan-2-yl)-1H-1,2,3-triazol-4 -yl)methylene)aminospiro [isoindoline-1,9 {\textquoteleft}-xanthen]-3-one (L1) is designed and synthesized for the selective recognition of Cu2+ ion. The sensor L1 allows naked eye detection of Cu2+ ion with a fast response (<1 min). Among the various metal ions tested, the sensor L1 shows selective binding with Cu2+ through turn-on fluorescence mechanism. The sensor shows 1 : 2 binding stoichiometry with binding constant}, keywords = {Cu2+ Sensor, DFT, Glycerol, Rhodamine B, Triazole}, issn = {2365-6549}, doi = {10.1002/slct.202102145}, author = {Verma, Abhishek and Gahlyan, Parveen and Bawa, Rashim and Dash, Soumya Ranjan and Prasad, Ashok K. and Kumar, Rakesh} } @article {47646, title = {Gold-catalyzed complementary nitroalkyne internal redox process: a DFT study}, journal = {Frontiers in Chemistry}, volume = {9}, year = {2021}, month = {JUL}, pages = {689780}, type = {Article}, abstract = {Gold-catalysis, in this century, is one of the most emerging and promising new areas of research in organic synthesis. During the last two decades, a wide range of distinct synthetic methodologies have been unveiled employing homogeneous gold catalysis and aptly applied in the synthesis of numerous natural products and biologically active molecules. Among these, the reactions involving alpha-oxo gold carbene/alpha-imino gold carbene intermediates are of contemporary interest, in view of their synthetic potential and also due to the need to understand the bonding involved in these complexes. In this manuscript, we document the theoretical investigations on the regio-selectivity dependence of substitution on the gold-catalyzed cycloisomerization of o-nitroarylalkyne derivatives. We have also studied the relative stabilities of alpha-oxo gold carbene intermediates.}, keywords = {alpha-Oxo Gold Carbene, cycloisomerization, DFT calculation, Gold-catalysis, internal redox}, issn = {2296-2646}, doi = {10.3389/fchem.2021.689780}, author = {Vipin Raj, K. and Dhote, Pawan S. S. and Vanka, Kumar and Ramana, Chepuri V. V.} } @article {47440, title = {Green route for carbonylation of amines by CO2 using Sn-Ni-O bifunctional catalyst and theoretical study for finding best suited active sites}, journal = {Chemical Engineering Journal }, volume = {419}, year = {2021}, month = {SEP}, pages = {129439}, type = {Article}, abstract = {

Reaction between n-alkylamine and CO2\ has gained interest due to the demand for the dialkylurea for various applications. For the first time, the tool\ Mathematica\ was used to analyze the experimental data with an idea to derive an equation which determines the best suited active sites for any given input set of dependent parameters. The equation can further be used to predict the product yield with the known values of active sites for a reaction. Among several Sn containing mixed oxides, Sn-Ni oxide (Sn-Ni-O) was found to be the better performing catalyst. The studies indicate that the formation of new defect sites when NiO and SnO2\ are in the mixed state and possibly a solid solution enhances the catalytic efficiency. There are two main reasons for improved catalytic performance; one, mixing of SnO2\ into NiO which reduces the number of holes (h+) localized on lattice oxygen (O2-+ h+{\textrightarrow} O{\textbullet}-) and two, smaller SnO2\ particles are dispersed on the bigger particle NiO which alters the acidic and basic active sites in the catalyst. FT-IR adsorption study with amine and CO2\ helped in deriving a plausible mechanism for this reaction. Under optimized reaction condition, Sn1.1-Ni-O-600 gave 77.3\% of n-butylamine conversion and 75.7\% of yield for 1,3-dibutylurea. The versatility of the catalyst was tested for carbonylation of different aliphatic and aromatic amines, diamine and hydroxy amine with CO2.

}, keywords = {amines, CO2, Mixed oxide catalyst and bi-functional catalyst, Substituted urea}, issn = {1385-8947}, doi = {10.1016/j.cej.2021.129439}, author = {Kulal, Nagendra and Vetrivel, Rajappan and Gopinath, Chinnakonda S. and Ravindran, Rahul K. and Rao, Vinod N. and Shetty, Manjunath and Shrikanth, R. and Rangappa, Dinesh and Shanbhag, Ganapati V.} } @article {47310, title = {Highly efficient and reusable Ru-NaY catalyst for the base free oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic acid}, journal = {Catalysis Today}, volume = {375}, year = {2021}, month = {SEP}, type = {Article}, abstract = {

Oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is an important reaction for the production of recyclable bio-based polymers. Herein, we report a series of Ru nanoparticles supported on NaY zeolites catalysts for the oxidation of HMF to FDCA. The catalysts were prepared by simple ion exchanged method. Among all the catalysts, the optimized 3 wt \% Ru-NaY catalyst showed superior catalytic activity under base free conditions with a shorter period of reaction time. The conversion of HMF was 100 \% with 94 \% FDCA yield. This catalyst was reused for fourth cycles, with an insignificant decrease in the yield of FDCA. H2-chemisorption and HRTEM studies confirmed that high metal dispersion and small size of Ru nanoparticles play vital roles for the HMF oxidation. In addition, the acidic hydroxyl groups of the supercage as well as higher amount of metallic Ru{\textdegree} are also responsible for the high yield and productivity of FDCA.

}, doi = {10.1016/j.cattod.2020.05.009}, author = {Kandasamy, Prabu and Gogoi, Pranjal and Venugopalan, Aswathy Thareparambil and Raja, Thirumalaiswamy} } @article {47125, title = {In silico studies, synthesis and antitubercular activity of some novel quinoline - azitidinone derivatives}, journal = {Current Computer-Aided Drug Design}, volume = {17}, year = {2021}, month = {JAN}, pages = {134-143}, type = {Article}, abstract = {

Background: Diarylquinolines like Bedaquiline have shown promising antitubercular activity by their action of Mycobacterial ATPase. Objective: The structural features necessary for a good antitubercular activity for a series of quinoline derivatives were explored through computational chemistry tools like QSAR and combinatorial library generation. In the current study, 3-Chloro-4-(2-mercaptoquinoline-3-yl)-1-substitutedphenylazitidin-2-one derivatives have been designed and synthesized based on molecular modeling studies as anti-tubercular agents. Methods: 2D and 3D QSAR analyses were used to designed compounds having a quinoline scaffold. The synthesized compounds were evaluated against active and dormant strains of Mycobacterium tuberculosis (MTB) H37 Ra and Mycobacterium bovis BCG. The compounds were also tested for cytotoxicity against MCF-7, A549 and Panc-1 cell lines using MTT assay. The binding affinity of designed compounds was gauged by molecular docking studies. Results: Statistically significant QSAR models generated by the SA-MLR method for 2D QSAR exhibited r(2) = 0.852, q(2) = 0.811, whereas 3D QSAR with SA-kNN showed q(2) = 0.77. The synthesized compounds exhibited MIC in the range of 1.38-14.59(mu g/ml). These compounds showed some crucial interaction with MTB ATPase. Conclusion: The present study has shown some promising results which can be further explored for lead generation.

}, keywords = {combilib, Molecular docking, mycobacterial ATPase, QSAR, Quinoline}, issn = {1573-4099}, doi = {10.2174/1573409916666200129095952}, author = {Chitre, Trupti S. and Asgaonkar, Kalyani D. and Vikhe, Amrut B. and Patil, Shital M. and Garud, Dinesh R. and Khedkar, Vijay M. and Sarkar, Dhiman and Nawale, Laxman U. and Yeware, Amar} } @article {47432, title = {In situ polymerization process: an essential design tool for lithium polymer batteries dagger}, journal = {Energy \& Environmental Science}, volume = {14}, year = {2021}, month = {MAY }, pages = {2708-2788}, type = {Review}, abstract = {

Polymer electrolytes (PEs), a type of solid-state electrolytes (SSEs), have been in contention for nearly half a century to replace organic liquid electrolytes (LEs) that are used in state-of-the-art lithium-ion batteries (LIBs). They are envisaged to accelerate the industrial-scale production of safe, energy-dense, flexible, and thin lithium polymer batteries (LPBs). LPBs are expected to be widely employed for electric propulsion and other futuristic applications, such as flexible electronics and the Internet of Things (IoT). Even though several polymer architectures and chemistries have been attempted so far, PEs that can outperform LEs remain a real challenge. Apart from inadequate Li+-ion transport properties, challenges concerning the integration of PEs and the engineering of compatible, robust, and durable interfaces and interphases at both the electrodes of LPBs must be appropriately addressed. Recently, the in situ polymerization process has been widely employed as a robust fabrication tool for surpassing the intricacies related to the integration of PEs in LPBs. Hence, in this review, we focus on the in situ polymerization processes that employ various polymerization methods (e.g., free-radical polymerization, ionic polymerization, electropolymerization, condensation polymerization, etc.), functional monomers and oligomers (e.g., acrylate, methacrylate, allyl and vinyl ethers, epoxides, etc.), and PE integration strategies for the fabrication of lithium (ion and metal) polymer batteries (LIPBs and LMPBs). Additionally, this review also evaluates the approaches that have been developed until now to implement the in situ processing of LPBs from large-sized pouch cells to flexible-/printable-batteries and even microbatteries.

}, issn = {1754-5692}, doi = {10.1039/d0ee03527k, Early Access Date = FEB 2021}, author = {Vijayakumar, Vidyanand and Anothumakkool, Bihag and Kurungot, Sreekumar and Winter, Martin and Nair, Jijeesh Ravi} } @article {46766, title = {In situ preparation of ionomer as a tool for triple-phase boundary enhancement in 3D graphene supported Pt catalyst}, journal = {Advanced Sustainable Systems}, volume = {5}, year = {2021}, month = {JAN}, pages = {2000125}, type = {Article}, abstract = {

For improving the performance of platinum electrocatalysts in polymer electrolyte membrane fuel cells (PEMFCs), it is important to enhance the Pt utilization level in the catalyst systems. A high performing electrocatalyst (Pt/3DNG) is developed for PEMFC applications by using nitrogen-doped 3D graphene (3DNG) as the support material and an in situ grafted active {\textquoteleft}{\textquoteleft}triple-phase boundary{\textquoteright}{\textquoteright} to more precisely control the formation of the proton conducting ionomer interface at the active sites. Considering the 3D morphology of the system, during the electrode fabrication for realistic single-cell evaluation, the concept of in situ generation of the proton conducting-ionomer based {\textquoteleft}{\textquoteleft}active triple-phase boundary{\textquoteright}{\textquoteright} is introduced, which could potentially replace the conventional method of using Nafion ionomer for the electrode preparation. The monomers owing to their small-size can access the pores and inner regions of the 3DNG support, which on UV-curing, undergo polymerization and transform into an ionomer with an extended interfacial network into the nanoregimes of 3DNG. Single cell evaluation of the membrane electrode assembly in a high-temperature PEMFC by using phosphoric acid doped polybenzimidazole membrane demonstrates the utility of the present strategy.

}, keywords = {electrocatalysts, fuel cells, graphene, oxygen reduction reaction}, issn = {2366-7486}, doi = {10.1002/adsu.202000125, Early Access Date = JUL 2020}, author = {Gangadharan, Pranav K. and Vijayakumar, Vidyanand and Nediyirakkal, Shijil A. and Fernandez, Roshni Tresa and Siddharthan, V. Adhrika and Kurungot, Sreekumar} } @article {47390, title = {Insights from a pan India Sero-epidemiological survey (Phenome-India Cohort) for SARS-CoV2}, journal = {eLife}, volume = {10}, year = {2021}, month = {APR }, pages = {e66537}, type = {Article}, abstract = {

To understand the spread of SARS-CoV2, in August and September 2020, the Council of Scientific and Industrial Research (India) conducted a serosurvey across its constituent laboratories and centers across India. Of 10,427 volunteers, 1058 (10.14\%) tested positive for SARS-CoV2 anti-nucleocapsid (anti-NC) antibodies, 95\% of which had surrogate neutralization activity. Three-fourth of these recalled no symptoms. Repeat serology tests at 3 (n = 607) and 6 (n = 175) months showed stable anti-NC antibodies but declining neutralization activity. Local seropositivity was higher in densely populated cities and was inversely correlated with a 30-day change in regional test positivity rates (TPRs). Regional seropositivity above 10\% was associated with declining TPR. Personal factors associated with higher odds of seropositivity were high-exposure work (odds ratio, 95\% confidence interval, p value: 2.23, 1.92-2.59, \<0.0001), use of public transport (1.79, 1.43-2.24, \<0.0001), not smoking (1.52, 1.16-1.99, 0.0257), non-vegetarian diet (1.67, 1.41-1.99, \<0.0001), and B blood group (1.36, 1.15-1.61, 0.001).

}, issn = {2050-084X}, doi = {10.7554/eLife.66537}, author = {Naushin, Salwa and Sardana, Viren and Ujjainiya, Rajat and Bhatheja, Nitin and Kutum, Rintu and Bhaskar, Akash Kumar and Pradhan, Shalini and Prakash, Satyartha and Khan, Raju and Rawat, Birendra Singh and Tallapaka, Karthik Bharadwaj and Anumalla, Mahesh and Chandak, Giriraj Ratan and Lahiri, Amit and Kar, Susanta and Mulay, Shrikant Ramesh and Mugale, Madhav Nilakanth and Srivastava, Mrigank and Khan, Shaziya and Srivastava, Anjali and Tomar, Bhawana and Veerapandian, Murugan and Venkatachalam, Ganesh and Vijayakumar, Selvamani Raja and Agarwal, Ajay and Gupta, Dinesh and Halami, Prakash M. and Peddha, Muthukumar Serva and Sundaram, Gopinath M. and Veeranna, Ravindra P. and Pal, Anirban and Agarwal, Vinay Kumar and Maurya, Anil Ku and Singh, Ranvijay Kumar and Raman, Ashok Kumar and Anandasadagopan, Suresh Kumar and Karuppanan, Parimala and Venkatesan, Subramanian and Sardana, Harish Kumar and Kothari, Anamika and Jain, Rishabh and Thakur, Anupama and Parihar, Devendra Singh and Saifi, Anas and Kaur, Jasleen and Kumar, Virendra and Mishra, Avinash and Gogeri, Iranna and Rayasam, Geethavani and Singh, Praveen and Chakraborty, Rahul and Chaturvedi, Gaura and Karunakar, Pinreddy and Yadav, Rohit and Singhmar, Sunanda and Singh, Dayanidhi and Sarkar, Sharmistha and Bhattacharya, Purbasha and Acharya, Sundaram and Singh, Vandana and Verma, Shweta and Soni, Drishti and Seth, Surabhi and Vashisht, Sakshi and Thakran, Sarita and Fatima, Firdaus and Singh, Akash Pratap and Sharma, Akanksha and Sharma, Babita and Subramanian, Manikandan and Padwad, Yogendra S. and Hallan, Vipin and Patial, Vikram and Singh, Damanpreet and Tripude, Narendra Vijay and Chakrabarti, Partha and Maity, Sujay Krishna and Ganguly, Dipyaman and Sarkar, Jit and Ramakrishna, Sistla and Kumar, Balthu Narender and Kumar, Kiran A. and Gandhi, Sumit G. and Jamwal, Piyush Singh and Chouhan, Rekha and Jamwal, Vijay Lakshmi and Kapoor, Nitika and Ghosh, Debashish and Thakkar, Ghanshyam and Subudhi, Umakanta and Sen, Pradip and Chaudhury, Saumya Ray and Kumar, Rashmi and Gupta, Pawan and Tuli, Amit and Sharma, Deepak and Ringe, Rajesh P. and Amarnarayan, D. and Kulkarni, Mahesh and Shanmugam, Dhansekaran and Dharne, Mahesh S. and Dastager, Sayed G. and Joshi, Rakesh and Patil, Amita P. and Mahajan, Sachin N. and Khan, Abujunaid Habib and Wagh, Vasudev and Yadav, Rakesh Kumar and Khilari, Ajinkya and Bhadange, Mayuri and Chaurasiya, Arvindkumar H. and Kulsange, Shabda E. and Khairnar, Krishna and Paranjape, Shilpa and Kalita, Jatin and Sastry, Narahari G. and Phukan, Tridip and Manna, Prasenjit and Romi, Wahengbam and Bharali, Pankaj and Ozah, Dibyajyoti and Sahu, Ravi Kumar and Babu, Elapavalooru Vssk and Sukumaran, Rajeev and Nair, Aiswarya R. and Valappil, Prajeesh Kooloth and Puthiyamadam, Anoop and Velayudhanpillai, Adarsh and Chodankar, Kalpana and Damare, Samir and Madhavi, Yennapu and Aggarwal, Ved Varun and Dahiya, Sumit and Agrawal, Anurag and Dash, Debasis and Sengupta, Shantanu} } @article {47602, title = {Insights into chemical reactions at the beginning of the universe: from HeH+ to H-3 (+)}, journal = {Frontiers in Chemistry}, volume = {9}, year = {2021}, month = {JUN }, pages = {679750}, type = {Article}, abstract = {At the dawn of the Universe, the ions of the light elements produced in the Big Bang nucleosynthesis recombined with each other. In our present study, we have tried to mimic the conditions in the early Universe to show how the recombination process would have led to the formation of the first ever formed diatomic species of the Universe: HeH+, as well as the subsequent processes that would have led to the formation of the simplest triatomic species: H-3 (+). We have also studied some special cases: higher positive charge with fewer number of hydrogen atoms in a dense atmosphere, and the formation of unusual and interesting linear, dicationic He chains beginning from light elements He and H in a positively charged atmosphere. For all the simulations, the ab initio nanoreactor (AINR) dynamics method has been employed.}, keywords = {ab initio molecular dynamics, ab initio nanoreactor, Density functional theory, origin of molecules in the universe, the earliest lewis acid}, issn = {2296-2646}, doi = {10.3389/fchem.2021.679750}, author = {Dash, Soumya Ranjan and Das, Tamal and Vanka, Kumar} } @article {46630, title = {Insights into the nature of self-extinguishing external donors for ziegler-natta catalysis: a combined experimental and DFT study}, journal = {ChemCatChem}, volume = {13}, year = {2021}, month = {JAN }, pages = {674-681}, type = {Article}, abstract = {

Developing donors for Ziegler-Natta (ZN) catalysis to control the polymerization reaction and produce polymers with desirable properties has always been challenging due to the multi-component nature of the catalytic systems. Here, we have developed a new synthetic protocol for making two external donors, D-1 (2,2,2-trifluoroethyl myristate) and D-2 (2,2,2-trifluoroethyl palmitate) that show self-extinguishing properties, followed by a systematic DFT study to understand this peculiar property of these donors. D-1 and D-2 can undergo parallel reactions with aluminum and titanium species present in the system to produce ketones and aldehydes, which are poisons for ZN catalytic systems, thus explaining their self-extinguishing nature. The non-covalent interaction between the long alkyl chain of the donors with the surface plays a vital role in determining the donors {\textquoteleft} self-extinguishing nature. There is a significant thermodynamic preference for the binding of the donor with the longer alkyl chain at the titanium center. The current work, therefore, provides interesting insights into how self-extinguishing donors function in ZN catalytic systems.

}, keywords = {DFT, donors, non-covalent interactions, self-extinguishing, Ziegler-Natta catalysis}, issn = {1867-3880}, doi = {10.1002/cctc.202001493, Early Access Date = NOV 2020}, author = {Vipin Raj, K. and Kumawat, Jugal and Dhamaniya, Sunil and Subaramanian, Murugan and Balaraman, Ekambaram and Kumar Gupta, Virendra and Vanka, Kumar and Grubbs, Robert H.} } @article {47073, title = {Interatomic Coulombic decay in Neon-Helium cluster: a complex absorbing potential based equation-of-motion coupled cluster investigation}, journal = {Molecular Physics}, volume = {119}, year = {2021}, month = {MAY}, pages = {e1884300}, type = {Article}, abstract = {

The interatomic Coulombic decay (ICD) of the Ne(2s(-1)) and Ne(2s(-1)2p(-1)) states in neon-helium dimer is studied using highly accurate complex absorbing potential based equation-of-motion coupled cluster (CAP-EOMCC) method. The ICD decay process for the Ne(2s(-1)) state in neon-helium dimer is closed at its equilibrium bond distance. However, the decay channel is open at large bond distance of 6.2 angstrom. The decay channel for the double ionised Ne(2s(-1)2p(-1)) state is open at 3.46 angstrom. From our calculations, we have noticed that the decay rate of Ne(2s(-1)2p(-1)) state in neon-helium dimer is four times faster compared to the Ne(2s(-1)) state. We have also investigated how the decay rate of Ne(2s(-1)) state in neon-helium cluster varies in the presence of different helium environment. [GRAPHICS] .

}, keywords = {double ionised state, equation-of-motion coupled cluster (EOMCC), He droplet, interatomic Coulombic decay (ICD)}, issn = {0026-8976}, doi = {10.1080/00268976.2021.1884300, Early Access Date = FEB 2021}, author = {Ghosh, Aryya and Pal, Sourav and Vaval, Nayana} } @article {47120, title = {Interconnected polyaniline nanostructures: enhanced interface for better supercapacitance retention}, journal = {Polymer}, volume = {212}, year = {2021}, month = {JAN }, pages = {123169}, type = {Article}, abstract = {

Polyaniline and its nanocomposites have emerged as desirable electrode materials for supercapacitors. However, achieving specific capacitance with long-term cyclic stability is still a challenge. The present study reports on novel hierarchically porous and cross-linked polyaniline synthesized by a method employing aniline (monomer) and phytic acid (dopant acid) in the presence of octyltrimethyl ammonium bromide (OTAB) surfactant. The electrochemical performance of the phytic acid doped sample has been compared with HCl doped samples, the former being superior, i.e., a specific capacitance of 523 and 325 F g(-1) at current densities of 0.25 and 10 A g(-1), respectively. Additionally, the same possess excellent cycling stability with retention of similar to 88\% of its initial capacitance over 10,000 charge-discharge cycles. Further, the phytic acid doped sample exhibited a lower equivalent series resistance (0.98 Omega cm(2)) than the HCl doped sample (1.26 Omega cm(2)). These results reveal the capability of the phytic acid doped hierarchical polyaniline sample as a promising active material for electrochemical applications.

}, keywords = {Cyclic stability, Hierarchical polyaniline, Supercapacitance retention}, issn = {0032-3861}, doi = {10.1016/j.polymer.2020.123169}, author = {Mooss, Vandana A. and Vijayakumar, Vidyanand and Kurungot, Sreekumar and Athawale, Anjali A.} } @article {47058, title = {Lithium compound catalyzed deoxygenative hydroboration of primary, secondary and tertiary amides}, journal = {Dalton Transactions}, volume = {50}, year = {2021}, month = {FEB}, pages = {2354-2358}, type = {Article}, abstract = {

A selective and efficient route for the deoxygenative reduction of primary to tertiary amides to corresponding amines has been achieved with pinacolborane (HBpin) using simple and readily accessible 2,6-di-tert-butyl phenolate lithium center dot THF (1a) as a catalyst. Both experimental and DFT studies provide mechanistic insight.

}, issn = {1477-9226}, doi = {10.1039/d1dt00364j}, author = {Bisai, Milan Kumar and Gour, Kritika and Das, Tamal and Vanka, Kumar and Sen, Sakya S.} } @article {47406, title = {Lithium silicate nanosheets with excellent capture capacity and kinetics with unprecedented stability for high-temperature CO2 capture}, journal = {Chemical Science}, volume = {12}, year = {2021}, month = {APR }, pages = {4825-4835}, type = {Article}, abstract = {

An excessive amount of CO2 is the leading cause of climate change, and hence, its reduction in the Earth{\textquoteright}s atmosphere is critical to stop further degradation of the environment. Although a large body of work has been carried out for post-combustion low-temperature CO2 capture, there are very few high temperature pre-combustion CO2 capture processes. Lithium silicate (Li4SiO4), one of the best known high-temperature CO2 capture sorbents, has two main challenges, moderate capture kinetics and poor sorbent stability. In this work, we have designed and synthesized lithium silicate nanosheets (LSNs), which showed high CO2 capture capacity (35.3 wt\% CO2 capture using 60\% CO2 feed gas, close to the theoretical value) with ultra-fast kinetics and enhanced stability at 650 degrees C. Due to the nanosheet morphology of the LSNs, they provided a good external surface for CO2 adsorption at every Li-site, yielding excellent CO2 capture capacity. The nanosheet morphology of the LSNs allowed efficient CO2 diffusion to ensure reaction with the entire sheet as well as providing extremely fast CO2 capture kinetics (0.22 g g(-1) min(-1)). Conventional lithium silicates are known to rapidly lose their capture capacity and kinetics within the first few cycles due to thick carbonate shell formation and also due to the sintering of sorbent particles; however, the LSNs were stable for at least 200 cycles without any loss in their capture capacity or kinetics. The LSNs neither formed a carbonate shell nor underwent sintering, allowing efficient adsorption-desorption cycling. We also proposed a new mechanism, a mixed-phase model, to explain the unique CO2 capture behavior of the LSNs, using detailed (i) kinetics experiments for both adsorption and desorption steps, (ii) in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy measurements, (iii) depth-profiling X-ray photoelectron spectroscopy (XPS) of the sorbent after CO2 capture and (iv) theoretical investigation through systematic electronic structure calculations within the framework of density functional theory (DFT) formalism.

}, issn = {2041-6520}, doi = {10.1039/d0sc06843h}, author = {Belgamwar, Rajesh and Maity, Ayan and Das, Tisita and Chakraborty, Sudip and Vinod, Chathakudath P. and Polshettiwar, Vivek} } @article {47337, title = {Micro-computed tomographic analysis of the marginal adaptation of a calcium silicate-based cement to radicular dentin after removal of three different intracanal medicaments - an in vitro study}, journal = {Journal of Conservative Dentistry}, volume = {23}, year = {2021}, month = {FEB}, pages = {598-603}, type = {Article}, abstract = {

Context:\ This study focuses on the marginal adaptation of a calcium silicate-based cement to the root dentin after retrieval of different intracanal medicaments.

Aim:\ This study compared the marginal adaptation of a calcium silicate-based cement to radicular dentin in the apical third of the root canal following the use of three different intracanal medicaments.

Materials and methods:\ Forty single-rooted premolar teeth (n\ = 40) were decoronated 13 mm above the root apices; then, 3 mm of the root tips were resected to standardize the root length. Orthograde cleaning and shaping were done using the rotary files and apical enlargement using peeso reamers. Depending on the intracanal medicament used, the samples were equally divided into four groups: Group 1 - control, Group 2 - Metapex, Group 3 - triple antibiotic paste (TAP), and Group 4 - calcium hydroxide with Propolis. Subsequently, the medicament was removed and a 3 mm apical barrier of BiodentineTM\ was placed and later scanned using an ex vivo micro-computed tomography scanner.

}, doi = {10.4103/JCD.JCD_561_20}, author = {Jain, Ruchika Nirmal and Abraham, Sathish and Karad, Rohini Ramesh and Najan, Harshal Balasaheb and Vaswani, Sneha Dhruvkumar and Torris, Arun} } @article {47054, title = {Mycology and mycotechnology on postal stamps}, journal = {Current Science}, volume = {120}, year = {2021}, month = {FEB}, pages = {628-636}, type = {Article}, abstract = {

Mycology, the study of fungal biology, and philately, the study of postage stamps, are rarely connected, as they are very different activities. However, philatelic mycology can raise awareness of the facets of fungi which contribute significantly to human welfare. Fungi are photogenic and exhibit physiological wonders such as luminescence. They are important in biotechnology for their secondary metabolites. So, stamps depicting fungi signal the recognition of problems and prospects of prosperity posed by fungi in nutrition and health, agriculture, engineering, industry and ecology. Many countries have issued thousands of stamps on fungi. India with a rich heritage of fungal diversity lags in this respect. This article hopes to inspire action by celebrating the beauty and significance of fungi in the art of philately.

}, keywords = {mycology, mycophilately, Mycotechnology, photogenic appeal, postal stamps}, issn = {0011-3891}, doi = {10.18520/cs/v120/i4/628-636}, author = {Ghormade, Vandana and Pathan, Ejaj and Jyoti, Jeevan and Vartak, Ajit and Deshpande, Mukund} } @article {47419, title = {Naphthalene dianhydride organic anode for a {\textquoteleft}rocking-chair{\textquoteright} zinc-proton hybrid ion battery}, journal = {Dalton Transactions}, volume = {50}, year = {2021}, month = {MAR }, pages = {4237-4243}, type = {Article}, abstract = {

Rechargeable batteries consisting of a Zn metal anode and a suitable cathode coupled with a Zn2+ ion-conducting electrolyte are recently emerging as promising energy storage devices for stationary applications. However, the formation of high surface area Zn (HSAZ) architectures on the metallic Zn anode deteriorates their performance upon prolonged cycling. In this work, we demonstrate the application of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), an organic compound, as a replacement for the Zn-metal anode enabling the design of a {\textquoteleft}rocking-chair{\textquoteright} zinc-proton hybrid ion battery. The NTCDA electrode material displays a multi-plateau redox behaviour, delivering a specific discharge capacity of 143 mA h g(-1) in the potential window of 1.4 V to 0.3 V vs. Zn|Zn2+. The detailed electrochemical characterization of NTCDA in various electrolytes (an aqueous solution of 1 M ZnOTF, an aqueous solution of 0.01 M H2SO4, and an organic electrolyte of 0.5 M ZnOTF/acetonitrile) reveals that the redox processes leading to charge storage involve a contribution from both H+ and Zn2+. The performance of NTCDA as an anode is further demonstrated by pairing it with a MnO2 cathode, and the resulting MnO2||NTCDA full-cell (zinc-proton hybrid ion battery) delivers a specific discharge capacity of 41 mA h g(total)(-1) (normalized with the total mass-loading of both anode and cathode active materials) with an average operating voltage of 0.80 V.

}, issn = {1477-9226}, doi = {10.1039/d0dt04404k}, author = {Ghosh, Meena and Vijayakumar, Vidyanand and Kurian, Maria and Dilwale, Swati and Kurungot, Sreekumar} } @article {47116, title = {One-pot cascade conversion of renewable furfural to levulinic acid over a bifunctional H3PW12O40SiO2 catalyst in the absence of external H-2}, journal = {Energy \& Fuels}, volume = {35}, year = {2021}, month = {JAN }, pages = {539-545}, type = {Article}, abstract = {

The conversion of biomass-derived furfural (FUR) to levulinic acid (LA), a versatile platform chemical, involves catalytic hydrogenation of FUR followed by acid hydrolysis to LA. However, this two-step process demands expensive separation and purification of the furfuryl alcohol (FAL) intermediate. Herein, we demonstrate an ingenious catalytic strategy for the one-pot cascade conversion of FUR to LA over a bifunctional catalyst without using pure external H-2. Isopropyl alcohol (IPA) served a dual role as a hydrogen donor and solvent while inhibiting the side reactions. Catalysts with a tunable surface area and acidity were synthesized by impregnating different percentages of H3PW12O40 (heteropolyacid) over a SiO2 support. The bifunctionality of the H3PW12O40/SiO2 catalyst is ascribed to the mutual coexistence of Lewis and Brvinsted acid sites. The Lewis acid sites imparted by active W metal sites adsorb hydrogen proton for catalytic transfer hydrogenation of FUR to FAL, while the predominant Brvinsted acid sites catalyze the hydrolysis of FAL to LA. Consequently, H3PW12O40/SiO2 revealed to be a potential catalyst producing an similar to 51\% LA yield under optimized reaction conditions. Moreover, the catalyst was found to be reusable for three catalytic cycles. This study paves the way to develop future biorefinery, particularly direct conversion of FUR to LA over a bifunctional catalyst with a liquid H-donor, in an environmentally benign manner and comply with the green chemistry principles.

}, issn = {0887-0624}, doi = {10.1021/acs.energyfuels.0c03326}, author = {Nandiwale, Kakasaheb Y. and Vishwakarma, Mona and Rathod, Simmy and Simakova, Irina and Bokade, Vijay V.} } @article {47068, title = {Operando generated ordered heterogeneous catalyst for the selective conversion of CO2 to methanol}, journal = {ACS Energy Letters}, volume = {6}, year = {2021}, month = {FEB }, pages = {509-516}, type = {Article}, abstract = {

The discovery of new materials for efficient transformation of carbon dioxide (CO2) into desired fuel can revolutionize large-scale renewable energy storage and mitigate environmental damage due to carbon emissions. In this work, we discovered an operando generated stable Ni-In kinetic phase that selectively converts CO2 to methanol (CTM) at low pressure compared to the state-of-the-art materials. The catalytic nature of a well-known methanation catalyst, nickel, has been tuned with the introduction of inactive indium, which enhances the CTM process. The remarkable change in the mechanistic pathways toward methanol production has been mapped by operando diffuse reflectance infrared Fourier transform spectroscopy analysis, corroborated by first-principles calculations. The ordered arrangement and pronounced electronegativity difference between metals are attributed to the complete shift in mechanism. The approach and findings of this work provide a unique advance toward the next-generation catalyst discovery for going beyond the state-of-the-art in CO2 reduction technologies.

}, issn = {2380-8195}, doi = {10.1021/acsenergylett.0c02614}, author = {Cherevotan, Arjun and Raj, Jithu and Dheer, Lakshay and Roy, Soumyabrata and Sarkar, Shreya and Das, Risov and Vinod, Chathakudath P. and Xu, Shaojun and Wells, Peter and Waghmare, V, Umesh and Peter, Sebastian C.} } @article {47409, title = {Orc4 spatiotemporally stabilizes centromeric chromatin}, journal = {Genome Research}, volume = {31}, year = {2021}, month = {APR}, pages = {607-621}, type = {Article}, abstract = {

The establishment of centromeric chromatin and its propagation by the centromere-specific histone CENPA is mediated by epigenetic mechanisms in most eukaryotes. DNA replication origins, origin binding proteins, and replication timing of centromere DNA are important determinants of centromere function. The epigenetically regulated regional centromeres in the budding yeast Candida albicans have unique DNA sequences that replicate earliest in every chromosome and are clustered throughout the cell cycle. In this study, the genome-wide occupancy of the replication initiation protein Orc4 reveals its abundance at all centromeres in C. albicans. Orc4 is associated with four different DNA sequence motifs, one of which coincides with tRNA genes (tDNA) that replicate early and cluster together in space. Hi-C combined with genome-wide replication timing analyses identify that early replicating Orc4-bound regions interact with themselves stronger than with late replicating Orc4-bound regions. We simulate a polymer model of chromosomes of C. albicans and propose that the early replicating and highly enriched Orc4-bound sites preferentially localize around the clustered kinetochores. We also observe that Orc4 is constitutively localized to centromeres, and both Orc4 and the helicase Mcm2 are essential for cell viability and CENPA stability in C. albicans. Finally, we show that new molecules of CENPA are recruited to centromeres during late anaphase/telophase, which coincides with the stage at which the CENPA-specific chaperone Scm3 localizes to the kinetochore. We propose that the spatiotemporal localization of Orc4 within the nucleus, in collaboration with Mcm2 and Scm3, maintains centromeric chromatin stability and CENPA recruitment in C. albicans.

}, issn = {1088-9051}, doi = {10.1101/gr.265900.120}, author = {Sreekumar, Lakshmi and Kumari, Kiran and Guin, Krishnendu and Bakshi, Asif and Varshney, Neha and Thimmappa, Bhagya C. and Narlikar, Leelavati and Padinhateeri, Ranjith and Siddharthan, Rahul and Sanyal, Kaustuv} } @article {47648, title = {Organoruthenium (II) complexes featuring pyrazole-linked thiosemicarbazone ligands: synthesis, DNA/BSA interactions, molecular docking, and cytotoxicity studies}, journal = {Applied Organometallic Chemistry}, volume = {35}, year = {2021}, month = {OCT}, pages = {e6343}, type = {Article}, abstract = {A series of pyrazol-derived thiosemicarbazone ligands (L1-L4) were synthesized and reacted with [Ru(p-cymene)(mu-Cl)Cl](2) to yield a series of {\textquoteleft}{\textquoteleft}piano-stool{\textquoteright}{\textquoteright}-type binuclear ruthenium (II)-arene-thiosemicarbazone complexes (C1-C8) of the general type [(Ru(eta(6)-p-cym)L)(2)(mu-im/azpy)] Cl1-2 (L = diphenylpyrazole thiosemicarbazone; cym = p-cymene; im = imidazole; azpy = 4,4 {\textquoteleft}-azopyridine). The thiosemicarbazone ligands act as N and S donors binding to the Ru(II) center via the imine nitrogen and the thione sulfur atoms. The complexes were characterized by NMR, FTIR, UV-Vis spectroscopy, and ESI+ mass spectrometry. The binding of the complexes to calf thymus deoxyribonucleic acid (CT-DNA) and bovine serum albumin (BSA) was evaluated, and it has been established that the binuclear complexes have good binding efficacies with DNA (K-b = 10(4)-10(5) M-1) and BSA (K-a = 10(5)-10(6) M-1). This is attributed to the arene moieties present in the ligands of the complexes that can have hydrophobic interactions with DNA/BSA. Ethidium bromide (EB) displacement studies and DNA viscosity measurements revealed intercalative interaction of the complexes with DNA. Static interaction of the complexes with BSA was revealed by fluorescence quenching studies. Molecular docking studies confirmed base stacking, H-bonding, and hydrophobic interactions with the biomolecules. In vitro antiproliferative studies of the complexes affirmed that the complexes are cytotoxic towards the HeLa (human cervical cancer) cell line with IC50 values in range of 17.3-41.3 mu M.}, keywords = {Binuclear ruthenium (II) complexes, BSA binding interactions, DNA, HeLa human cervical carcinoma, pyrazole-derived thiosemicarbazone}, issn = {0268-2605}, doi = {10.1002/aoc.6343}, author = {Khanvilkar, Priyanka and Dash, Soumya R. and Banerjee, Devjani and Vohra, Aliasgar and Devkar, Ranjitsinh and Chakraborty, Debjani} } @article {47607, title = {Pd(II)-catalyzed chemoselective acetoxylation of C(sp(2))-H and C(sp(3))-H bonds in tertiary amides}, journal = {Journal of Organic Chemistry}, volume = {86}, year = {2021}, month = {JUN }, pages = {8172-8181}, type = {Article}, abstract = {Palladium-catalyzed chemoselective C(sp(2))-H and C(sp(3))-H acetoxylation of synthetically useful tertiary amides is reported under relatively mild reaction conditions. This protocol proceeds through the assistance of a weakly coordinated directing group (C = O) and requires low catalyst (1.0 mol \%) loading. Diverse functionalities, such as C(sp(2))-Cl, C(sp(3))-Cl, -CF3, -COOEt, and -NO2 groups, including morpholinyl, piperazinyl, and pyrrolidinyl heterocycles, are compatible under the reaction conditions. Further functionalization of this protocol is demonstrated by hydrolysis to alcohols, alcohol-acids, as well as reduction to tertiary amines. A preliminary kinetic isotope effect study supported the rate-limiting C-H bond activation process.}, issn = {0022-3263}, doi = {10.1021/acs.joc.1c00629}, author = {Vijaykumar, Muniyappa and Punji, Benudhar} } @article {47329, title = {Pharmacore maping based on docking, ADME/toxicity, virtual screening on 3,5-dimethyl-1,3,4-hexanetriol and dodecanoic acid derivates for anticancer inhibitors}, journal = {Journal of Biomolecular Structure \& Dynamics}, volume = {39}, year = {2021}, month = {JAN}, pages = {4490-4500}, type = {Article}, abstract = {

Plants produced natural generating products play a significant role in drug discovery of new bioactive compounds and these are used for advancement of innovative curative drugs for specific target health diseases. In this study Docking and ADME/T virtual screening method are apply for in drug discovery and can be divided into ligand- and target structure-based. The aim of this study was to analyze theDecalepis hamiltoniiisolated compounds by using the evaluation of molecular docking and virtual screening of anticancer drugs. MOE docking ADME/Toxicity and virtual screening approaches. A docking energy -12.97 kcal/mol; -9.93- kcal/mol on cancer responsible protein was targeted. Further, the compounds were filtered through the rule of five, ADME/Toxicity risk and synthetic accessibility. The active compound were then docked to recognize the possible target binding pocket to obtain a set of a ligand poses and to prioritize the predicted active compounds. The scrutinize compounds, as well as their metabolites were evaluated for different pharmacokinetics parameter such as ADME/Toxicity. Therefore, the result shows that a large number of compounds were found to be ADME/toxicity positive to be a positive drug molecule against cancer, selected compounds under study satisfies parameters for ADME and Toxicity properties. The present study demonstrate to identifying the novel structures which are having similar structural feature with like activity with respect to the compounds 3,5-Dimethyl-1,3,4-Hexanetriol and Dodecanoic acid that are shown best binding energy with the receptors 4igk and 4b3z respectively. This study may provide significant clues for discovery novel drug inhibitors for cancer properties.

}, keywords = {ADME, Decalepis hamiltonii, docking, drug discovery, Toxicity, virtual screening}, issn = {0739-1102}, doi = {10.1080/07391102.2020.1778533}, author = {Prakash, Palanisamy and Vijayasarathi, Durairaj and Selvam, Kuppusamy and Karthi, Sengodan and Manivasagaperumal, Rengarajan} } @article {47594, title = {Phosphite mediated asymmetric N to C migration for the synthesis of chiral heterocycles from primary amines}, journal = {Chemical Science}, volume = {12}, year = {2021}, month = {JUL}, pages = {8996-9003}, type = {Article}, abstract = {A phosphite mediated stereoretentive C-H alkylation of N-alkylpyridinium salts derived from chiral primary amines was achieved. The reaction proceeds through the activation of the N-alkylpyridinium salt substrate with a nucleophilic phosphite catalyst, followed by a base mediated [1,2] aza-Wittig rearrangement and subsequent catalyst dissociation for an overall N to C-2 alkyl migration. The scope and degree of stereoretention were studied, and both experimental and theoretical investigations were performed to support an unprecedented aza-Wittig rearrangement-rearomatization sequence. A catalytic enantioselective version starting with racemic starting material and chiral phosphite catalyst was also established following our understanding of the stereoretentive process. This method provides efficient access to tertiary and quaternary stereogenic centers in pyridine systems, which are prevalent in drugs, bioactive natural products, chiral ligands, and catalysts.}, issn = {2041-6520}, doi = {10.1039/d1sc01217g}, author = {Rani, Soniya and Dash, Soumya Ranjan and Bera, Asish and Alam, Md Nirshad and Vanka, Kumar and Maity, Pradip} } @article {47061, title = {Photoactivatable prodrug for simultaneous release of mertansine and CO along with a BODIPY derivative as a luminescent marker in mitochondria: a proof of concept for NIR image-guided cancer therapy}, journal = {Chemical Science}, volume = {12}, year = {2021}, month = {FEB}, pages = {2667-2673}, type = {Article}, abstract = {

Controlled and efficient activation is the crucial aspect of designing an effective prodrug. Herein we demonstrate a proof of concept for a light activatable prodrug with desired organelle specificity. Mertansine, a benzoansamacrolide, is an efficient microtubule-targeting compound that binds at or near the vinblastine-binding site in the mitochondrial region to induce mitotic arrest and cell death through apoptosis. Despite its efficacy even in the nanomolar level, this has failed in stage 2 of human clinical trials owing to the lack of drug specificity and the deleterious systemic toxicity. To get around this problem, a recent trend is to develop an antibody-conjugatable maytansinoid with improved tumor/organelle-specificity and lesser systematic toxicity. Endogenous CO is recognized as a regulator of cellular function and for its obligatory role in cell apoptosis. CO blocks the proliferation of cancer cells and effector T cells, and the primary target is reported to be the mitochondria. We report herein a new mitochondria-specific prodrug conjugate (Pro-DC) that undergoes a photocleavage reaction on irradiation with a 400 nm source (1.0 mW cm(-2)) to induce a simultaneous release of the therapeutic components mertansine and CO along with a BODIPY derivative (BODIPY(PPH3)(2)) as a luminescent marker in the mitochondrial matrix. The efficacy of the process is demonstrated using MCF-7 cells and could effectively be visualized by probing the intracellular luminescence of BODIPY(PPH3)(2). This provides a proof-of-concept for designing a prodrug for image-guided combination therapy for mainstream treatment of cancer.

}, issn = {2041-6520}, doi = {10.1039/d0sc06270g}, author = {Tiwari, Rajeshwari and Shinde, Prashant S. and Sreedharan, Sreejesh and Dey, Anik Kumar and Vallis, Katherine A. and Mhaske, Santosh B. and Pramanik, Sumit kumar and Das, Amitava} } @article {47682, title = {Prominence of Cu in a plasmonic Cu-Ag alloy decorated SiO2@S-doped C3N4 core-shell nanostructured photocatalyst towards enhanced visible light activity}, journal = {Nanoscale Advances}, volume = {4}, year = {2021}, month = {DEC}, pages = {150-162}, type = {Article}, abstract = {A series of Cu-Ag bimetal alloys decorated on SiO2 and the fabrication of few-layer S-doped graphitic carbon nitride (SC) warped over it to form a core-shell nanostructured morphology have been demonstrated and well characterized through various physiochemical techniques. HRTEM data confirmed the formation of a compact nanojunction between the SiO2 and SC, where Cu-Ag is embedded uniformly with an average particle size of 1.3 nm. The Ag : Cu (1 : 3) between SiO2 and SC produces 1730 mu mol h(-1) g(-1) of H-2 under visible light illumination. Moreover, 6.2-fold current enhancement in the case of Ag : Cu (1 : 3) as compared to the Ag-loaded core-shell nanostructured photocatalyst indicates higher electron-hole-pair separation. The excellent activity was due to the synergistic alloying and plasmonic effect of Ag and Cu. DFT studies reveal that the Cu atom in the Cu-Ag bimetal alloy plays a pivotal role in the generation of H-2, and the reaction proceeds via a 4-membered transition state. The mechanistic insight proceeds from the generation of hot electrons due to the LSPR effect and their transfer to the SC layer via a compact nanojunction.}, issn = {2516-0230}, doi = {10.1039/d1na00633a}, author = {Babu, Pradeepta and Dash, Soumya Ranjan and Behera, Arjun and Vijayaraghavan, T. and Ashok, Anuradha and Parida, Kulamani} } @article {47094, title = {Promoted mesoporous Fe-alumina catalysts for the non-oxidative dehydrogenation of isobutane}, journal = {Catalysis Communications}, volume = {150}, year = {2021}, month = {FEB}, pages = {106263}, type = {Article}, abstract = {

Production of isobutene is commercially consequential and highly demanding from the end-use industries being a key platform molecule as well as an intermediate for a variety of value-added chemicals. Traditionally, isobutene is prepared via steam cracking and fluid catalytic cracking methods. However, the catalysts used in these conventional methods have disadvantages like coke formation, sintering, etc. In this study, the catalytic non-oxidative dehydrogenation of isobutane over acidic, alkaline, and noble metal promoted mesoporous iron-doped catalysts was investigated. Iron doping has a significant function in controlling isobutene selectivity. The synthesis method is crucial to achieve successful metal doping in the mesoporous alumina matrix. Promoted catalysts exhibited a notable difference in isobutane conversion with a marginal change in dehydrogenation selectivity. Silver promoted catalyst showed slightly higher isobutene yield due to the optimal catalytic properties. This catalyst was stable for a considerable duration, and coke deposition, as well as particle agglomeration, were observed to faintly inhibit the catalytic activity.

}, keywords = {iron, Isobutane, Isobutene, Mesoporous alumina, Non-oxidative dehydrogenation}, issn = {1566-7367}, doi = {10.1016/j.catcom.2020.106263}, author = {Venugopalan, Aswathy Thareparambil and Kandasamy, Prabu and Gupta, Nikitra Nihalchand and Thirumalaiswamy, Raja} } @article {47464, title = {Reactions of 2,3-dibromonaphthalene-1,4-dione and pyridyl amines: X-ray structures, DFT investigations, and selective detection of the Hg2+ and Ni2+ ions}, journal = {Engineered Science}, volume = {14}, year = {2021}, month = {FEB}, pages = {78-93}, type = {Article}, abstract = {

In this work, the products formed by the reaction between 2,3-dibromonaphthalene-1,4-dione with (pyridine-2-yl)methanamine and (pyridine-4-yl)methanamine are discussed in detial. The products 2-amino-3-bromonaphthalene-1,4-dione (A) and 2-aminonaphthalene-1,4-dione (B(1)) obtained are characterized through\ 1H and\ 13C-NMR, FTIR, mass spectrometry, single-crystal X-ray diffraction experiments, which are in conjunction with wB97X based density functional theory.\ compound\ A\ can effectively and selectively detect Hg2+\ and Ni2+\ ions, and proposes a potential mechanism of action.

}, issn = {2576-9898}, doi = {10.30919/es8d427}, author = {Aggrwal, Gunjan and Salunke-Gawali, Sunita and Gejji, Shridhar P. and Nikalje, Milind and Chakravarty, Debamitra and Verma, Prakash L. and Gosavi-Mirkute, Prajkta and Harihar, Shital and Jadhav , Mahesh and Puranik, Vedavati G.} } @article {47621, title = {Readily available lithium compounds as catalysts for the hydroboration of carbodiimides and esters}, journal = {Journal of Organometallic Chemistry}, volume = {949}, year = {2021}, month = {SEP 15}, pages = {121924}, type = {Article}, abstract = {Selective and efficient hydroboration of esters and carbodiimides to alcohols and amines by two welldefined and readily accessible lithium complexes, 2,6-di-tert-butyl phenolate lithium (1a ) and 1,1{\textquoteright}-dilithioferrocene (1b ) are described. A range of aliphatic, aromatic, and cyclic esters with various functional groups were selectively converted into the corresponding boronate esters. Similarly, the single hydroboration of carbodiimides with aliphatic and aromatic substituents on the nitrogen atoms was studied. A possible mechanistic pathway of the hydroboration of carbodiimides with HBpin has been proposed using NMR studies and DFT calculations. These reactions are convenient alternatives to stoichiometric hydride reduction or hydrogenation. The employing of lithium complexes is also significant, because of the need to find cheap and green alternatives to noble metal complexes. (C) 2021 Elsevier B.V. All rights reserved.}, issn = {0022-328X}, doi = {10.1016/j.jorganchem.2021.121924}, author = {Bisai, Milan Kumar and Gour, Kritika and Das, Tamal and Vanka, Kumar and Sen, Sakya S.} } @article {47358, title = {Resonance study: effect of partial triples excitation using complex absorbing potential-based Fock-space multi-reference coupled cluster}, journal = {International Journal of Quantum Chemistry}, volume = {121}, year = {2021}, month = {SEP}, pages = {e26738}, type = {Article; Early Access}, abstract = {

Resonances are metastable states with finite lifetime. They play important role in physics, chemistry and biology. The theoretical calculation of resonance state is a challenging problem. In this paper we have studied the shape resonance of Be, Mg, N-2 and CO. We have used correlated independent particle approximation to the Fock space multi-reference coupled cluster singles-doubles with third-order triples (CAP-CIP-FSMRCCSD(T)) method augmented by complex absorption potential. The resonance energy and decay widths are obtained by solving a non-Hermitian eigen-value problem within FSMRCC framework. The effects of the lowest order triples on the resonance energy and decay are studied.

}, keywords = {complex absorbing potential, electron affinity, Fock\&\#8208, negative ion resonance, partial triples, space MRCC}, issn = {0020-7608}, doi = {10.1002/qua.26738, Early Access Date = MAY 2021}, author = {Jana, Irina and Basumallick, Suhita and Pal, Sourav and Vaval, Nayana} } @article {47416, title = {Reusable magnetic nanocatalyst for bio-fuel additives: the ultrasound-assisted synthesis of solketal dagger}, journal = {Sustainable Energy \& Fuels }, volume = {5}, year = {2021}, month = {APR}, pages = {2362-2372}, type = {Article}, abstract = {

Acetalization of glycerol into solketal, a potential fuel additive, is a promising approach to utilizing the large waste-stream of glycerol from the biodiesel industry. Herein, we report an efficient ultrasound-assisted room temperature synthesis of solketal by acetalization of glycerol with acetone using an easily recoverable sulfonic acid-functionalized, silica-coated Fe3O4 magnetic nanoparticle (Fe3O4@SiO2@SO3H MNP, FSS MNP) catalyst. The morphology, chemical composition and magnetic properties of the catalyst were elucidated. The acetalization of glycerol was carried out under ultrasonication at room temperature, resulting in 97\% glycerol conversion after 15 minutes and 95\% isolated yield of solketal with 100\% selectivity for this acetal. The facile magnetic retrievability of the catalyst imparted operational simplicity to the solketal synthetic protocol, avoiding complicated catalyst separation and product purification processes. The FSS catalyst was magnetically recycled for up to five catalytic experiments, maintaining a glycerol conversion of 95\% and without deterioration in its selectivity, composition, morphology or magnetic properties, thereby ameliorating the green aspects of the protocol.

}, issn = {2398-4902}, doi = {10.1039/d0se01900c, Early Access Date = MAR 2021}, author = {Rajkumari, Kalyani and Changmai, Bishwajit and Meher, Ananta Kumar and Vanlalveni, Chhangte and Sudarsanam, Putla and Wheatley, Andrew E. H. and Rokhum, Samuel Lalthazuala} } @article {47634, title = {Role of metal-support interaction for atmospheric pressure CO2 hydrogenation over Pd/(Ti)-SBA-15 catalyst: effect of titanium composition on products selectivity}, journal = {Molecular Catalysis}, volume = {511}, year = {2021}, month = {JUL}, pages = {111732}, type = {Article}, abstract = {The potential role of metal-support interaction for tuning the product selectivity during atmospheric pressure CO2 hydrogenation has been demonstrated on Pd/(Ti)-SBA-15 catalyst. Highly dispersed Pd NPs on SBA-15 (Pd/ SBA-15) was synthesized and further modified with titanium of varying composition. Comparison of catalytic activity of Pd/Ti-SBA-15 with its counterparts (Pd/SBA-15 and Pd/TiO2) illustrated the significance of strong PdTi interface in this catalyst and its role in tuning the product selectivity of CO2 hydrogenation. The generation of an ample amount of oxygen vacancies in the Pd/Ti-SBA-15 catalyst with maximum metallic Pd sites in close vicinity of Ti is proposed to boost the CO2 hydrogenation activity.}, keywords = {CO2 hydrogenation, Metal-support interaction, Modified deposition precipitation, oxygen vacancies, Titanosilicates}, issn = {2468-8231}, doi = {10.1016/j.mcat.2021.111732}, author = {Soni, Yogita and Gupta, Sharad and Vinod, C. P.} } @article {47405, title = {Silk fibroin and ceramic scaffolds: comparative in vitro studies for bone regeneration}, journal = {Bioengineering \& Translational Medicine}, year = {2021}, month = {APR}, pages = {e10221}, type = {Article; Early Access}, abstract = {

Synthetic bone void fillers based on calcium ceramics are used to fill cavities in the bone and promote bone regeneration. More recently, silk fibroin (SF), a protein polymer obtained from Bombyx mori silkworm, has emerged as a promising material in bone void filling. In this work, we have compared the safety and efficacy of two types of silk fibroin-based bone void fillers with currently used and commercially available ceramic bone void fillers (based on calcium sulphate, beta tricalcium phosphate, and beta tricalcium phosphate with hydroxyapatite). Further, we have also evaluated these two types of SF scaffolds, which have strikingly different structural attributes. The biocompatibility of these scaffolds was comparable as assessed by cytotoxicity assay, cellular adhesion assay, and immunogenic assay. Ability of the scaffolds to support differentiation of human mesenchymal stem cells (hMSCs) into an osteoblastic lineage was also evaluated in an in vitro differentiation experiment using reverse transcriptase polymerase chain reaction analysis. These results revealed that cells cultured on SF scaffolds exhibit higher expression of early to late markers such as Runx2, BMPs, collagen, osterix, osteopontin, and osteocalcin as compared with ceramic-based scaffolds. This observation was further validated by studying the expression of alkaline phosphatase and calcium deposition. We also show that scaffolds made from same material of SF, but characterized by very different pore architectures, have diverse outcome in stem cell differentiation.

}, keywords = {beta tricalcium phosphate, bone regeneration, bone void filler, calcium sulphate, hMSCs, hydroxyapatite, osteoblasts, scaffold, Silk fibroin}, doi = {10.1002/btm2.10221, Early Access Date = APR 2021}, author = {Deshpande, Rucha and Shukla, Swati and Sayyad, Raeesa and Salunke, Shalmali and Nisal, Anuya and Venugopalan, Premnath} } @article {47729, title = {Structure-tailored non-noble metal-based ternary chalcogenide nanocrystals for pt-like electrocatalytic hydrogen production}, journal = {ChemSusChem}, volume = {14}, year = {2021}, month = {AUG }, pages = {3074-3083}, type = {Article}, abstract = {A facile microwave-assisted strategy was employed to synthesize Ni3Bi2S2 nanocrystals. Variation in the synthesis conditions tuned the composition of monoclinic and orthorhombic phases of Ni3Bi2S2. The electrochemical hydrogen evolution activity of the catalyst with highest percentage of monoclinic phase demonstrated a negligible onset potential of only 24 mV close to that of state-of-the-art Pt/C with an overpotential as low as 88 mV. Density functional theory calculations predicted the monoclinic phase exhibit the lowest adsorption free energy corresponding to hydrogen adsorption (Delta GadsH*) and, therefore, the highest hydrogen evolution activity amongst the considered phases. The quasi-2D structure of monoclinic phase facilitated an increased charge-transfer between Ni and Bi, favoring the downward shift of the d-band center to enhance the catalytic activity.}, keywords = {charge transfer, electrocatalysis, hydrogen evolution reaction, Nanomaterials, ternary chalcogenides}, issn = {1864-5631}, doi = {10.1002/cssc.202100967}, author = {Sarkar, Shreya and Rawat, Abhishek and Das, Tisita and Gaboardi, Mattia and Chakraborty, Sudip and Vinod, C. P. and Peter, Sebastian C.} } @article {47733, title = {Study on the failure of guide ropes used in mines}, journal = {Insight}, volume = {63}, year = {2021}, month = {JUN}, pages = {357-361}, type = {Article}, abstract = {The skips/cages in mine hoisting have to be guided to achieve high hoisting rates. Steel guide ropes are used in hoisting because they can safely guide the skips/cages and have been observed to be economical. Guide ropes are static in nature and are thus more prone to corrosion. An investigation into the causes of failure of a guide rope is discussed in this paper. The study consists of physical examination, examination of wear and corrosion, macro- and micro- examination, examination of the breaking load and individual tensile strength measurement of the rod. The main cause of failure is found to be corrosion. Heavy abrasion and corrosion together causes a substantial reduction in diameter of more than 60\%. Corrosion raises the stress level and thereby weakens the grains, which is indicated by the cracks that have developed all along the grains as revealed through micro-examination. This affects the breaking strength and reveals a 37\% loss of strength, as a result of which failure occurs.}, keywords = {corrosion on steel guide rope, guide rope failure, steel guide rope, wear}, issn = {1354-2575}, doi = {10.1784/insi.2021.63.6.357}, author = {Singh, M. K. and Mallick, M. and Verma, M. K.} } @article {47382, title = {Substrate, catalyst, and solvent: the triune nature of multitasking reagents in hydroboration and cyanosilylation}, journal = {Organometallics}, volume = {40}, year = {2021}, month = {APR}, pages = {1104-1112}, type = {Article}, abstract = {

A truly green chemical process would avoid the use of an external catalyst, while still achieving high efficiency. This has been realized in the very recent past for hydroboration, cyanosilylation, acetalization, and the aza-Michael addition, among other reactions. The current combined computational and experimental study unlocks the secret to how this highly desirable outcome is accomplished: one of the reactants in the process also acts as the catalyst. Specifically, this is shown (i) for the important hydroboration reaction, with pinacolborane (HBpin) as the hydroborating reagent and benzaldehyde, acetophenone, benzoic acid and p-methoxyphenylacetylene as the hydroborated substrates, and (ii) for cyanosilylation, with trimethylcyanosilane (TMSCN) as the cyanosilylating agent and benzaldehyde as the substrate. The mechanistic understanding thus gained has then been further exploited experimentally to bring hydroboration and cyanosilylation closer to experimental conditions in catalysis. These insights can potentially be expanded to the rapidly growing area of solvent-free and internal catalyst chemistry.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.1c00070}, author = {Dixit, Ruchi and Bisai, Milan Kumar and Yadav, Sandeep and Yadav, Vinita and Sen, Sakya S. and Vanka, Kumar} } @article {47603, title = {Sulfonated polyvinyl alcohol ionomer membrane favoring smooth electrodeposition of zinc for aqueous rechargeable zinc metal batteries}, journal = {Sustainable Energy \& Fuels}, volume = {5}, year = {2021}, month = {OCT}, pages = {5557-5564}, type = {Article}, abstract = {One of the failure mechanisms of aqueous rechargeable zinc metal batteries (AZMBs) involves high surface area zinc (HSAZ)/dendrite-like deposits over the Zn-metal anode during long-term cycling. Negatively charged (anionic) polymeric ionomer electrolyte membranes and separators are known for suppressing the dendrite-/HSAZ-induced failure of AZMBs. However, the preparation of cost-effective and non-fluorinated ionomers from cheap and environmentally friendly polymers is essential to leverage the feasibility of AZMBs. The current work demonstrates the potential of an ionomer electrolyte membrane (P-AS-C-Zn) made by the crystallization-induced physical cross-linking of sulfonated poly (vinyl alcohol) (PVS) and poly (vinyl alcohol) (PVA) as a dendrite-/HSAZ-inhibiting separator for AZMBs. The P-AS-C-Zn membranes exhibited excellent Zn plating/stripping behavior with a stable voltage vs. time profile beyond 1100 h, compared to their neutral PVA-C-Zn counterpart without any ionomer character (cell failure at close to 280 h). Applying the optimized P-AS-C-Zn membrane in a MnO2||Zn full cell helps retain about 50\% of the initial capacity close to 600 cycles in the absence of extra manganese salt in the electrolyte, which is indeed promising.}, issn = {2398-4902}, doi = {10.1039/d1se00865j}, author = {Vijayakumar, Vidyanand and Torris, Arun and Kurian, Maria and Mathew, Megha Mary and Ghosh, Meena and Khairnar, Ajay B. and Badiger, Manohar V. and Kurungot, Sreekumar} } @article {47605, title = {Synthesis of four diastereomers of notoryne and their C-13 NMR chemical shifts analysis}, journal = {Journal of Chemical Sciences}, volume = {133}, year = {2021}, month = {SEP}, pages = {76}, type = {Article}, abstract = {In this manuscript we document the details of the synthesis of four diastereomers of notoryne. The synthesis of one of the diastereomer having a similar relative stereochemistry of substituents on the both THF rings like notoryne, however, being the relative stereochemistry between the bridging carbon of these two THF units is changed from anti to syn has been executed mainly to learn how the ring carbon chemical shifts vary with this change. Interestingly, the deviations are found mainly for the carbons of THF ring that bears the Br-group. In addition to this isomer, three more diastereomers having the relative stereochemistry of substituents on either of the THF rings varied have been also synthesized. All four diastereomers have been subjected for extensive NMR studies and their C-13 NMR chemical shifts have been compared with notoryne and laurendecumenyne B. In addition, chemical shifts for the four diastereomers along with these natural products were calculated with the help of DFT calculations and compared to the experimentally obtained chemical shift values.}, issn = {0974-3626}, doi = {10.1007/s12039-021-01929-y}, author = {Senapati, Sibadatta and Das, Shyamsundar and Dixit, Ruchi and Vanka, Kumar and Ramana, V, Chepuri} } @article {47690, title = {Three in one: triple G-C-T base-coded brahma nucleobase amino acid: synthesis, peptide formation, and structural features}, journal = {Journal of Organic Chemistry}, volume = {86}, year = {2021}, month = {NOV }, pages = {15689-15694}, type = {Article}, abstract = {This note reports the synthesis and peptide formation of a novel triple G-C-T nucleobase amino acid (NBA) building block featuring three recognition faces: DDA (G mimic), DAA (C mimic), and ADA (T mimic). Readily obtainable in multigram scale in a remarkably easy one-step reaction, this unique NBA building block offers scope for wide ranging applications for nucleic acid recognition and nucleic acid peptide/protein interaction studies.}, issn = {0022-3263}, doi = {10.1021/acs.joc.1c01228}, author = {Wagh, Mahendra A. and Maity, Rahul and Bhosale, Rohit J. and Semwal, Divyam and Tothadi, Srinu and Vaidhyanathan, Ramanathan and Sanjayan, Gangadhar J.} } @article {47705, title = {Total synthesis of the pseudoindoxyl class of natural products}, journal = {Organic \& Biomolecular Chemistry}, volume = {19}, year = {2021}, month = {OCT}, pages = {7970-7994}, type = {Review}, abstract = {The pseudoindoxyl sub-structural motif, amongst the large set of the indole class of alkaloids, represents a unique subset of the oxygenated indole class of the alkaloid family. A majority of this class of natural products contains complex bridged/polycyclic scaffolds with interesting biological profiles. They are thus attractive synthetic targets. Starting from 1963, twenty-eight natural products having the pseudoindoxyl scaffold have been isolated, among which the synthesis of 13 natural products has been accomplished. In this review, we highlight the completed as well as the formal total synthesis of the natural products with a spiro-pseudoindoxyl ring, with a focus on their development. The challenges and the future perspective based on the recent developments in the field will also be discussed. We strongly believe that this review will not only update but also attract the attention of researchers in dealing with the synthesis of pseudoindoxyl compounds.}, issn = {1477-0520}, doi = {10.1039/d1ob01285a}, author = {Dhote, Pawan S. and Patel, Pitambar and Vanka, Kumar and Ramana, Chepuri V.} } @article {47450, title = {Unprecedented stability in Au@Co core-shell bimetallic catalyst supported on SBA-15 (Au@Co/SBA-15) for atmospheric pressure CO hydrogenation}, journal = {Materials Today Sustainability }, volume = {13}, year = {2021}, month = {SEP}, pages = {100068}, type = {Article}, abstract = {

Bimetallic nanoparticles demonstrating\ synergistic effect\ (electronic or geometric modification) often show distinct chemical and physical properties compared with the parent metals. In catalysis, this provides opportunities to engineer solid materials with appreciable activity, selectivity, and stability. In the present study, we have synthesized Au@Co core{\textendash}shell bimetallic nanoparticles by colloidal synthesis approach with a focus to study and explore the synergistic effect between Au and Co in Au@Co\ bimetallic catalyst\ supported on SBA-15 on\ Fischer Tropsch\ (FT) reaction. The deactivation of catalyst is a significant drawback in CO hydrogenation (syngas conversion/FT synthesis), and the present study provides the design of a new material, which resists the surface cobalt oxide formation\ and inactive coke formation and gives efficient CO conversion with high stability.

}, doi = {10.1016/j.mtsust.2021.100068}, author = {Jain, P. and Chimote, M. and Vinod, C. P.} } @article {47654, title = {Unsymmetrical sp(2)-sp(3) disilenes}, journal = {Angewandte Chemie-International Edition}, volume = {60}, year = {2021}, month = {SEP }, pages = {20706-20710}, type = {Article}, abstract = {Disilenes with differently coordinated silicon atoms are not known. Here, we have shown the high yield synthesis of a range of disilenes (2-4 and 6) upon reaction of a hypersilyl silylene PhC(NtBu)(2)SiSi(SiMe3)(3) (1) with aliphatic chlorophosphines. The most striking characteristic of these disilenes is the presence of two differently coordinated Si atoms (one is three-coordinated, the other four-coordinated). The analogous reaction with Ph2PCl did not afford the desired disilene, but, surprisingly, led to the first tetraphosphinosilane (8). DFT calculations were performed to understand the bonding in disilenes and differences in reactivity of the complexes.}, keywords = {chlorophosphine, DFT, disilene, hypersilylsilylene}, issn = {1433-7851}, doi = {10.1002/anie.202107847}, author = {Bisai, Milan Kumar and Das, Tamal and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {47105, title = {Unveiling the roles of lattice strain and descriptor species on pt-like oxygen reduction activity in Pd-Bi catalysts}, journal = {ACS Catalysis}, volume = {11}, year = {2021}, month = {JAN}, pages = {800-808}, type = {Article}, abstract = {

A facile non-template-assisted mechanical ball milling technique was employed to generate a PdBi alloy catalyst. The induced lattice strain upon the milling time caused a shift of the d-band center, thereby enhancing the oxygen reduction reaction (ORR) catalytic activity. Additionally, the Pd-O reduction potential and adsorbed OH coverage used as descriptors stipulated the cause of the enhanced ORR activity upon the increased milling interval. Redox properties of surface Pd are directly correlated with a positive shift in the Pd-O reduction potential and OH surface coverage. Hence, by deconvoluting the lattice strain and the role of the descriptor species we achieved a catalyst system with a specific activity 5.4X higher than that of commercial Pt/C, as well as an improved durability. The experimental observation is well-corroborated by a theoretical simulation done by inducing strain to the system externally.

}, keywords = {charge-transfer, electrocatalysis, fuel cell, Lattice strain, oxygen reduction, Pt-like activity}, issn = {2155-5435}, doi = {10.1021/acscatal.0c03415}, author = {Sarkar, Shreya and Ramarao, S. D. and Das, Tisita and Das, Risov and Vinod, C. P. and Chakraborty, Sudip and Peter, Sebastian C.} } @article {47076, title = {Utilizing the oxygen carrier property of cerium iron oxide for the low-temperature synthesis of 1,3-butadiene from 1-butene}, journal = {Catalysis Letters}, volume = {151}, year = {2021}, month = {OCT}, pages = {3057-3066}, type = {Article}, abstract = {

Low-temperature oxidative dehydrogenation (ODH) of 1-butene to 1,3-butadiene is one of the challenging reactions in the polymer industry. Towards this a highly dispersed cerium iron oxide was synthesized by citrate gel combustion method and employed for the synthesis of 1,3-butadiene (BD) from 1-butene. The reaction was carried out at low temperature under an oxygen-free atmosphere in a continuous flow mode fixed bed reactor. A decrease in the lattice parameters observed from PXRD and high-resolution TEM analysis proved that iron occupies cerium sites in the crystal lattice. XPS, TPR, and oxygen uptake studies quantified the nature and abundance of different oxygen species. ODH was observed through consuming lattice oxygens. The vacancies generated could be filled by re-oxidation with an external supply of oxygen which will restore the catalytic activity demonstrating the Mars van Krevelen mechanism. [GRAPHICS] .

}, keywords = {1, 1-butene, 3-butadiene, Cerium, iron, Lattice oxygen, oxidative dehydrogenation}, issn = {1011-372X}, doi = {10.1007/s10562-020-03512-5, Early Access Date = FEB 2021}, author = {Venugopalan, Aswathy T. and Kandasamy, Prabu and Gogoi, Pranjal and Ratneshkumar, Jha and Thirumalaiswamy, Raja} } @article {47668, title = {ZCTs knockdown using antisense LNA GapmeR in specialized photomixotrophic cell suspensions of Catharanthus roseus: Rerouting the flux towards mono and dimeric indole alkaloids}, journal = {Physiology and Molecular Biology of Plants}, volume = {27}, year = {2021}, month = {JUL}, pages = {1437-1453}, type = {Article}, abstract = {The present study was carried out to silence the transcription factor genes ZCT1, ZCT2 and ZCT3 via lipofectamine based antisense LNA GapmeRs transfection into the protoplasts of established photomixotrophic cell suspensions. The photomixotrophic cell suspensions with a threshold of 0.5\% sucrose were raised and established using two-tiered CO2 providing flasks kept under high light intensity. The photomixotrophic cell suspensions showed morphologically different thick-walled cells under scanning electron microscopic analysis in comparison to the simple thin-walled parenchymatous control cell suspensions. The LC-MS analysis registered the vindoline production (0.0004 +/- 0.0001 mg/g dry wt.) in photomixotrophic cell suspensions which was found to be absent in control cell suspensions. The protoplasts were isolated from the photomixotrophic cell suspensions and subjected to antisense LNA GapmeRs silencing. Three lines, viz. Z1A, Z2C and Z3G were obtained where complete silencing of ZCT1, ZCT2 and ZCT3 genes, respectively, was observed. The Z3G line was found to show maximum production of vindoline (0.038 +/- 0.001 mg/g dry wt.), catharanthine (0.165 +/- 0.008 mg/g dry wt.) and vinblastine (0.0036 +/- 0.0003 mg/g dry wt.). This was supported by the multifold increment in the gene expression of TDC, SLS, STR, SGD, d4h, dat, CrT16H and Crprx. The present work indicates the master regulation of ZCT3 knockdown among all three ZCTs transcription factors in C. roseus to enhance the terpenoid indole alkaloids production. The successful silencing of transcription repressor genes has been achieved in C. roseus plant system by using photomixotrophic cell cultures through GapmeR based silencing. The present study is a step towards metabolic engineering of the TIAs pathway using protoplast transformation in C. roseus.}, keywords = {Catharanthine, LC-MS, Protoplast, TIAs, Vinblastine, Vindoline}, issn = {0971-5894}, doi = {10.1007/s12298-021-01017-y}, author = {Verma, Priyanka and Khan, Shamshad Ahmad and Parasharami, Varsha and Mathur, Ajay Kumar} } @article {46626, title = {Adsorption of toxic Pb(II) on activated carbon derived from agriculture waste (Mahogany fruit shell): isotherm, kinetic and thermodynamic study}, journal = {International Journal of Environmental Analytical Chemistry}, volume = {102}, year = {2022}, month = {DEC}, pages = {8270-8286}, type = {Article}, abstract = {

An adsorbent, mahogany fruit shell activated carbon(MFSAC), was derived from environmental friendly raw material, i.e. agriculture waste and explored for bench scale adsorption of toxic Pb(II). A facile MFSAC material was synthesised using a chemical activation method using concentrated sulphuric acid as an impregnating (activating) reagent. So derived adsorbent material was characterised by FTIR, XRD, BET, SEM, EDAX, TGA and XPS techniques to know the properties and plausible adsorption mechanism. Bench scale adsorption of toxic Pb(II) and maximum adsorption capacity of MFSAC were exhibited through batch adsorption experiments. The effect of physico-chemical parameters such as pH (1-7), MFSAC amount (0.5-5.0 g L-1), Pb(II) concentration (200-1000 mgL(-1)), contact period (60-600 min) and orbital shaking speed (60-200 rpm) was studied for maximum removal of Pb(II) upto 99.70 +/- 0.17\%. The experimental data follow the Langmuir adsorption isotherm with a maximum monolayer adsorption capacity 322.28 mg g(-1)and pseudo-second-order kinetic uptake rate. The thermodynamic and temperature study revealed that the adsorption process was spontaneous and endothermic in nature (Delta H-o = 43.37 kJ mole(-1), Delta S-o = 158.02 J mol(-1)K(-1)). Most importantly, the MFSAC adsorbent was successfully regenerated and reused with conspicuous performance up to five consecutive cycles. The bench-scale adsorption with simple synthesis route, good stability and remarkable regeneration capability makes the MFSAC as an encouraging adsorbent for wastewater treatment.

}, keywords = {activated carbon, Adsorption, mahogany fruit shell, Pb(II), sulphuric acid}, issn = {0306-7319}, doi = {10.1080/03067319.2020.1849648}, author = {Patil, Suryakant A. and Suryawanshi, Umesh P. and Harale, Namdev S. and Patil, Sandip K. and Vadiyar, Madgonda M. and Luwang, Meitram N. and Anuse, Mansing A. and Kim, Jin H. and Kolekar, Sanjay S.} } @article {48221, title = {Algal biomass-loaded hydrogel scaffolds as a biomimetic platform with antibacterial and wound healing activities}, journal = {ACS Applied Polymer Materials}, volume = {4}, year = {2022}, month = {AUG}, pages = {5800-5812}, type = {Article}, abstract = {

The confluence of hydrogel scaffolds and dried algal biomass (AB), consisting of all the bioactive compounds, offers the possibility to facilitate wound healing while simultaneously instilling antibacterial benefits. For this purpose, a single-step synthesis of algal (Chlorella sorokiniana) biomass-loaded hydrogel scaffolds (AHS) was achieved. C. sorokiniana has been used in different areas for several years and has proved attractive to the pharmaceutical and cosmetic industries. Of note, the presence of phytochemicals and various bioactive compounds provides an added health benefit. Hitherto, we report AHS with accelerated wound healing along with potent anti-inflammatory and antibacterial properties. AHS consisting of different concentrations of AB was applied for 14 days on excisional wounds in mice. Microscopic analyses, assessment of proinflammatory and anti-inflammatory cytokines, and histological studies were performed to investigate wound healing. These scaffolds were extensively characterized and studied using Fourier transform infrared, X-ray diffraction, Raman, atomic force microscopy, transmission electron microscopy, scanning electron microscopy, swelling, rheological, thermal, and mechanical analyses. AHS have excellent biocompatibility in addition to significant antibacterial activity against Escherichia coli (99\%) and Staphylococcus aureus (98\%). We believe that the as-synthesized AHS have the potential to broaden the arsenal of more effective wound healing processes along with antibacterial activities.

}, keywords = {antibacterial activity, Biomass, hydrogel scaffold, microalgae, wound Healing}, issn = {2637-6105}, doi = {10.1021/acsapm.2c00722}, author = {Agarwal, Aakanksha and Kumar, Arun and Garg, Piyush and Chakraborty, Arnab and Verma, Ranjan and Sarwat, Maryam and Gupta, Ajay and Sasmal, Pijus K. and Verma, Yogesh Kumar and Chowdhury, Chiranjit and Mukherjee, Monalisa} } @article {48116, title = {Antimicrobial two-dimensional covalent organic nanosheets (2D-CONs) for the fast and highly efficient capture and recovery of phosphate ions from water}, journal = {Journal of Materials Chemistry A}, volume = {10}, year = {2022}, month = {MAR }, pages = {4585-4593}, type = {Article}, abstract = {

The retrieval of depleting resources from wastewater could help resolve the mounting demands for resources in our society. Phosphate is an essential nutrient for all living things. However, the diminution of global reserves of phosphate rock could significantly affect our food security in the near future. At the same time, the removal of phosphates and pathogens is of great importance for water security and de-eutrophication. The specific pH-dependent adsorption and desorption of phosphate ions by water-insoluble adsorbents is an exciting strategy for removing and recovering phosphates from contaminated water. Herein, we report the development of new two-dimensional guanidine-containing covalent organic nanosheets (2D-gCONs). This water-insoluble amorphous polymer (exfoliated) selectively sequestered phosphate ions in the presence of other competing anions and could be reused for multiple cycles. The polymer showed a fast removal of phosphate ions with a maximum adsorption capacity of 398 mg g(-1) (pH 7.0). The sequestered phosphate ions could be easily reclaimed, and the polymer could be recycled just by altering the pH (similar to 10.0) of the aqueous solution. The guanidinium moieties played a pivotal role in exfoliation in aqueous medium and in the antibacterial activities against Gram-negative and Gram-positive bacteria. We hypothesize that the current study may advance the design of water-insoluble CONs to remove and recover phosphate ions from wastewater and could help alleviate the negative impact of water eutrophication. This strategy can also be tweaked to address other severe environmental challenges.

}, issn = {2050-7488}, doi = {10.1039/d1ta10911a}, author = {Dey, Subhasis and Das, Sribash and Patel, Anjali and Raj, K. Vipin and Vanka, Kumar and Manna, Debasis} } @article {48093, title = {Assembly, annotation, and comparative whole genome sequence of fusarium verticillioides isolated from stored maize grains}, volume = {11}, year = {2022}, month = {JUL}, pages = {810}, type = {Article}, abstract = {

Fusarium verticillioides is a plant pathogenic fungus affecting a wide range of crops worldwide due to its toxigenic properties. F. verticillioides BIONCL4 strain was isolated from stored maize grain samples in India, and produces high amount of fumonisin B1 (FB1). We report a comparative genomic analysis of F. verticillioides, covering the basic genome information, secretome, and proteins involved in host-pathogen interactions and mycotoxin biosynthesis. Whole-genome sequencing (WGS) was performed using the Illumina platform with an assembly size of 42.91 Mb, GC content of 48.24\%, and 98.50\% coverage with the reference genome (GCA000149555). It encodes 15,053 proteins, including 2058 secretory proteins, 676 classical secretory proteins, and 569 virulence and pathogenicity-related proteins. There were also 1447 genes linked to carbohydrate active enzymes (CaZymes) and 167 genes related to mycotoxin production. Furthermore, F. verticillioides genome comparison revealed information about the species{\textquoteright} evolutionary history. The overall study helps in disease prevention and management of mycotoxins to ensure food safety.

}, keywords = {comparative genomics, Fusarium verticillioides, mycotoxin biosynthesis, plant-pathogen interaction, Secretome, whole-genome sequencing}, doi = {10.3390/pathogens11070810}, author = {Navale, Vishwambar D. and Sawant, Amol M. and Gowda, Varun U. and Vamkudoth, Koteswara Rao} } @article {47900, title = {Biosynthetic process and strain improvement approaches for industrial penicillin production}, journal = {Biotechnology Letters}, volume = {44}, year = {2022}, month = {FEB}, pages = {179-192}, type = {Review}, abstract = {

Penicillins and cephalosporins are the most important class of beta (beta) lactam antibiotics, accounting for 65\% total antibiotic market. Penicillins are produced by Penicillium rubens (popularly known as P. chrysogenum) were used to synthesize the active pharmaceutical intermediate (API), 6-aminopenicillinic acid (6-APA) employed in semisynthetic antibiotic production. The wild strains produce a negligible amount of penicillin (Pen). High antibiotic titre-producing P. chrysogenum strains are necessitating for industrial Pen production to meet global demand at lower prices. Classical strain improvement (CSI) approaches such as random mutagenesis, medium engineering, and fermentation are the cornerstones for high-titer Pen production. Since, Sir Alexander Fleming Discovery of Pen, great efforts are expanded to develop at a commercial scale antibiotics producing strains. Breakthroughs in genetic engineering, heterologous expression and CRISPR/Cas9 genome editing tools opened a new window for Pen production at a commercial scale to assure health crisis. The current state of knowledge, limitations of CSI and genetic engineering approaches to Pen production are discussed in this review.

}, keywords = {beta-lactam antibiotic, Classical strain improvement (CSI), Genetic engineering, Penicillin, Penicillium chrysogenum}, issn = {0141-5492}, doi = {10.1007/s10529-022-03222-5}, author = {Sawant, Amol M. and Vamkudoth, Koteswara Rao} } @article {47795, title = {Cardol: Cashew nut shell liquid (CNSL) - derived starting material for the preparation of partially bio-based epoxy resins}, journal = {European Polymer Journal}, volume = {166}, year = {2022}, month = {MAR}, pages = {111029}, type = {Article}, abstract = {Cardol is one of the interesting constituents of cashew nut shell liquid (CNSL) - a by-product of cashew processing industry- and it amounts to 15{\textendash}20\% by weight in natural CNSL. Chemically, cardol is a 15-carbon chain-substituted resorcinol wherein the side chain predominately contains mixture of one, two and three double bonds. Cardol on reaction with epichlorohydrin in the presence of sodium hydroxide afforded diglycidyl ether of cardol (DGEC). DGEC is a viscous free-flowing liquid (bulk viscosity 70 cP at 25~{\textdegree}C) and thus offers advantages in terms of ease of processing. DGEC and various compositions of DGEC with commercially available diglycidyl ether of bisphenol A (DGEBA) were cured with two amine hardeners, namely, isophorone diamine (IPDA) and diethylene triamine (DETA). The effects of different ratios of amine/epoxy (nah/ne) on cure characteristics were studied. The epoxy thermosets were characterized by DSC, TGA, DMA and tensile testing. DSC analysis showed glass transition temperature (Tg) values in the range 63{\textendash}155~{\textdegree}C for IPDA-cured thermosets, while DETA-cured thermosets exhibited Tg values in the range 45{\textendash}145~{\textdegree}C. Td5\% values, determined by TG analysis of epoxy thermosets, were in the range 347{\textendash}359~{\textdegree}C indicating their reasonably good thermal stability. Dynamic mechanical analysis showed storage modulus (E{\textquoteright}) in the range 0.75{\textendash}2.54 GPa and 0.51{\textendash}2.24 GPa for IPDA-cured and DETA-cured thermosets, respectively. The E{\textquoteright} value of epoxy thermosets was found to decrease with increase in molar proportion of DGEC in the formulations with DGEBA while elongation at break was found to increase from 3.1\% to 9.7\% and 2.8\% to 5.1\% for IPDA- and DETA-cured systems, respectively. SEM images of cryogenically fractured surfaces of cured thermosets based on studied compositions of DGEBA and DGEC did not indicate any phase separation implying homogeneous mixing of both the epoxy resins.}, keywords = {bio-based, Cardol, cashew nut shell liquid (CNSL), Epoxy resins, Storage modulus}, issn = {0014-3057}, doi = {https://doi.org/10.1016/j.eurpolymj.2022.111029}, url = {https://www.sciencedirect.com/science/article/pii/S0014305722000337}, author = {Ketan Makwana and Amol B. Ichake and Vinayak Valodkar and G. Padmanaban and Manohar V. Badiger and Prakash P. Wadgaonkar} } @article {48152, title = {Comparative study of polycaprolactone electrospun fibers and casting films enriched with carbon and nitrogen sources and their potential use in water bioremediation}, journal = {Membranes}, volume = {12}, year = {2022}, month = {MAR}, pages = {327}, type = {Article}, abstract = {

Augmenting bacterial growth is of great interest to the biotechnological industry. Hence, the effect of poly (caprolactone) fibrous scaffolds to promote the growth of different bacterial strains of biological and industrial interest was evaluated. Furthermore, different types of carbon (glucose, fructose, lactose and galactose) and nitrogen sources (yeast extract, glycine, peptone and urea) were added to the scaffold to determinate their influence in bacterial growth. Bacterial growth was observed by scanning electron microscopy; thermal characteristics were also evaluated; bacterial cell growth was measured by ultraviolet-visible spectrophotometry at 600-nm. Fibers produced have an average diameter between 313 to 766 nm, with 44\% superficial porosity of the scaffolds, a glass transition around similar to 64 degrees C and a critical temperature of similar to 338 degrees C. The fibrous scaffold increased the cell growth of Escherichia coli by 23\% at 72 h, while Pseudomonas aeruginosa and Staphylococcus aureus increased by 36\% and 95\% respectively at 48 h, when compared to the normal growth of their respective bacterial cultures. However, no significant difference in bacterial growth between the scaffolds and the casted films could be observed. Cell growth depended on a combination of several factors: type of bacteria, carbon or nitrogen sources, casted films or 3D scaffolds. Microscopy showed traces of a biofilm formation around 3 h in culture of P. aeruginosa. Water bioremediation studies showed that P. aeruginosa on poly (caprolactone)/Glucose fibers was effective in removing 87\% of chromium in 8 h.

}, keywords = {bacterial growth, carbon source, electrospinning, nitrogen source, poly (caprolactone)}, doi = {10.3390/membranes12030327}, author = {Alejandra Pompa-Monroy, Daniella and Leticia Iglesias, Ana and Gulam Dastager, Syed and Namdeo Thorat, Meghana and Olivas-Sarabia, Amelia and Valdez-Castro, Ricardo and Angelica Hurtado-Ayala, Lilia and Manuel Cornejo-Bravo, Jose and Lizeth Perez-Gonzalez, Graciela and Jesus Villarreal-Gomez, Luis} } @article {48383, title = {Computational insights into hydroboration with acyclic alpha-Borylamido-germylene and stannylene catalysts: Cooperative dual catalysis the key to system efficiency}, journal = {Polyhedron}, volume = {222}, year = {2022}, month = {AUG}, pages = {115907}, type = {Article}, abstract = {

The chemistry of low valent main group compounds has grown as an alternative to the chemistry of less abundant and less green transition metal complexes. It has been found that low valent compounds such as carbenes, silylenes, stannylenes and germylenes are efficient for activating small molecules and for catalysis. However, the reaction mechanism and the factors that affect the rate of reaction are not completely understood. In this computational investigation with density functional theory (DFT), we investigate and demonstrate the efficiency of a new mechanism for the hydroboration of aldehydes by germylenes and stannylenes, in the presence of the common hydroborating agent, pinacolborane, HBpin. This mechanism involves an HBpin molecule as an additional catalyst that cooperates with the germylene or stannylene catalyst to efficiently carry out the hydroboration. This mechanism is first demonstrated to work for experimentally reported systems, and then shown to be efficient for newly proposed germylene and stannylene systems. These new systems are alpha-Borylamido-germylene ((2,6-iPr(2)C(6)H(3)NBCy(2))(2)Ge(II)) and alpha-Borylamido-stannylene((2,6-iPr(2)C(6)H(3)NBCy(2))(2)Sn(II)). These new insights will help researchers look into low valent germylene and stannylene chemistry from a new perspective.

}, keywords = {Catalysis of hydroboration, computational chemistry, Germylenes and stannylenes, Main group chemistry, New mechanism}, issn = {0277-5387}, doi = {10.1016/j.poly.2022.115907}, author = {Banerjee, Subhrashis and Vanka, Kumar} } @article {47994, title = {Controlled exchange bias behavior of manganese nanoparticles}, journal = {Journal of Magnetism and Magnetic Materials}, volume = {559}, year = {2022}, month = {OCT}, pages = {169504}, type = {Article}, abstract = {

Mn(0) colloids were synthesized by solvated metal atom dispersion approach utilizing hexadecylamine, toluene, and THF as coordinating ligands. Mn-toluene and Mn-THF nanoparticles were found to be highly pyrophoric in nature and demand careful handling whereas, Mn-HDA nanoparticles undergo slow oxidation. TEM micrographs revealed formation of nanoparticles between 3 and 6 nm. Magnetic studies of these three samples displayed shift in the field-cooled M-H hysteresis loop which has been attributed to exchange bias behavior. The exchange bias field, HE measured at 5 K varies with change in coordinating ligands around the Mn center which are 1217 Oe, 4408 Oe and, 6350 Oe for Mn-HDA, Mn-toluene and Mn-THF nanoparticles, respectively. The large exchange bias field has been attributed to the presence of uncompensated antiferromagnetic surface spins and the exchange interactions at the nanoparticle surface due to surface oxidation.

}, keywords = {Antiferromagnetism, exchange bias, Ferromagnetism, Manganese nanoparticles, Uncompensated spins}, issn = {0304-8853}, doi = {10.1016/j.jmmm.2022.169504}, author = {Tiwari, Garima and Vinod, C. Prabhakaran and Jagirdar, Balaji R.} } @article {48067, title = {Coordination flexibility aided CO2-specific gating in an iron isonicotinate MOF}, journal = {Chemistry-an Asian Journal}, volume = {17}, year = {2022}, month = {FEB}, pages = {e202101305}, type = {Article}, abstract = {

Coordination flexibility assisted porosity has been introduced into an Iron-isonicotinate metal-organic framework (MOF), (Fe(4-PyC)(2) . (OH). The framework showed CO2-specific gate opening behavior, which gets tuned as a function of temperature and pressure. The MOF {\textquoteleft} s physisorptive porosity towards CO2, CH4, and N-2 was investigated; it adsorbed only CO2 via a gate opening phenomenon. The isonicotinate, representing a borderline soft base, is bound to the hard Fe3+ centre through monodentate carboxylate and pyridyl nitrogen. This moderately weak binding enables isonicotinate to spin like a spindle under the CO2 pressure opening the gate for a sharp increase in CO2 uptake at 333 mmHg (At 298 K, the CO2 uptake increases from 0.70 to 1.57 mmol/g). We investigated the MOF {\textquoteleft} s potential for CO2/N-2 and CO2/CH4 gas separation aided by this gating. IAST model reveals that the CO2/N-2 selectivity jumps from 325 to 3131 when the gate opens, while the CO2/CH4 selectivity increases three times. Interestingly, this Fe-isonicotinate MOF did not follow the trend set by our earlier reported Hard-Soft Gate Control (established for isostructural M2+-isonicotinate MOFs (M=Mg, Mn)). However, we account for this discrepancy using the different oxidation state of metals confirmed by X-ray photoelectron spectroscopy and magnetism.

}, keywords = {CO2 capture, flexible MOF, gating, Isonicotinic}, issn = {1861-4728}, doi = {10.1002/asia.202101305}, author = {Singh, Himan Dev and Nandi, Shyamapada and Chakraborty, Debanjan and Singh, Kirandeep and Vinod, Chathakudath P. and Vaidhyanathan, Ramanathan} } @article {48070, title = {Covalent organic framework with electrodeposited copper nanoparticles - a desirable catalyst for the Ullmann coupling reaction}, journal = {Journal of Materials Chemistry A}, volume = {10}, year = {2022}, month = {JUL}, pages = {15647-15656}, type = {Article}, abstract = {

A covalent organic framework is a porous covalently-linked polymeric assembly built from molecular lego blocks, the monomers. A COF{\textquoteright}s high surface area, ordered pores, and intrinsic low density makes it a perfect heterogeneous catalyst component. Dispersing catalytic metal nanoparticles into the porous COF matrix in a {\textquoteleft}capping-agent-free{\textquoteright} manner can aid the maximal utilization of the active sites. To generate single-site catalysts, metals have been anchored to dense supports, or metal ions have been coordinated to the porous organic framework. The latter has superior atom efficiency and a substrate diffusion advantage. Stably nestling neutral metallic clusters into open-framework supports with no specifically strong binding groups requires a different approach. If infused from extremely dilute electrolytes, metal clusters can be nanoconfined into electrically activated COFs. At low-loadings, it can resemble a single-site catalyst with high atom efficiency. Herein, we report the larger scale synthesis of IISERP-COF15 and electrochemical loading of copper nanoparticles into its pores at loadings as low as 3.34 wt\%. We employed classical Ullmann reactions to adjudge its activity. Typical turnover numbers for the catalysts reported in the literature are approximately 50-100. A Cu@COF shows high activity with a very low catalyst loading of 0.25 mol\% (TON around similar to 300-350 vs. 4 for neat CuCl2 center dot 2H(2)O (homogeneous catalyst) and turnover frequency (similar to 15-17 h(-1))). We recycled it for up to 3 cycles. Furthermore, we report a multi-fold Ullmann reaction producing an unreported hexaaldehyde to demonstrate the latitude of the catalyst. Our work points to the potential of a dilutely loaded metal@COF as a mimic of the single-site catalyst for synthesizing valuable C-O linked molecules. Our findings from computational modeling shed light on the role of the COF as an active nanoporous support for Ullmann C-O coupling.

}, issn = {2050-7488}, doi = {10.1039/d2ta01326f}, author = {Chandran, Chandana and Singh, Himan Dev and Leo, Liya S. and Shekhar, Pragalbh and Rase, Deepak and Chakraborty, Debanjan and Vinod, Chathakudath P. and Vaidhyanathan, Ramanathan} } @article {48105, title = {Decay processes in cationic alkali metals in microsolvated clusters: a complex absorbing potential based equation-of-motion coupled cluster investigation}, journal = {Journal of Chemical Theory and Computation}, volume = {18}, year = {2022}, month = {FEB }, pages = {807-816}, type = {Article}, abstract = {

We have employed the highly accurate complex absorbing potential based ionization potential equation-of-motion coupled cluster singles and doubles (CAP-IP-EOM-CCSD) method to study the various intermolecular decay processes in ionized metals (Li+, Na+, K+) microsolvated by water molecules. For the Li atom, the electron is ionized from the 1s subshell. However, for Na and K atoms, the electron is ionized from 2s and both 2s and 2p subshells, respectively. We have investigated decay processes for the Li+-(H2O)(n) (n = 1-3) systems, as well as Na+-(H2O)(n) (n = 1, 2), and K+-H2O. The lithium cation in water can decay only via electron transfer mediated decay (ETMD) as there are no valence electrons in lithium. We have investigated how the various decay processes change in the presence of different alkali metal atoms and how the increasing number of water molecules play a significant role in the decay of microsolvated systems. To see the effect of the environment, we have studied Li+-NH3 in comparison to Li+-H2O. In the case of Na+-H2O, we have studied the impact of bond distance on the decay width. The effect of polarization on decay width was checked for the X+-H2O (X = Li, Na) systems. We used the PCM model to study the polarization effect. We have compared our results with existing theoretical and experimental results wherever available in the literature.

}, issn = {1549-9618}, doi = {10.1021/acs.jctc.1c01036}, author = {Kumar, Ravi and Ghosh, Aryya and Vaval, Nayana} } @article {48146, title = {Design and synthesis of eugenol/isoeugenol glycoconjugates and other analogues as antifungal agents against Aspergillus fumigatus}, journal = {RSC Medicinal Chemistry}, volume = {13}, year = {2022}, month = {AUG}, pages = {955-962}, type = {Article}, abstract = {

Glycoconjugates are biologically significant molecules as they tend to serve a wide range of intra- and extra-cellular processes depending on their size and complexity. The secondary metabolites of the plant Myristica fragrans, eugenol and isoeugenol, have shown antifungal activities (IC50 1900 mu M). Therefore, we envisioned that glycoconjugates based on these two scaffolds could prove to be potent antifungal agents. Triazole-containing compounds have shown prominent activities as antifungal agents. Based on this, we opined that a Cu(i) catalyzed click reaction could serve as the bridging tool between a eugenol/isoeugenol moiety and sugars to synthesize eugenol/isoeugenol based glycoconjugates. In our present work, we have coupled propargylated eugenol/isoeugenol and azido sugar to furnish eugenol/isoeugenol based glycoconjugates. In another approach, we have carried out hydroxylation of the double bond of eugenol and subsequent azidation of a primary alcohol followed by intramolecular coupling reactions leading to various other analogues. All the synthesized compounds were assayed against an opportunistic pathogenic fungus, Aspergillus fumigatus. Among the synthesized compounds, two analogues have exhibited significant antifungal activities with IC50 values of 5.42 and 9.39 mu M, respectively. The study suggested that these two analogues inhibit cell wall-associated melanin hydrophobicity along with the number of conidia. The synthesized compounds were found to be non-cytotoxic to an untransformed cell line.

}, doi = {10.1039/d2md00138a}, author = {Goswami, Lakshmi and Gupta, Lovely and Paul, Sayantan and Vermani, Maansi and Vijayaraghavan, Pooja and Bhattacharya, Asish K.} } @article {48069, title = {Direct (hetero)arylation (DHAP) polymerization of conjugated polymers - new A-B-A monomer design for P(NDI2OD-T2) \& the challenges of adopting DHAP for continuous flow processes}, journal = {Journal of Materials Chemistry C}, volume = {10}, year = {2022}, month = {SEP}, pages = {13025-13039}, type = {Article}, abstract = {

P(NDI2OD-T2), also known as Polyera ActivInk N2200, was synthesized by the atom-economic direct hetero arylation polymerization (DHAP) route using a newly designed A-B-A monomer. The new monomer design involved flanking naphthalene diimide with bithiophene units in the bay position, which was further polymerized with bay substituted 1,4-dibromo naphthalene diimide, to afford the same polymer structure as P(NDI2OD-T2). The new monomer design resulted in a very high molecular weight (M-n: 99.5 kDa, D-M: 2.8) defect-free polymer in a quantitative yield by the DHAP batch process using 1,2,4-trichlorobenzene (TCB) as the solvent. DFT studies revealed that the abstraction of the alpha-proton from the naphthalene diimide substituted 2,2 {\textquoteleft}-bithiophene was favorable by 2.6 kcal mol(-1) (Delta Delta G) as compared to that from 2,2 {\textquoteleft}-bithiophene. The reason for this improved C-H activation at the alpha position can be attributed to the presence of C-HMIDLINE HORIZONTAL ELLIPSIS pi stabilizing interactions in naphthalene diimide substituted 2,2 {\textquoteleft}-bithiophene, which strengthens upon the extended charge delocalization throughout the ring, thus stabilizing the conjugate base generated after the proton abstraction. Continuous flow polymerization was carried out by pumping the DHAP reaction mixture including the monomers, catalyst, and additive (pivalic acid) solubilized in degassed TCB through a pre-heated glass condenser packed with K2CO3 and Celite under aerobic conditions. Reproducible molecular weights of M-n: 29.5 kDa, D-M: 1.7 were obtained at much lower concentrations of reactant mixture compared to that for batch polymerization. This is the first report of the synthesis of P(NDI2OD-T2) by a Continuous Flow Process adopting the DHAP route to obtain a defect-free polymer with reasonable molecular weights. P(NDI2OD-T2) was also synthesized by Stille polymerization as a reference control sample to compare the thermal and charge carrier transport properties of the DHAP polymers. Organic field-effect (OFET) mobility measurements indicated mobility values in the order of 10(-3) cm(2) V-1 s(-1) for the DHAP batch polymer (using the novel monomer design). The P(NDI2OD-T2) synthesized by DHAP batch using the commonly used starting materials - bisbromo naphthalene diimide and bithiophene, exhibited OFET mobilities which were one order less, similar to 10(-4) cm(2) V-1 s(-1). This observation highlights the importance of structural design in the monomer to enhance reactivity and thereby the bulk properties using the DHAP route.

}, issn = {2050-7526}, doi = {10.1039/d2tc02514k}, author = {Kakde, Navnath R. and Bharathkumar, H. J. and Wavhal, Bhaiyyasaheb A. and Nikam, Arun and Patil, Suneha and Dash, Soumya Ranjan and Vanka, Kumar and Krishnamoorthy, K. and Kulkarni, Amol and Asha, S. K.} } @article {48096, title = {Direct oxidation of bromo-derived Fischer-Borsche oxo-ring using molecular iodine with combined experimental and computational study}, journal = {Organic \& Biomolecular Chemistry}, volume = {20}, year = {2022}, month = {JUL}, pages = {5726-5729}, type = {Article}, abstract = {

A direct oxidation of the bromo-derived Fischer-Borsche oxo-ring leading to carbazolequinone has been developed by using molecular iodine. This unprecedented transformation has been used for the modular synthesis of the anti-cardiotonic agent murrayaquinone. Furthermore, the present method has been generalized to a broad range of functional groups, with good to excellent yield.

}, issn = {1477-0520}, doi = {10.1039/d2ob00793b}, author = {Humne, Vivek T. and Ghom, Monica H. and Naykode, Mahavir S. and Dangat, Yuvraj and Vanka, Kumar and Lokhande, Pradeep} } @article {48027, title = {Divergent annulation of spiro[indoline-pyran] and fused (Epoxyetheno)indeno-furan from 1,2-diketone and 1-cyanoketone}, journal = {European Journal of Organic Chemistry}, volume = {2022}, year = {2022}, month = {AUG}, pages = {e202101534}, type = {Article}, abstract = {

A simple and efficient method for the construction of spiro[indoline-pyran] and fused (epoxyetheno)indeno[1,2-b]furan compounds from 1-cyanoketones and 1,2-diketone has been developed. The synthesis proceeded via the Knoevenagel and Michael adduct through intramolecular/Paal-Knorr cyclization under similar reaction condition. The less commonly used 1-cyanoketones and active carbonyl compounds served as the indole containing pyran and bicyclic furan source for the preparation of a new series of heterocyclic compounds. This heterocyclic structure allows one and more than one tetra-substituted carbon center and sequential hexa- and penta-cyclic core under very mild conditions and shows excellent chemo and regioselectivity. In addition, the synthesis of spiro[indoline-pyran] and (epoxyetheno)indeno[1,2-b]furan was demonstrated in a gram scale.

}, keywords = {Diverse synthesis, Intramolecular, Knoevenagel and Michael adduct, molecular diversity, Oxygen heterocycles, Paal-Knorr cyclization}, issn = {1434-193X}, doi = {10.1002/ejoc.202101534}, author = {Yadav, Maruti B. and Vagh, Sandip S. and Jeong, Yeon Tae} } @article {47761, title = {Donor-acceptor based solvent-free organic liquid hybrids with exciplex emission and room temperature phosphorescence}, journal = {Chemical Communications}, volume = {58}, year = {2022}, month = {FEB }, pages = {1998-2001}, type = {Article}, abstract = {Solvent-free organic liquids are well-known for their excellent luminescence features. Hence, the recent developments in this area have marked them as potential emitters with high quantum yield and enhanced processability. The support of an available liquid matrix enables doping to deliver hybrid liquids with intriguing luminescence features. In this direction, we report solvent-free liquid donor-acceptor pairs with exciplex emission and room temperature phosphorescence at very low acceptor loading. The underlying weak intermolecular interactions have been revealed by 2D NMR techniques and theoretical calculations. The formation of large-area thin films by exciplex and phosphorescent liquid hybrids will encourage the development of scalable lighting and display materials.}, issn = {1359-7345}, doi = {10.1039/d1cc07082g}, author = {Wakchaure, Vivek Chandrakant and Veer, Sairam D. and Nidhankar, Aakash D. and Goudappagouda and Nayak, Rashmi and Asokan, Kiran and Ravindranathan, Sapna and Babu, Sukumaran Santhosh} } @article {48186, title = {Electrodeposited layered sodium vanadyl phosphate (NaxVOPO4 center dot nH(2)O) as cathode material for aqueous rechargeable zinc metal batteries}, journal = {Energy \& Fuels}, volume = {36}, year = {2022}, month = {JUN }, pages = {6520-6531}, type = {Article}, abstract = {

Aqueous rechargeable zinc metal batteries (ARZMBs) present a safer and cost-effective solution for energy storage in stationary applications. However, a major challenge is the lack of suitable cathode materials simultaneously exhibiting high operating voltage and long cycling stability. Herein, we report the polyanionic sodium-intercalated layered vanadyl phosphate [NaxVOPO4 center dot nH(2)O (NVP)] as a suitable high-voltage and stable cathode for ARZMBs. This work employs a simpler electrochemical route (electrodeposition) for the synthesis of NVP over functionalized carbon fiber substrates and its application as a binder-free cathode in ARZMBs. The electrodeposited NVP possesses a morphology of vertically aligned well-separated nanosheet bundles resembling a flower. When used as the ARZMB cathode, the NVP electrode delivers a specific discharge capacity of 100 mA h g(-1) at 0.033 A g(-1) and high cycling stability (98\% retention of the initial capacity over 1100 cycles at 0.333 A g(-1)) in a mild aqueous electrolyte with moderate zinc salt concentration. The observed electrochemical performance of NVP is credited to the synergistic effect of unique nanoflower morphology, the pillaring effect offered by the intercalated Na, and the intimate contact of the active material with the carbon fiber network. These factors are favorable for enhancing the transport of the electrolyte ions and electrons and maintaining the structural stability of the electrode during long-term cycling. The NVP electrode could also deliver appreciable performance (a discharge capacity of 73 mA h g(-) 1 and a current density of 0.033 A g(-1)) in quasi-solidstate ARZMB cells employing PVA/Zn(CF3SO3)(2) gel electrolyte.

}, issn = {0887-0624}, doi = {10.1021/acs.energyfuels.2c00831}, author = {Dilwale, Swati and Ghosh, Meena and Vijayakumar, Vidyanand and Kurungot, Sreekumar} } @article {48410, title = {Elliptically birefringent chemically tuned liquid crystalline nanocellulose composites for photonic applications}, journal = {Journal of Molecular Liquids}, volume = {366}, year = {2022}, month = {NOV }, pages = {120326}, type = {Article}, abstract = {

Cellulose nanocrystals (CNCs) based photonic materials are one of the promising materials in the recent trends. The liquid crystalline behavior of the CNCs can be tailored to different advanced applications. The proposed research investigates the potential of CNCs as an optically active material. CNCs were tuned to hydroxypropyl nano cellulose (HPNC) with the degree of substitution 1.39. The prepared liquid crystalline HPNC were dispersed in various concentrations of monomethyl ether of polyethylene glycol to get waterborne materials with specific optical anisotropy. The extraction, modification, and morphology of the CNCs were investigated using NMR (Nuclear Magnetic Resonance), TEM (Transmission Electron Microscopy), XRD (X-ray Powder Diffraction), and FESEM (Field Emission Scanning Electron Microscopy) analysis. The prepared HPNC was analyzed using a hot stage POM (Polarized Optical Microscope) for optical anisotropy. The thermal stability of prepared CNCs and HPNC was also investigated. Upon optimization using rheology and POM, it was found that at the ratio of 1:1, HPNC (5 wt\%) and mPEG (40 wt\%) had the most distinct optical properties. The potential of the prepared materials can be further explored in sensing, smart coating, and security materials. (C) 2022 Elsevier B.V. All rights reserved.

}, keywords = {bagasse, Cellulose nanocrystals, Elliptical birefringence, liquid crystals, optical anisotropy}, issn = {0167-7322}, doi = {10.1016/j.molliq.2022.120326}, author = {Singh, Shiva and Bhardwaj, Shakshi and Verma, Chhavi and Chhajed, Monika and Balayan, Kajal and Ghosh, Kaushik and Maji, Pradip K.} } @article {48137, title = {Enantioselective Cu(I)-catalyzed borylative cyclization of enone-tethered cyclohexadienones and mechanistic insights}, journal = {Nature Communications}, volume = {13}, year = {2022}, month = {FEB }, pages = {854}, type = {Article}, abstract = {

Rapidly building molecular structures with both elements of complexity and flexibility is a key goal of organic synthesis. Here the authors show a tandem copper-catalyzed beta-borylation/Michael addition on prochiral enone-tethered 2,5-cyclohexadienones, to generate bicyclic borylated products in high yield and enantioselectivity. The catalytic asymmetric borylation of conjugated carbonyls followed by stereoselective intramolecular cascade cyclizations with in situ generated chiral enolates are extremely rare. Herein, we report the enantioselective Cu(I)-catalyzed beta-borylation/Michael addition on prochiral enone-tethered 2,5-cyclohexadienones. This asymmetric desymmetrization strategy has a broad range of substrate scope to generate densely functionalized bicyclic enones bearing four contiguous stereocenters with excellent yield, enantioselectivity, and diastereoselectivity. One-pot borylation/cyclization/oxidation via the sequential addition of sodium perborate reagent affords the corresponding alcohols without affecting yield and enantioselectivity. The synthetic potential of this reaction is explored through gram-scale reactions and further chemoselective transformations on products. DFT calculations explain the requirement of the base in an equimolar ratio in the reaction, as it leads to the formation of a lithium-enolate complex to undergo C-C bond formation via a chair-like transition state, with a barrier that is 22.5 kcal/mol more favourable than that of the copper-enolate complex.

}, issn = {0039-7881}, doi = {10.1038/s41467-022-28288-7}, author = {Jadhav, Sandip B. and Dash, Soumya Ranjan and Maurya, Sundaram and Nanubolu, Jagadeesh Babu and Vanka, Kumar and Chegondi, Rambabu} } @article {47801, title = {Flow visualization by Matlab{\textregistered} based image analysis of high-speed polymer melt extrusion film casting process for determining necking defect and quantifying surface velocity profiles}, journal = {Advanced Industrial and Engineering Polymer Research}, volume = {5}, year = {2022}, month = {JAN}, pages = {1-11}, type = {Article}, abstract = {The primary objective of this research paper is to detect and quantify the necking defect and surface velocity profiles in high-speed polymer melt extrusion film casting (EFC) process using Matlab{\textregistered} based image processing techniques. Extrusion film casting is an industrially important manufacturing process and is used on an industrial scale to produce thousands of kilograms of polymer films/sheets and coated products. In this research, the necking defect in an EFC process has been studied experimentally and the effects of macromolecular architecture such as long chain branching (LCB) on the extent of necking have been determined using image processing methodology. The methodology is based on the analysis of a sequence of image frames taken with the help of a commercial CCD camera over a specific target area of the EFC process. The image sequence is then analyzed using Matlab{\textregistered} based image processing toolbox wherein a customized algorithm is written and executed to determine the edges of the extruded molten polymeric film to quantify the necking defect. Alongwith the necking defect, particle tracking velocimetry (PTV) technique is also used in conjunction with the Matlab{\textregistered} software to determine the centerline and transverse velocity profiles in the extruded molten film. It is concluded from this study that image processing techniques provide valuable insights into quantifying both the necking defect and the associated velocity profiles in the molten extruded film.}, keywords = {Edge detection, Extrusion, Film, image analysis, Necking, Velocity measurement}, issn = {2542-5048}, doi = {10.1016/j.aiepr.2021.02.003}, author = {Aarati Vagga and Swapnil Aherrao and Harshawardhan Pol and Vivek Borkar} } @article {48107, title = {Free base phthalocyanine coating as a superior corrosion inhibitor for copper surfaces: a combined experimental and theoretical study}, journal = {Colloids and Surfaces A-Physicochemical and Engineering Aspects}, volume = {648}, year = {2022}, month = {SEP }, pages = {129138}, type = {Article}, abstract = {

In the quest of novel, eco-benign copper corrosion inhibitors, free base and a set of six metal Phthalocyanine (Pc) coatings (where metal is Zn, Cu, Fe, Co, Ni, Mn) are systematically evaluated for their corrosion inhibition efficiency. The study demonstrates that the free base Phthalocyanine coatings are superior corrosion inhibitors for Cu surface in HCl with a corrosion inhibition efficiency of 88\% as compared to its metal counterparts. A detailed and indepth study involving concerted electrochemical polarisation, impedance measurements at various concentrations of HCl assert the superior corrosion inhibition efficiency of free base Pc coatings as compared to its metal counterparts. Underlying factors/interface chemistry contributing to it is brought out using first principle based studies. First principles based computational studies establish that superior corrosion inhibition ability of free base phthalocyanine molecule is attributed to its innate binding ability with copper surface and its better inter-molecular packing. Thus, the theoretical adsorption trends of various studied phthalocyanine molecules while clearly following the experimental corrosion inhibition efficiency trends undermine the importance of contribution of chelating factors for the formation of a stable and efficient corrosion inhibition coating on a surface and that the adhesion/adsorption strength of a molecule correlates directly to its corrosion inhibition efficiency. The experimental observations are further substantiated through FE-SEM, EDAX and XPS studies. The corrosion inhibition efficiency of free base phthalocyanine is followed by its zinc based counterpart at 85\%.

}, keywords = {Copper surface, Corrosion inhibitors, DFT studies, Impedance, Phthalocyanine coatings}, issn = {0927-7757}, doi = {10.1016/j.colsurfa.2022.129138}, author = {Samal, Pragnya Paramita and Dekshinamoorthy, Amuthan and Arunachalam, Shivakami and Vijayaraghavan, Saranyan and Krishnamurty, Sailaja} } @article {48099, title = {Green transformation of CO2 to ethanol using water and sunlight by the combined effect of naturally abundant red phosphorus and Bi2MoO6}, journal = {Energy \& Environmental Science}, volume = {15}, year = {2022}, month = {MAY }, pages = {1967-1976}, type = {Article}, abstract = {

Direct photocatalytic conversion of CO2 to ethanol remains a scientific challenge because of the sluggish kinetics of C-C coupling and complex multielectron transfer processes. To achieve a green transformation of CO2 to C1+ products using naturally abundant sunlight and water requires the smart design of an efficient catalyst by selecting the right combination of atoms either in elemental or in compound form. Herein, we report a composite photocatalyst composed of earth abundant red phosphorus (RP) in nano-sheet morphology decorated with Bi2MoO6 nano-particles. The composite synthesised by a facile ultrasonication method produces 51.8 mu mol g(-1) h(-1) of ethanol from CO2. The ability of RP for the conversion of CO2 to C1 has been altered by the introduction of Bi2MoO6. In situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and Kinetic Isotopic Effect (KIE) analysis shed light on the mechanistic pathway, which propose that the presence of Bi-Mo dual sites play a crucial role in the C-C coupling toward the formation of ethanol. Spectroscopic evidence and isotope labeling experiments suggest that the intermediate OCH3* is the key active species for ethanol formation via self-coupling followed by proton transfer.

}, issn = {1754-5692}, doi = {10.1039/d1ee02976b}, author = {Das, Risov and Das, Kousik and Ray, Bitan and Vinod, Chathakudath P. and Peter, Sebastian C.} } @article {46653, title = {Homo and heterologous expression of the HpPKS2 gene in Hypericum perforatum and Bacopa monnieri}, journal = {Plant Cell Tissue and Organ Culture}, year = {2022}, month = {JAN}, pages = {215-215}, type = {Article}, abstract = {

Hypericum perforatum has been known to produce hypericin and hyperforin that are used in treating mild to moderate depression. The HpPKS2 (H. perforatum polyketide synthase 2) gene is assumed to play a role in hypericin biosynthesis. The HpPKS2 gene was overexpressed in homologous H. perforatum in vitro grown plants through Agrobacterium tumefaciens-mediated genetic transformations. It leads to the establishment of seven glass house acclimatized transgenic lines. Among them, the HP12 transgenic plant showed 9.8 fold enhancement in hypericin content (379.4 +/- 10.3 mu g/g dry wt) followed by 3-fold in HP41 (117.1 +/- 4.5 mu g/g dry wt) as compared to control plants. This was further supported by the real-time PCR studies where it registered up to 5 fold enhancement of HpPKS2 gene expression. On the other hand, the heterologous expression of the HpPKS2 gene in Bacopa monnieri resulted in the establishment of five transgenic plant clones that were successfully acclimatized under glasshouse conditions. Among them, BT4 was found to be very slow-growing. The BT3 line showed maximum expression of the HpPKS2 gene which surprisingly also upregulates the expression of the other metabolic pathway genes of B. monierri namely isopentyl- diphosphate delta isomerase (IDDI), squaline synthase (SQS) and acetyl CoA C acetyltransferase (AA). The HPLC analysis in the heterologous system revealed the maximum production of bacopaside I (9.86 +/- 1.0 mg/g dry wt), bacopaside II (5.89 +/- 0.9 mg/g dry wt) and bacopasaponin C (3.59 +/- 0.3 mg/g dry wt) by transgenic lines BT8, BT3 and BT4, respectively. This enhancement in bacopaside I, bacopaside II and bacopasaponin C production was more than 26-fold, 5-fold and 21-fold, respectively in comparison to the control non transformed plants. Key message Overexpression of the HpPKS2 gene in H. perforatum led to higher hypericin content in the native system while its expression in the heterologous system i.e. B. monnieri also improves bacopaside I, bacopaside II and bacopasaponin C production.

}, keywords = {Agrobacterium tumefacience, Bacopa monnieri, Bacopasides, Heterologous expression, HpPKS2, Hypericin, Hypericum perforatum, Transgenics}, issn = {0167-6857}, doi = {10.1007/s11240-020-01965-5}, author = {Khan, Shamshad Ahmad and Verma, Priyanka and Parasharami, Varsha A.} } @article {48210, title = {Improvement in oxygen evolution performance of NiFe layered double hydroxide grown in the presence of 1T-Rich MoS2}, journal = {ACS Applied Materials \& Interfaces}, volume = {14}, year = {2022}, month = {JUL}, pages = {31951-31961}, type = {Article}, abstract = {

NiFe layered double hydroxide (NiFe LDH) grown in the presence of MoS2 (rich in 1T phase) shows exceptional performance metrics for alkaline oxygen evolution reaction (OER) in this class of composites. The as-prepared NiFe LDH/MoS2 composite (abbreviated as MNF) exhibits a low overpotential (eta(10)) of 190 mV; a low Tafel slope of 31 mV dec(-1); and more importantly, a high stability in its performance manifested by the delivery of current output for 45 h. It is important to note that this could be achieved with an exceedingly low loading of 0.14 mg cm(-2). The mass activity of this composite (97 A g(-1)) is about 14 times greater than that of the conventional RuO2 (7 A g(-1) ) at eta = 200 mV. When normalized with respect to the total metal content, a mass activity of 1000 A g(-1) (eta = 300 mV) was achieved. Impedance analysis further reveals that the significant reduction in charge-transfer resistance and hence high current density (5 times greater as compared to NiFe LDH at eta = 300 mV) observed for MNF is associated with interfacial adsorption kinetics of intermediates (R-1). Significant enhancement in the intrinsic activity of MNF over LDH has been observed through normalization of current with the electrochemically active surface area. Computational studies suggest that the Ni centers in the composite act as the active sites for OER, which is well-corroborated with the observed postreaction appearance of Ni3+ species.

}, keywords = {Impedance, LDH-MoS2 hybrid electrocatalyst, mass activity, OER, overpotential}, issn = {1944-8244}, doi = {10.1021/acsami.2c06210}, author = {Chakraborty, Soumita and Marappa, Shivanna and Agarwal, Sakshi and Bagchi, Debabrata and Rao, Ankit and Vinod, Chathakudath P. and Peter, Sebastian C. and Singh, Abhishek and Eswaramoorthy, Muthusamy} } @article {48132, title = {Incorporating conducting polypyrrole into a polyimide COF for carbon-free ultra-high energy supercapacitor}, journal = {Advanced Energy Materials}, volume = {12}, year = {2022}, month = {SEP}, pages = {2200754}, type = {Article}, abstract = {

Redox-active covalent organic frameworks (COFs) store charges but possess inadequate electronic conductivity. Their capacitive action works by storing H+ ions in an acidic electrolyte and is typically confined to a small voltage window (0-1 V). Increasing this window means higher energy and power density, but this risks COF stability. Advantageously, COF{\textquoteright}s large pores allow the storage of polarizable bulky ions under a wider voltage thus reaching higher energy density. Here, a COF-electrode-electrolyte system operating at a high voltage regime without any conducting carbon or redox active oxides is presented. Conducting polypyrrole (Ppy) chains are synthesized within a polyimide COF to gain electronic conductivity (approximate to 10 000-fold). A carbon-free quasi-solid-state capacitor assembled using this composite showcases high pseudo-capacitance (358 mF cm(-2)@1 mA cm(-2)) in an aqueous gel electrolyte. The synergy among the redox-active polyimide COF, polypyrrole and organic electrolytes allows a wide-voltage window (0-2.5 V) leading to high energy (145 mu Wh cm(-2)) and power densities (4509 mu W cm(-2)). Amalgamating the polyimide-COF and the polypyrrole as one material minimizes the charge and mass transport resistances. Computation and experiments reveal that even a partial translation of the modules/monomers intrinsic electronics to the COF imparts excellent electrochemical activity. The findings unveil COF-confined polymers as carbon-free energy storage materials.

}, keywords = {carbon free capacitors, cation-anion co-storage, conductivity, high energy capacitors, polypyrrole doped COFs}, issn = {1614-6832}, doi = {10.1002/aenm.202200754}, author = {Haldar, Sattwick and Rase, Deepak and Shekhar, Pragalbh and Jain, Chitvan and Vinod, Chathakudath Prabhakaran and Zhang, En and Shupletsov, Leonid and Kaskel, Stefan and Vaidhyanathan, Ramanathan} } @article {48356, title = {Influence of ice templating on oxygen reduction catalytic activity of metal-free heteroatom-doped mesoporous carbon derived from polypyrrole for zinc-air batteries}, journal = {Energy Technology}, volume = {10}, year = {2022}, month = {DEC}, type = {Article}, abstract = {

The development of highly active, cost-effective, and durable, noble metal-free oxygen reduction electrocatalysts is inevitable for the full-fledged implementation of fuel cells and zinc-air batteries. This work reports the synthesis of heteroatom (N, P, S)-doped metal-free mesoporous carbon-based electrocatalyst derived from polypyrrole by combining the ice templating, freeze-drying, and carbonization processes. The correlation between the structure and electrochemical activity of the polypyrrole-derived carbon-based electrocatalyst in the presence and absence of ice templating is investigated. The optimized electrocatalyst, aided by the ice-templating and freeze-drying step, shows an onset and half-wave potential (E-1/2) of 0.94 and 0.78 V vs reversible hydrogen electrode, respectively, in an alkaline electrolyte (0.1 m KOH). Later, the application of the optimized electrocatalyst is demonstrated in a primary zinc-air battery (ZAB) cell. The results prove that the ZAB device performance based on the homemade catalyst is on par with that of the state-of-the-art Pt/C cathode. The catalyst performance is correlated with the heteroatom doping and the enhanced porosity of the sample benefitted from ice templating. Ultimately, this work depicts a facile and rational synthesis of a truly metal-free electrocatalyst for the primary ZABs that can be a potential replacement for state-of-the-art systems.

}, keywords = {metal-free electrocatalysts, oxygen reduction reaction, zinc-air batteries}, issn = {2194-4288}, doi = {10.1002/ente.202200840}, author = {Kurian, Maria and Ghosh, Meena and Vijayakumar, Vidyanand and Puthiyaveetil, Priyanka Pandinhare and Torris, Arun and Kurungot, Sreekumar} } @article {48188, title = {Influence of support textural property on CO2 to methane activity of Ni/ SiO2 catalysts}, journal = {Applied Catalysis B-Environmental}, volume = {317}, year = {2022}, month = {NOV}, pages = {121692}, type = {Article}, abstract = {

In this work, we elucidated the role of physicochemical textural properties of inert support on the catalyst ac-tivity by impregnating Ni on ordered mesoporous silica (SBA-15 and MCM-41) and non-mesoporous silica (nMPS). The catalyst Ni/SBA-15 exhibited the best CO2 conversion (83\%) and product selectivity (99.9 \%) followed by Ni/MCM-41 and the least by Ni/nMPS. The difference in the nature of the catalyst, degree of nanoparticle distribution and nanoparticle encapsulation by different silica support were studied by N2 adsorption-desorption and X-ray photoelectron spectroscopy (XPS) experiments. The Operando Diffused Reflec-tance Infrared Fourier Transform Spectroscopy were used to understand the variance in reaction pathway which is accredited to the textural properties of the support. The SBA-15 supported Ni catalyst followed dissociative CO pathway while MCM-41 and nMPS reacted through associative formate mechanism as major pathway. These findings provide a novel perspective on CO2 hydrogenation over Ni-silica, allowing us to tune both activity and selectivity.

}, keywords = {CO2 methanation, DRIFTS, Mesoporous silica support, Textural properties}, issn = {0926-3373}, doi = {10.1016/j.apcatb.2022.121692}, author = {Cherevotan, Arjun and Ray, Bitan and Churipard, Sathyapal R. and Kaur, Komalpreet and Gautam, Ujjal K. and Vinod, Chathakudath P. and Peter, Sebastian C.} } @article {48087, title = {Instabilities as the origin of large-area self-assembled and aligned organic semiconductor nanocrystals}, journal = {ACS Applied Electronic Materials}, volume = {4}, year = {2022}, month = {APR}, pages = {1815-1822}, type = {Article}, abstract = {

Aligned nanocrystals of organic semiconductors (OSCs) are highly desirable for electronic devices and biomedical and photonic applications. Solution-based wet processing routes have the potential to produce aligned nanocrystals over large areas in small time frames. Herein, we demonstrate that by optimizing the hydrodynamic evaporative processes, controlled long-range crystalline assemblies of OSCs can be achieved (longest nanocrystal similar to 3 mm) purely through physical processes: namely, from fingering instabilities. Self-assembly is achieved here without strong noncovalent interactions such as hydrogen-bonding interactions. Experimentally our approach involves just placing a drop of a solution on an inclined substrate. Nanocrystals with widths of 300-800 nm and lengths of millimeters (length/width aspect ratios \>10(5)) are formed in less than 2-8 s. A hydrazine chemiresistive sensor based on the aligned crystalline patterns show unprecedented responsivity (similar to 10(-6)), 2 orders greater than those of stick-slip patterns. Finally, experimental parameters that need optimization to achieve nanocrystal patterns are investigated in detail and pointers to fabricate such OSC nanocrystals are provided.

}, keywords = {aligned fibers, diketopyrrolopyrrole, fingering instability, nanocrystal arrays, naphthalenediimide, organic semiconductors}, doi = {10.1021/acsaelm.2c00061}, author = {Venugopalan, Vijay and Jain, Bhanprakash and Mahale, Rajashree Y. and Subramani, Kumar and Krishnamoorthy, Kothandam} } @article {48148, title = {Isoeugenol affects expression pattern of conidial hydrophobin gene RodA and transcriptional regulators MedA and SomA responsible for adherence and biofilm formation in Aspergillus fumigatus}, journal = {Archives of Microbiology}, volume = {204}, year = {2022}, month = {APR}, pages = {214}, type = {Article}, abstract = {

Aspergillus fumigatus is one of the major pathogenic fungal species, causing life-threatening infections. Due to a limited spectrum of available antifungals, exploration of new drug targets as well as potential antifungal molecules has become pertinent. Rodlet layer plays an important role in adherence of fungal conidia to hydrophobic cell surfaces in host, which also leads to A. fumigatus biofilm formation, contributing factor to fungal pathogenicity. From decades, natural sources have been known for the development of new active molecules. The present study investigates effect of isoeugenol on genes responsible for hydrophobins (RodA), adhesion as well as biofilm formation (MedA and SomA) of A. fumigatus. Minimum inhibitory concentrations (MIC and IC50) of isoeugenol against A. fumigatus were determined using broth microdilution assay. The IC50 results showed reduced hydrophobicity and biofilm formation as well as eradication after treatment with the compound and electron micrograph data corroborated these findings. The qRT-PCR showed a significant downregulation of genes RodA, MedA, SomA and pksP involved in hydrophobicity and biofilm formation. SwissADME studies potentiated drug-like propensity for isoeugenol which formed four hydrogen bonds with low binding energy (- 4.54 kcal/mol) at the catalytic site of RodA protein studied via AutoDock4. Hence, the findings conclude that isoeugenol inhibits conidial hydrophobicity and biofilm formation of A. fumigatus and further investigations are warranted in this direction.

}, keywords = {Aspergillus fumigatus, Hydrophobicity, Isoeugenol, Transcription regulators, Virulence}, issn = {0302-8933}, doi = {10.1007/s00203-022-02817-w}, author = {Gupta, Lovely and Sen, Pooja and Bhattacharya, Asish K. and Vijayaraghavan, Pooja} } @article {48154, title = {Luminescent magnesium complexes with intra- and inter-ligand charge transfer}, journal = {Chemical Communications}, volume = {58}, year = {2022}, month = {OCT}, pages = {11843-11846}, type = {Article}, abstract = {

Herein, we report two 2,2{\textquoteright}-pyridylpyrrolide (PyPyrH) ligand supported magnesium complexes (1 and 2), which demonstrate bright luminescence with a quantum yield of 22\% and 14\% in the solid state, respectively. Theoretical calculations reveal that their emissive properties originate from the intra- and inter-ligand charge transfer.

}, issn = {1359-7345}, doi = {10.1039/d2cc04142a}, author = {Kumar, Rohit and Pahar, Sanjukta and Chatterjee, Joy and Dash, Soumya Ranjan and Gonnade, Rajesh G. and Vanka, Kumar and Sen, Sakya S.} } @article {48236, title = {Machine learning-based approach to determine infection status in recipients of BBV152 (Covaxin) whole-virion inactivated SARS-CoV-2 vaccine for serological surveys}, journal = {Computers in Biology and Medicine}, volume = {146}, year = {2022}, month = {JUL}, pages = {105419}, type = {Article}, abstract = {

Data science has been an invaluable part of the COVID-19 pandemic response with multiple applications, ranging from tracking viral evolution to understanding the vaccine effectiveness. Asymptomatic breakthrough infections have been a major problem in assessing vaccine effectiveness in populations globally. Serological discrimination of vaccine response from infection has so far been limited to Spike protein vaccines since whole virion vaccines generate antibodies against all the viral proteins. Here, we show how a statistical and machine learning (ML) based approach can be used to discriminate between SARS-CoV-2 infection and immune response to an inactivated whole virion vaccine (BBV152, Covaxin). For this, we assessed serial data on antibodies against Spike and Nucleocapsid antigens, along with age, sex, number of doses taken, and days since last dose, for 1823 Covaxin recipients. An ensemble ML model, incorporating a consensus clustering approach alongside the support vector machine model, was built on 1063 samples where reliable qualifying data existed, and then applied to the entire dataset. Of 1448 self-reported negative subjects, our ensemble ML model classified 724 to be infected. For method validation, we determined the relative ability of a random subset of samples to neutralize Delta versus wild-type strain using a surrogate neutralization assay. We worked on the premise that antibodies generated by a whole virion vaccine would neutralize wild type more efficiently than delta strain. In 100 of 156 samples, where ML prediction differed from self-reported uninfected status, neutralization against Delta strain was more effective, indicating infection. We found 71.8\% subjects predicted to be infected during the surge, which is concordant with the percentage of sequences classified as Delta (75.6\%-80.2\%) over the same period. Our approach will help in real-world vaccine effectiveness assessments where whole virion vaccines are commonly used.

}, keywords = {BBV152, Covaxin, COVID-19, Ensemble methods, Infection, machine learning, SARS-CoV-2}, issn = {0010-4825}, doi = {10.1016/j.compbiomed.2022.105419}, author = {Singh, Prateek and Ujjainiya, Rajat and Prakash, Satyartha and Naushin, Salwa and Sardana, Viren and Bhatheja, Nitin and Singh, Ajay Pratap and Barman, Joydeb and Kumar, Kartik and Gayali, Saurabh and Khan, Raju and Rawat, Birendra Singh and Tallapaka, Karthik Bharadwaj and Anumalla, Mahesh and Lahiri, Amit and Kar, Susanta and Bhosale, Vivek and Srivastava, Mrigank and Mugale, Madhav Nilakanth and Pandey, C. P. and Khan, Shaziya and Katiyar, Shivani and Raj, Desh and Ishteyaque, Sharmeen and Khanka, Sonu and Rani, Ankita and Promila and Sharma, Jyotsna and Seth, Anuradha and Dutta, Mukul and Saurabh, Nishant and Veerapandian, Murugan and Venkatachalam, Ganesh and Bansal, Deepak and Gupta, Dinesh and Halami, Prakash M. and Peddha, Muthukumar Serva and Veeranna, Ravindra P. and Pal, Anirban and Singh, Ranvijay Kumar and Anandasadagopan, Suresh Kumar and Karuppanan, Parimala and Rahman, Syed Nasar and Selvakumar, Gopika and Venkatesan, Subramanian and Karmakar, Malay Kumar and Sardana, Harish Kumar and Kothari, Anamika and Parihar, Devendra Singh and Thakur, Anupma and Saifi, Anas and Gupta, Naman and Singh, Yogita and Reddu, Ritu and Gautam, Rizul and Mishra, Anuj and Mishra, Avinash and Gogeri, Iranna and Rayasam, Geethavani and Padwad, Yogendra and Patial, Vikram and Hallan, Vipin and Singh, Damanpreet and Tirpude, Narendra and Chakrabarti, Partha and Maity, Sujay Krishna and Ganguly, Dipyaman and Sistla, Ramakrishna and Balthu, Narender Kumar and Kumar, Kiran A. and Ranjith, Siva and Kumar, B. Vijay and Jamwal, Piyush Singh and Wali, Anshu and Ahmed, Sajad and Chouhan, Rekha and Gandhi, Sumit G. and Sharma, Nancy and Rai, Garima and Irshad, Faisal and Jamwal, Vijay Lakshmi and Paddar, Masroor Ahmad and Khan, Sameer Ullah and Malik, Fayaz and Ghosh, Debashish and Thakkar, Ghanshyam and Barik, S. K. and Tripathi, Prabhanshu and Satija, Yatendra Kumar and Mohanty, Sneha and Khan, Md Tauseef and Subudhi, Umakanta and Sen, Pradip and Kumar, Rashmi and Bhardwaj, Anshu and Gupta, Pawan and Sharma, Deepak and Tuli, Amit and Chaudhuri, Saumya Ray and Krishnamurthi, Srinivasan and Prakash, L. and Rao, V. Ch and Singh, B. N. and Chaurasiya, Arvindkumar and Chaurasiya, Meera and Bhadange, Mayuri and Likhitkar, Bhagyashree and Mohite, Sharada and Patil, Yogita and Kulkarni, Mahesh and Joshi, Rakesh and Pandya, Vaibhav and Mahajan, Sachin and Patil, Amita and Samson, Rachel and Vare, Tejas and Dharne, Mahesh and Giri, Ashok and Mahajan, Sachin and Paranjape, Shilpa and Sastry, G. Narahari and Kalita, Jatin and Phukan, Tridip and Manna, Prasenjit and Romi, Wahengbam and Bharali, Pankaj and Ozah, Dibyajyoti and Sahu, RaviKumar and Dutta, Prachurjya and Singh, Moirangthem Goutam and Gogoi, Gayatri and Tapadar, Yasmin Begam and Babu, Elapavalooru V. S. S. K. and Sukumaran, Rajeev K. and Nair, Aishwarya R. and Puthiyamadam, Anoop and Valappil, Prajeesh Kooloth and Prasannakumari, Adrash Velayudhan Pillai and Chodankar, Kalpana and Damare, Samir and Agrawal, Ved Varun and Chaudhary, Kumardeep and Agrawal, Anurag and Sengupta, Shantanu and Dash, Debasis} } @article {48357, title = {Maltooligosaccharide forming amylases and their applications in food and pharma industry}, journal = {Journal of Food Science and Technology-Mysore}, volume = {59}, year = {2022}, month = {OCT}, pages = {3733-3744}, type = {Review}, abstract = {

Oligosaccharides are low molecular weight carbohydrates with a wide range of health benefits due to their excellent bio-preservative and prebiotic properties. The popularity of functional oligosaccharides among modern consumers has resulted in impressive market demand. Organoleptic and prebiotic properties of starch-derived oligosaccharides are advantageous to food quality and health. The extensive health benefits of oligosaccharides offered their applications in the food, pharmaceuticals, and cosmetic industry. Maltooligosaccharides and isomaltooligosaccharides comprise 2-10 glucose units linked by alpha-1-4 and alpha-1-6 glycoside bonds, respectively. Conventional biocatalyst-based oligosaccharides processes are often multi-steps, consisting of starch gelatinization, hydrolysis and transglycosylation. With higher production costs and processing times, the current demand cannot meet on a large-scale production. As a result, innovative and efficient production technology for oligosaccharides synthesis holds paramount importance. Malto-oligosaccharide forming amylase (EC 3.2.1.133) is one of the key enzymes with a dual catalytic function used to produce oligosaccharides. Interestingly, Malto-oligosaccharide forming amylase catalyzes glycosidic bond for its transglycosylation to its inheritance hydrolysis and alternative biocatalyst to the multistep technology. Genetic engineering and reaction optimization enhances the production of oligosaccharides. The development of innovative and cost-effective technologies at competitive prices becomes a national priority.

}, keywords = {Glycosyl hydrolases, Isomaltooligosaccharides, Maltooligosaccharide, Maltooligosaccharide forming amylase, Transglycosylation}, issn = {0022-1155}, doi = {10.1007/s13197-021-05262-7}, author = {Shinde, Vidhya K. and Vamkudoth, Koteswara Rao} } @article {47999, title = {Manganese-catalyzed C(sp(2))-H alkylation of indolines and arenes with unactivated alkyl bromides}, journal = {Chemistry-an Asian Journal}, volume = {17}, year = {2022}, month = {MAY}, pages = {e202200103}, type = {Article}, abstract = {

Selective C(sp(2))-H bond alkylation of indoline, carbazole and (2-pyridinyl)arenes with unactivated alkyl bromides is achieved using MnBr2 catalyst in the absence of an external ligand. The alkylation uses a simple LiHMDS base and avoids the necessity of Grignard reagent, unlike other Mn-catalyzed C-H functionalization. This reaction proceeded either through a five- or a less-favored six-membered metallacycle, and tolerated diverse functionalities, including alkenyl, alkynyl, silyl, aryl ether, pyrrolyl, indolyl, carbazolyl and alkyl bearing fatty alcohol and polycyclic-steroid moieties. Alkylation follows a single electron transfer (SET) pathway involving 1e oxidative addition of alkyl bromide and a rate-limiting C-H metalation.

}, keywords = {Alkylation, C-H activation, indoline, ligand-free, manganese}, issn = {1861-4728}, doi = {10.1002/asia.202200103}, author = {Verma, Suryadev K. and Punji, Benudhar} } @article {48202, title = {Mechanistic insight into differential interactions of iron oxide nanoparticles with native, glycated albumin and their effect on erythrocytes parameters}, journal = {International Journal of Biological Macromolecules}, volume = {212}, year = {2022}, month = {JUL }, pages = {232-247}, type = {Article}, abstract = {

Nanoparticles and protein bioconjugates have been studied for multiple biomedical applications. We sought to investigate the interaction and structural modifications of bovine serum albumin (BSA) with iron oxide nanoparticles (IONPs). The IONPs were green synthesized using E. crassipes aqueous leaf extract following characterization using transmission electron microscopy, energy dispersive X-ray analysis and X-ray diffraction. Two different concentrations of native/glycated albumin (0.5 and 1.5 mg/ml) with IONPs were allowed to interact for 1 h at 37 degrees C. Glycation markers, protein modification markers, cellular antioxidant, and hemolysis studies showed structural modifications and conformational changes in albumin due to the presence of IONPs. UV-visible absorbance resulted in hyperchromic and bathochromic effects of IONPs-BSA conjugates. Fluorescence measurements of tyrosine, tryptophan, advanced glycated end products, and ANS binding assay were promising and quenching effects proved IONPs-BSA conjugate formation. In FTIR of BSA-IONPs, transmittance was increased in amide A and B bands while decreased in amide I and II bands. In summary, native PAGE, HPLC, and FTIR analysis displayed a differential behaviour of IONPs with native and glycated BSA. These results provided an understanding of the interaction and structural modifications of glycated and native BSA which may provide fundamental repercussions in future studies.

}, keywords = {Albumin, Glycation, iron oxide nanoparticles}, issn = {0141-8130}, doi = {10.1016/j.ijbiomac.2022.05.106}, author = {Nisar, Akib and Ajabia, Devangi K. and Agrawal, Sanskruthi B. and Varma, Sanjana and Chaudhari, Bhushan P. and Tupe, Rashmi S.} } @article {47899, title = {Mechanistically guided one pot synthesis of phosphine-phosphite and its implication in asymmetric hydrogenation}, journal = {European Journal of Organic Chemistry}, volume = {2022}, year = {2022}, month = {JAN}, pages = {e202101447}, type = {Article}, abstract = {

Although hybrid bidentate ligands are known to yield highly enantioselective products in asymmetric hydrogenation (AH), synthesis of these ligands is an arduous process. Herein, a one pot, atom-economic synthesis of a hybrid phosphine-phosphite (L1) is reported. After understanding the reactivity difference between an 0-nucleophile versus C-nucleophile, one pot synthesis of Senphos (L1) was achieved (72\%). When L1 was treated with [Rh], P-31 NMR revealed bidentate coordination to Rh. Senphos, in the presence of rhodium, catalyzes the AH of Methyl-2-acetamido-3-phenylacrylate and discloses an unprecedented turn over frequency of 2289, along with excellent enantio-selectivity (92\%). The generality is demonstrated by hydrogenating an array of alkenes. The AH operates under mild conditions of 1-2 bar H-2 pressure, at room temperature. The practical relevance of Ll is demonstrated by scaling-up the reaction to 1 g and by synthesizing DOPA, a drug widely employed for the treatment of Parkinson{\textquoteright}s disease. Computational insights indicate that the R isomer is preferred by 3.8 kcal/mol over the S isomer.

}, keywords = {asymmetric hydrogenation, catalysis, DOPA synthesis, One pot synthesis, Phosphine-phosphite ligand}, issn = {1434-193X}, doi = {10.1002/ejoc.202101447}, author = {Sen, Anirban and Kumar, Rohit and Pandey, Swechchha and Raj, K. Vipin and Kumar, Pawan and Vanka, Kumar and Chikkali, Samir H.} } @article {48157, title = {Morphology-tuned Pt3Ge accelerates water dissociation to industrial-standard hydrogen production over a wide pH range}, journal = {Advanced Materials}, volume = {34}, year = {2022}, month = {JUL}, pages = {2202294}, type = {Article}, abstract = {

The discovery of novel materials for industrial-standard hydrogen production is the present need considering the global energy infrastructure. A novel electrocatalyst, Pt3Ge, which is engineered with a desired crystallographic facet (202), accelerates hydrogen production by water electrolysis, and records industrially desired operational stability compared to the commercial catalyst platinum is introduced. Pt3Ge-(202) exhibits low overpotential of 21.7 mV (24.6 mV for Pt/C) and 92 mV for 10 and 200 mA cm(-2) current density, respectively in 0.5 m H2SO4. It also exhibits remarkable stability of 15 000 accelerated degradation tests cycles (5000 for Pt/C) and exceptional durability of 500 h (@10 mA cm(-2)) in acidic media. Pt3Ge-(202) also displays low overpotential of 96 mV for 10 mA cm(-2) current density in the alkaline medium, rationalizing its hydrogen production ability over a wide pH range required commercial operations. Long-term durability (\>75 h in alkaline media) with the industrial level current density (\>500 mA cm(-2)) has been demonstrated by utilizing the electrochemical flow reactor. The driving force behind this stupendous performance of Pt3Ge-(202) has been envisaged by mapping the reaction mechanism, active sites, and charge-transfer kinetics via controlled electrochemical experiments, ex situ X-ray photoelectron spectroscopy, in situ infrared spectroscopy, and in situ X-ray absorption spectroscopy further corroborated by first principles calculations.

}, keywords = {Electrochemistry, hydrogen production, intermetallics, water electrolysis}, issn = {0935-9648}, doi = {10.1002/adma.202202294}, author = {Mondal, Soumi and Sarkar, Shreya and Bagchi, Debabrata and Das, Tisita and Das, Risov and Singh, Ashutosh Kumar and Prasanna, Ponnappa Kechanda and Vinod, C. P. and Chakraborty, Sudip and Peter, Sebastian C.} } @article {48415, title = {Noble-metal-free heterojunction photocatalyst for selective CO2 reduction to methane upon induced strain relaxation}, journal = {ACS Catalysis}, volume = {12}, year = {2022}, month = {JAN }, pages = {687-697}, type = {Article}, abstract = {

Sunlight-driven CO2 hydrogenation has drawn tremendous attention. However, selective CH4 formation via CO2 photoreduction is very challenging. Herein, we report a metal oxide semiconductor heterojunction consisting of BiVO4 and WO3 as a photocatalyst for the efficient conversion of carbon dioxide (CO2) selectively to methane (105 mu mol g(-1) h(-1)) under visible light in the absence of a sacrificial agent. Wise selection of the reaction medium and the strategically tuned heterojunction upon strain relaxation suppresses the competitive hydrogen generation reaction. The detailed photophysical, photoelectrochemical, and X-ray absorption spectroscopy studies pointed to the Z-scheme mechanism of electron transfer, which favors superior electron and hole separation compared to the individual components of the composite catalyst and other well-known photocatalysts reported for CO2 reduction. The observations are further corroborated by experimental diffuse reflectance infrared Fourier transform spectroscopy and theoretical density-functional theory calculations, which reveal that the heterojunction has a lower free-energy barrier for CO2 conversion to CH4 due to the larger stabilization of the *CH2O intermediate on the strain-relaxed heterojunction surface, in comparison to the pristine BiVO4 surface. The present work provides fundamental insights for constructing high-performance heterojunction photocatalysts for the selective conversion of CO2 to desired chemicals and fuels.

}, keywords = {CO2 reduction, heterostructure, methane, Photocatalysis, Z-scheme}, issn = {2155-5435}, doi = {10.1021/acscatal.1c04587}, author = {Das, Risov and Sarkar, Shreya and Kumar, Ritesh and Ramarao, Seethiraju D. and Cherevotan, Arjun and Jasil, Mohammed and Vinod, Chathakudath P. and Singh, Abhishek Kumar and Peter, Sebastian C.} } @article {47593, title = {Novel lignin as natural-biodegradable binder for various sectors-A review}, journal = {Journal of Applied Polymer Science}, volume = {139}, year = {2022}, month = {APR }, pages = {e51951}, type = {Review}, abstract = {Lignin functions as an essential polymer in plants that forms the plant body{\textquoteright}s structural framework. The natural glue holds the cellulosic fibers together in the plant body, thereby providing rigidity and strength. Despite this, lignin shows promising relevance for biomaterial production due to its abundance, nontoxic nature and biodegradability. Considerably, adhesive components were derived from petroleum, which is increasingly more expensive. Hence, lignin, the natural glue in plant materials, gained much popularity because of its phenolic nature, making it an attractive substitute for adhesives. Lignin-based binders are produced through phenols substitution in phenol-formaldehyde resins with lignin due to their similar structural framework. Many researchers have confirmed the multifunctional applications of lignin, such as wood adhesive in fiber board, plywood and particleboard, a binder in printed wiring boards, abrasive tools, epoxy asphalts, epoxy wood composites, 3D printing, adhesive hydrogels, soil suppressants, lignocellulosic paper and coatings. This review presents a comprehensive description of the utilization of lignin-based binders for different applications. The present work highlights the discussion on the various methods by which lignin can be used to replace synthetic binders. This review focuses on global research work introducing lignin in different chemical adhesives for a more cost-effective and less harmful alternative.}, keywords = {binder, biodegradable, lignin, multifunctional}, issn = {0021-8995}, doi = {10.1002/app.51951}, author = {Mili, Medha and Hashmi, Sayed Azhar Rasheed and Ather, Madeeha and Hada, Vaishnavi and Markandeya, Nishant and Kamble, Sanjay and Mohapatra, Mamata and Rathore, Sanjai Kumar Singh and Srivastava, Avanish Kumar and Verma, Sarika} } @article {47777, title = {One-pot concurrent biosynthesis of biphasic CuxO (cuprous and cupric oxide) nanoparticles using leaf extract of Eichhornia crassipes and investigation of their potent healthcare applications}, journal = {Emergent Materials}, year = {2022}, month = {FEB}, type = {Article}, abstract = {Eichhornia crassipes, an aquatic weed, has been used for the one-pot quick synthesis of cuprous and cupric oxide nanoparticles in this report. The identification and validation of the formed nanoparticles were successfully done by sophisticated characterization techniques such as UV{\textendash}visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. Their biomedical interventions were assessed by their antioxidant and anticancer activities. The synthesized nanoparticles have a spherical morphology with an average diameter of 10~nm. Antioxidant assay performed showed an increasing trend in a dose-dependent manner with the percentage radical scavenging activity up to 94.70\% at a much higher concentration of 1000~{\textmu}g/ml. The antioxidant potential at such higher concentration is suspected to invoke a change in the cytotoxic potential of the nanoparticles which is then verified by the MTT assay. A significant cytotoxic activity against HeLa (cervical cancer) and HCT 116 (colorectal carcinoma) cell lines was detected with noted IC50 values of 17.17 and 13.70~{\textmu}g/ml respectively. The conclusive findings obtained are enough to substantiate the use of these nanoparticles in biomedical areas specifically in anticancer treatment due to their high toxicities. The hazards imposed by Eichhornia crassipes can be alleviated by using them as biofactories for the synthesis of a variety of nanomaterials. This helps in curbing the water pollution issues as well as the developing synthesis protocols for robust and stable nanoparticles.}, isbn = {2522-574X}, doi = {10.1007/s42247-022-00347-1}, url = {https://doi.org/10.1007/s42247-022-00347-1}, author = {Moudgil, Aliesha and Varma, Sanjana and Shinde, Manish D. and Vamkudoth, Koteswara Rao and Sarkar, Dhiman M. and Shende, Rajnigandha A. and Amalnerkar, Dinesh and Chaudhari, Bhushan P.} } @article {48427, title = {Pectinase production by aspergillus niger and its applications in fruit juice clarification}, journal = {Journal of Pure and Applied Microbiology}, volume = {16}, year = {2022}, month = {NOV}, pages = {2724-2737}, type = {Article}, abstract = {

Pectinases (EC 3.2.1.15) are a class of enzymes that catalyze the depolymerization or de-esterification reactions that degrade pectic substances. In the present study, we have isolated the\ Aspergillus niger\ strain from soil samples, in India and evaluated pectinase production. The highest pectinase producing\ A. niger\ strain was further evaluated and optimized with various agricultural wastes. Plackett-Burman design (PBD) and Central composite design {\textquoteleft}(CCD){\textquoteright} were used to determine the best parameters for maximum pectinase production. Pectinase activity was increased to 99.21 U/ml after optimizing the production medium using PBD and CCD statistical analysis. A positive correlation of pectinase activity between predicted (112.65 U/ml) and experimental (99.21 U/ml with SD=0.005) optimum was observed. Maximum pectinase was produced by\ A. niger\ under submerged fermentation, utilizing orange peel, which is a cost-effective, adaptable, and environmentally friendly approach. The partially purified pectinase showed significant application for apple juice clarification and showed the ability to degrade pectin and therefore the colour change was observed in apple juice within 120 min. Maximum pectinase was produced by\ A. niger\ using agricultural waste orange peel under submerged fermentation which is an economical, versatile and eco-friendly process and pectinase showed a significant application for apple juice clarification.

}, doi = {10.22207/JPAM.16.4.43}, author = {Wagh, Vrushali and Patel, Hirvitaben and Patel, Nafisa and Vamkudoth, Koteswara Rao and Ajmera, Shanthipriya} } @article {48145, title = {Pendant propargyloxy-functionalized aromatic (co)polycarbonates: synthesis, thermal crosslinking and chemical modification}, journal = {Journal of Macromolecular Science Part A-Pure and Applied Chemistry}, volume = {59}, year = {2022}, month = {NOV}, pages = {752-763}, type = {Article}, abstract = {

A bisphenol monomer bearing pendant propargyloxy group viz, 1, 1-bis (4-hydoxyphenyl)-1-(4 {\textquoteleft}-propargyloxyphenyl) ethane (BPP) was synthesized starting from commercially available 1, 1, 1-tris (4-hydroxyphenyl) ethane (THPE) by mono O-propargylation reaction using propargyl bromide. A new series of pendant propargyloxy-functionalized aromatic (co)polycarbonates was synthesized by low-temperature solution polycondensation of BPP or different molar ratios of BPP and bisphenol-A with triphosgene in dichloromethane in the presence of triethylamine. The formation of reasonably high molecular weight (co)polycarbonates was confirmed by inherent viscosity (0.52-0.83 dL/g) and gel permeation chromatography (M-n 37,000-69,800 g/mol, polystyrene standards) measurements. C-13 NMR spectral studies supported formation of random copolycarbonates in copolymerization of BPP and BPA with triphosgene. The 10\% weight loss temperature (T-10) values of (co)polycarbonates, determined by thermogravimetric analysis under nitrogen atmosphere, were in the range 427-438 degrees C indicating their good thermal stability. The glass transition temperature (T-g) values of (co)polycarbonates were observed in the range 147-152 degrees C. The crosslinking ability of (co)polycarbonates involving pendant propargyloxy groups leading to formation of networked structure was evaluated via non-isothermal curing studies by DSC. As a proof-of-concept, the post-modification of a representative polycarbonate bearing pendant propargyloxy groups with 1-octane thiol as a model compound via thiol-yne click reaction was briefly studied.

}, keywords = {Aromatic polycarbonate, Chemical modification, propargyloxy groups, thermal crosslinking, thiol-yne click reaction}, issn = {1060-1325}, doi = {10.1080/10601325.2022.2117055}, author = {Nagane, Samadhan S. and Maher, Deepak M. and Verma, Savita and Talanikar, Aniket A. and Wadgaonkar, Prakash P.} } @article {48124, title = {Polymorphs of green fluorescence protein chromophore analogue: fluorescence switching with thermal stimuli}, journal = {Crystal Growth \& Design}, volume = {22}, year = {2022}, month = {MAR }, pages = {1892-1905}, type = {Article}, abstract = {

Polymorphs of fluorescent organic materials offer significant implications in optoelectronics and advanced materials as they modulate photoluminescence properties. A slight alteration in the conformation/packing of molecules in the crystals shows variation in photoluminescence. This necessitates the polymorph screening of these materials to develop novel crystalline forms with distinct fluorescence emissions for broader application. In continuation of our work on the polymorph screening of Green Fluorescence Protein Chromophore (GFPc), we have synthesized a new imidazoline derivative, ethyl (Z)-2-(2-methyl-5-oxo-4-(3,4,5-trimethoxybenzylidene)-4,5-dihydro-1H-imi dazol-1- yl)acetate (1). Polymorph screening of 1 under different crystallization conditions revealed three polymorphs, Form I (needle), Form II (block), and Form III (polycrystalline material). Forms I and II are the outcome of solution crystallization, whereas Form III was produced from the melt crystallization of Forms I and II. DSC, HSM, and powder and single-crystal XRD studies indicate the conversion of Form I and Form III crystals to Form II crystals on thermal stimuli. The photoluminescence studies revealed cyan, yellow, and yellowish-green fluorescence emission for Forms I, II, and III crystals, respectively. The difference in photoluminescence could be due to the variance in aggregation modes like H-aggregation in Form I and J-aggregation in Form II crystals. Form I, Form II, and Form III crystals also showed irreversible thermal fluorescent switching from cyan-yellow-green due to polymorphic phase transitions. The study correlates the direct observation of the modulation of the excited-state transition under thermal stimuli in the crystalline phase. It will help augment the pace in the research of thermally responsive fluorescent materials.

}, issn = {1528-7483}, doi = {10.1021/acs.cgd.1c01459}, author = {Mali, Bhupendra P. and Dash, Soumya Ranjan and Biswas, Anupam and Vanka, Kumar and Manoj, Kochunnoonny and Gonnade, Rajesh G.} } @article {48094, title = {Potential- and time-dependent dynamic nature of an oxide-derived pdin nanocatalyst during electrochemical CO2 reduction}, journal = {ACS Nano}, volume = {16}, year = {2022}, month = {APR}, pages = {6185-6196}, type = {Article}, abstract = {

Electrochemical reduction of CO2 into valuable fuels and chemicals is a promising route of replacing fossil fuels by reducing CO2 emissions and minimizing its adverse effects on the climate. Tremendous efforts have been carried out for designing efficient catalyst materials to selectively produce the desired product in high yield from CO2 by the electrochemical process. In this work, a strategy is reported to enhance the electrochemical CO2 reduction reaction (ECO2RR) by constructing an interface between a metal-based alloy (PdIn) nanoparticle and an oxide (In2O3), which was synthesized by a facile solution method. The oxide-derived PdIn surface has shown excellent eCO(2)RR activity and enhanced CO selectivity with a Faradaic efficiency (FE) of 92.13\% at -0.9 V (vs RHE). On the other hand, surface PdO formation due to charge transfer on the bare PdIn alloy reduces the CO2RR activity. With the support of in situ (EXAFS and IR) and ex situ (XPS, Raman) spectroscopic techniques, the optimum presence of the Pd-In-O interface has been identified as a crucial parameter for enhancing eCO(2)RR toward CO in a reducing atmosphere. The influence of eCO(2)RR duration is reported to affect the overall performance by switching the product selectivity from H-2 (from water reduction) to CO (from eCO(2)RR) on the oxide-derived alloy surface. This work also succeeded in the multifold enhancement of the current density by employing the gas diffusion electrode (GDE) and optimizing its process parameters in a flow cell configuration.

}, keywords = {CO2 reduction, Electrochemistry, heterostructure interface, in situ mechanism, nanocatalyst}, issn = {1936-0851}, doi = {10.1021/acsnano.1c11664}, author = {Bagchi, Debabrata and Sarkar, Shreya and Singh, Ashutosh Kumar and Vinod, Chathakudath P. and Peter, Sebastian C.} } @article {48057, title = {Predicting the redox potentials of phenazine derivatives using DFT-assisted machine learning}, journal = {ACS Omega}, volume = {7}, year = {2022}, month = {APR }, pages = {11742-11755}, type = {Article}, abstract = {

This study investigates four machine-learning (ML) models to predict the redox potentials of phenazine derivatives in dimethoxyethane using density functional theory (DFT). A small data set of 151 phenazine derivatives having only one type of functional group per molecule (20 unique groups) was used for the training. Prediction accuracy was improved by a combined strategy of feature selection and hyperparameter optimization, using the external validation set. Models were evaluated on the external test set containing new functional groups and diverse molecular structures. High prediction accuracies of R2 \> 0.74 were obtained on the external test set. Despite being trained on the molecules with a single type of functional group, models were able to predict the redox potentials of derivatives containing multiple and different types of functional groups with good accuracies (R2 \> 0.7). This type of performance for predicting redox potential from such a small and simple data set of phenazine derivatives has never been reported before. Redox flow batteries (RFBs) are emerging as promising candidates for energy storage systems. However, new green and efficient materials are required for their widespread usage. We believe that the hybrid DFT-ML approach demonstrated in this report would help in accelerating the virtual screening of phenazine derivatives, thus saving computational and experimental costs. Using this approach, we have identified promising phenazine derivatives for green energy storage systems such as RFBs.

}, issn = {2470-1343}, doi = {10.1021/acsomega.1c06856}, author = {Ghule, Siddharth and Dash, Soumya Ranjan and Bagchi, Sayan and Joshi, Kavita and Vanka, Kumar} } @article {48133, title = {Reactivity of four coordinate iridium complex towards hydrogen: an experimental and computational study}, journal = {Journal of Organometallic Chemistry}, volume = {965}, year = {2022}, month = {MAY}, pages = {122317}, type = {Article}, abstract = {

Reaction of a four coordinate, 16-electron Ir complex, [Ir-(iPr)4(POCOP)(PPh3)] (4 ) (((iPr)4)(POCOP= 2,6-bis(di-isopropyl phosphinito)benzene, kappa(3)-C6H3-1,3-[OP((iPr))(2)](2)), with H-2 resulted in an oxidative addition product, cis-dihydride complex, cis-[Ir(H)(2) ((iPr)4)(POCOP)(PPh3)] ( cis-5 ) presumably via the intermediacy of a sigma complex, [Ir(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)]. The cis-dihydride complex completely isomerizes to the trans-dihydride complex trans-[Ir(H)(2) ((iPr)4)(POCOP)(PPh3)] ( trans-5 ) under ambient conditions in about 3 h. It was found that the steric and electronic features on the iridium center have significant influence on the approach of H-2 onto the metal center followed by oxidative addition and isomerization. The isomerization process was studied in detail and all the mechanistic aspects have been elucidated using a combination of both experimental work and computation. The cis-dihydride complex isomerizes to the trans-dihydride by compensating the trans influence of the strongly trans-directing hydride ligand. A mechanism involving the exchange of the position of PPh3 with a hydride ligand cis to itself via PPh3 dissociation and re-coordination thereby resulting in the formation of the trans-dihydride complex, has been proposed for the isomerization. The cis-dihydride was found to be a highly active catalyst for hydrogenation of ethy-lene. A competing reactivity study of cis-dihydride between isomerization versus insertion of C2H4 into the Ir-H bond, was studied experimentally and computationally. (c) 2022 Elsevier B.V. All rights reserved.

}, keywords = {Hydrogenation, Insertion, iridium complex, isomerization, Oxidative addition, Reductive elimination}, issn = {0022-328X}, doi = {10.1016/j.jorganchem.2022.122317}, author = {Agrawal, Nisha K. and Dash, Soumya R. and Vanka, Kumar and Nethaji, Munirathinam and Jagirdar, Balaji R.} } @article {48125, title = {Regio-isomerism directed electrocatalysis for energy efficient zinc-air battery}, journal = {iScience}, volume = {25}, year = {2022}, month = {OCT }, pages = {105179}, type = {Article}, abstract = {

We have investigated the role of ligand isomerism in modulating the mechanisms and kinetics associated with charge/ discharge chemistry of an aqueous metal-air battery. The dominant electron-withdrawing inductive effect (-I effect) and the diminished electron-withdrawing resonance effect (-R effect) in the alpha-NO2 isomer noticeably diminishes the rate of oxygen reduction (ORR) and oxygen evolution reactions (OER) on the catalytic Co-center. In their beta-counterpart, the cumulative -I and -R effects noticeably enhance the OER and ORR kinetics on the same catalytic Co-center. Therefore, the regioisomerism of the -NO2 functionality amplifies the kinetics of ORR/OER without influencing their mechanistic pathways. When isomeric electrocatalysts are integrated to aid the charge chemistry of a Zn-air battery, the overpotential could be decreased by similar to 250mV with beta-NO2 isomer leading to a round-trip efficiency as high as 60\%. This work contributes to the design of novel molecular platforms to target the overall round-trip efficiency of energy storage and conversion devices.

}, doi = {10.1016/j.isci.2022.105179}, author = {Mukhopadhyay, Sanchayita and Devendrachari, Mruthyunjayachari Chattanahalli and Kanade, Sandeep C. and Vinod, Chathakudath Prabhakaran and Kotresh, Harish Makri Nimbegondi and Thotiyl, Musthafa Ottakam} } @article {48058, title = {Regioselective synthesis of 1,4,5-trisubstituted 1,2,3-triazole derivatives from alpha,beta-unsaturated carbonyls}, journal = {European Journal of Organic Chemistry}, volume = {2022}, year = {2022}, month = {JUL}, pages = {e202200317}, type = {Article}, abstract = {

The copper-catalyzed oxidative azide-olefin cycloaddition (OAOC) reaction of differently substituted alpha,beta-unsaturated carbonyls with azides provided an efficient method for preparing biologically active 1,4,5-trisubstituted 1,2,3-triazoles. In this study, the cycloaddition reaction was found to be a simple and powerful method for constructing diverse mono- and bis-(1,4,5-trisubstituted 1,2,3-triazole) functionalized heterocyclic compounds in moderate to high yields with great regioselectivity. The XRD-analysis data of one of the bis-triazole derivatives supported the regioselectivity as well as the conformity of the method in the construction of the triazole nucleus. The preliminary antifungal profile against C. albicans was observed with cinnamaldehyde-based triazole derivatives demonstrating promising results.

}, keywords = {alpha, antifungal, beta-Unsaturated carbonyls, Cycloaddition, Dibenzalacetone, Triazole}, issn = {1434-193X}, doi = {10.1002/ejoc.202200317}, author = {Verma, Naimish K. and Bera, Smritilekha and Gonnade, Rajesh and Mondal, Dhananjoy} } @article {48103, title = {Review on computational analysis of big data in breast cancer for predicting potential biomarkers}, journal = {Current Topics in Medicinal Chemistry}, volume = {22}, year = {2022}, month = {SEP}, pages = {1793-1810}, type = {Review}, abstract = {

Breast cancer is the most predominantly occurring cancer in the world. Several genes and proteins have been recently studied to predict biomarkers that enable early disease identification and monitor its recurrence. In the era of high-throughput technology, studies show several applications of big data for identifying potential biomarkers. The review aims to provide a comprehensive overview of big data analysis in breast cancer towards the prediction of biomarkers with emphasis on computational methods like text mining, network analysis, next-generation sequencing technology (NGS), machine learning (ML), deep learning (DL), and precision medicine. Integrating data from various computational approaches enables the stratification of cancer patients and the identification of molecular signatures in cancer and their subtypes. The computational methods and statistical analysis help expedite cancer prognosis and develop precision cancer medicine (PCM). As a part of case study in the present work, we constructed a large gene-drug interaction network to predict new biomarkers genes. The gene-drug network helped us to identify eight genes that could serve as novel potential biomarkers.

}, keywords = {Big data, Biomarkers, Breast cancer, Driver genes, Network analysis, text mining}, issn = {1568-0266}, doi = {10.2174/1568026622666220907121942}, author = {Shaikh, Nilofer and Bapat, Sanket and Karthikeyan, Muthukumarasamy and Vyas, Renu} } @article {48102, title = {Room temperature chemoselective hydrogenation of C=C, C=O and C=N bonds by using a well-defined mixed donor Mn(I) pincer catalyst}, journal = {Chemical Science}, volume = {13}, year = {2022}, month = {NOV }, pages = {13764-13773}, type = {Article}, abstract = {

Chemoselective hydrogenation of C=C, C=O and C=N bonds in alpha,beta-unsaturated ketones, aldehydes and imines is accomplished at room temperature (27 degrees C) using a well-defined Mn(I) catalyst and 5.0 bar H-2. Amongst the three mixed-donor Mn(I) complexes developed, kappa(3)-((PNNPyz)-P-R2-N-3)Mn(CO)(2)Br (R = Ph, Pr-i, Bu-t); the Bu-t -substituted complex ((PNNPyz)-P-tBu2-N-3)Mn(CO)(2)Br shows exceptional chemoselective catalytic reduction of unsaturated bonds. This hydrogenation protocol tolerates a range of highly susceptible functionalities, such as halides (-F, -Cl, -Br, and -I), alkoxy and hydroxy, including hydrogen-sensitive moieties like acetyl, nitrile, nitro, epoxide, and unconjugated alkenyl and alkynyl groups. Additionally, the disclosed method applies to indole, pyrrole, furan, thiophene, and pyridine-containing unsaturated ketones leading to the corresponding saturated ketones. The C=C bond is chemoselectively hydrogenated in alpha,beta-unsaturated ketones, while the aldehyde{\textquoteright}s C=O bond and imine{\textquoteright}s C=N bond are preferentially reduced over the C=C bond. A detailed mechanistic study highlighted the non-innocent behavior of the ligand in the ((PNNPyz)-P-tBu2-N-3) Mn(I) complex and indicated a metal-ligand cooperative catalytic pathway. The molecular hydrogen (H-2) acts as a hydride source, whereas MeOH provides a proton for hydrogenation. DFT energy calculations supported the facile progress of most catalytic steps, involving a crucial turnover-limiting H-2 activation.

}, issn = {2041-6520}, doi = {10.1039/d2sc05274a}, author = {Shabade, Anand B. and Sharma, Dipesh M. and Bajpai, Priyam and Gonnade, Rajesh G. and Vanka, Kumar and Punji, Benudhar} } @article {47731, title = {Selective production of C9 monomeric phenols via hydrogenolysis of lignin using Pd-(W/Zr/Mo oxides)-supported on biochar catalyst}, journal = {Fuel}, volume = {308}, year = {2022}, month = {JAN }, pages = {121818}, type = {Article}, abstract = {Valorizing lignin to phenolic monomers and fine chemicals is an essential component of a sustainable biorefinery that uses lignocellulosic feedstocks. In this study, Pd-metal oxides (ZrO2, WOx, MoO3) supported on activated biochar (ABC) catalysts were developed for hydrogenolysis of lignin. The metals (2\% Pd, 5\% Zr, 5\% W, 5\% Mo) were supported on activated biochar using the wetness impregnation method, and the catalysts were extensively characterized. The effect of addition of secondary metals on active surface properties such as acidity, Pd metal particle size and dispersion were also evaluated. The selectivity to C9 monomeric phenols followed the trend: 2Pd-5Mo/ABC (57.3\%) > 2Pd-5Zr/ABC (49.2\%) > 2Pd-5W/ABC (45\%) > 2Pd/ABC (42.9\%). The maximum C9 phenolic monomer yield achieved in this study was similar to 22 wt\%. The fractional conversion of lignin was 67-69\% with Pd-metal oxide catalysts. The presence of Mo in the catalyst inhibited the hydrogenation of aliphatic C-alpha = C-beta in lignin and led to the formation of t-isoeugenol, while the presence of W and Zr resulted in selective formation of the hydrogenated product, propyl guaiacol. Using model compounds, it is proved that the formation of propyl guaiacol is via hydrogenation of t-isoeugenol, and not through dehydroxylation of propanol guaiacol. The dehydroxylation activity of the catalysts is attributed to the higher Lewis acidity and electropositive nature of the metals. A notable carbon atom economy of 47-50\% towards total phenolic monomers was achieved with 2Pd/ABC, 2Pd-5Mo/ABC and 2Pd-5Zr/ABC catalysts.}, keywords = {Activated biochar, Guaiacol, Hydrogenolysis, lignin, Metal oxides, Palladium}, issn = {0016-2361}, doi = {10.1016/j.fuel.2021.121818}, author = {Gurrala, Lakshmiprasad and Kumar, M. Midhun and Sharma, Shweta and Paek, Changyub and Vinu, R.} } @article {48178, title = {{\textquoteleft}Self-activating{\textquoteright} Bi3TaO7-Bi4TaO8Br photocatalyst and its use in the sustainable production of pro-fluorophoric rhodamine-110}, journal = {Green Chemistry}, volume = {24}, year = {2022}, month = {JUL}, pages = {5514-5523}, type = {Article}, abstract = {

We counter two common notions that (i) photocatalysts are likely to degrade during use with barely any strategy to counter it and (ii) rhodamine-B (RhB) photo-degradation lacks any useful or commercial prospects even after 53 years of its discovery by developing a photocatalyst that continues to improve its activity for similar to 300 h due to a leaching induced {\textquoteleft}self-activation{\textquoteright} process. Rhodamine-110 (Rh110) is a widely used pro-fluorophore in biological studies. However, its commercial production is highly challenging due to the formation of various side-products originating from the presence of the two labile amino side-groups that induce the pro-fluorophore activity, leading to purification difficulties, low yield, and unusually high costs. Herein, we demonstrate a facile strategy to produce pure Rh110 using extremely inexpensive RhB and Bi3TaO7-Bi4TaO8Br heterostructures as a catalyst in sunlight. The catalyst is not just stable over 30 catalytic cycles but also gets activated continuously in successive cycles to produce a reaction yield as high as 88\%. The role of the heterostructure, the origin of surface activation, and the RhB -\> Rh110 transformation mechanism have been established. Based on 150 days of sunlight experiments, large-scale production prospects (similar to 4000 times scale-up) and isolation of Rh110 have also been realized, paving a novel way for its production by anyone, inexpensive biological essaying, and device fabrication. Continuously improving catalysts are unknown and compensatory leaching of metal atoms from the catalyst surface may pave the way to realize them.

}, issn = {1463-9262}, doi = {10.1039/d2gc01574a}, author = {Banoo, Maqsuma and Chatterjee, Kaustav and Mondal, Sanjit and Vinod, C. P. and Gautam, Ujjal K.} } @article {48079, title = {Silk fibroin microparticle scaffold for use in bone void filling: safety and efficacy studies}, journal = {ACS Biomaterials Science \& Engineering}, volume = {8}, year = {2022}, month = {MAR}, pages = {1226-1238}, type = {Article}, abstract = {

Silk fibroin (SF) is a natural biocompatible protein polymer extracted from cocoons of silkworm Bombyx mori. SF can be processed into a variety of different forms and shapes that can be used as scaffolds to support bone regeneration. Threedimensional (3D) SF scaffolds have shown promise in bone-void -filling applications. In in vitro studies, it has been demonstrated that a microparticle-based SF (M-RSF) scaffold promotes the differentiation of stem cells into an osteoblastic lineage. The expression of differentiation markers was also significantly higher for M-RSF scaffolds as compared to other SF scaffolds and commercial ceramic scaffolds. In this work, we have evaluated the in vitro and in vivo biocompatibility of M-RSF scaffolds as per the ISO 10993 guidelines in a Good Laboratory Practice (GLP)-certified facility. The cytotoxicity, immunogenicity, genotoxicity, systemic toxicity, and implantation studies confirmed that the M-RSF scaffold is biocompatible. Further, the performance of the MRSF scaffold to support bone formation was evaluated in in vivo bone implantation studies in a rabbit model. Calcium sulfate (CaSO4) scaffolds were chosen as reference material for this study as they are one of the preferred materials for bone-void -filling applications. M-RSF scaffold implantation sites showed a higher number of osteoblast and osteoclast cells as compared to CaSO4 implantation sites indicating active bone remodeling. The number density of osteocytes was double for M-RSF scaffold implantation sites, and these M-RSF scaffold implantation sites were characterized by enhanced collagen deposition, pointing toward a finer quality of the new bone formed. Moreover, the M-RSF scaffold implantation sites had a negligible incidence of secondary fractures as compared to the CaSO4 implantation sites (similar to 50\% sites with secondary fracture), implying a reduction in postsurgical complications. Thus, the study demonstrates that the M-RSF scaffold is nontoxic for bone-void -filling applications and facilitates superior healing of fracture defects as compared to commercial calcium-based bone void fillers.

}, keywords = {Biocompatibility, biological safety, bone void filler, ISO 10993, M-RSF, Serioss, Silk fibroin}, issn = {2373-9878}, doi = {10.1021/acsbiomaterials.1c01103}, author = {Deshpande, Rucha and Shukla, Swati and Kale, Amod and Deshmukh, Narendra and Nisal, Anuya and Venugopalan, Premnath} } @article {48405, title = {Silver dependent enantiodivergent gold(i) catalysed asymmetric intramolecular hydroamination of alkenes: a theoretical study}, journal = {Catalysts}, volume = {12}, year = {2022}, month = {NOV}, pages = {1392}, type = {Article}, abstract = {

We report a theoretical study of the first silver-dependent enantiodivergent gold-catalysed reaction. The combination of a single chiral binuclear gold(I) chloride complex and silver perchlorate catalyses the asymmetric intramolecular hydroamination of alkenes and affords both enantiomers of the products by applying a simple solvent change from toluene to methanol. A gold-silver chloride adduct that occurs only in methanol appears to control the enantioinversion. If one gold atom coordinates and activates the alkene moiety, the other gold is included in an adduct with silver chloride, which coordinates a methanol solvent molecule and further interacts with the amine function. If the use of toluene implies free anions and affords (S)-enantiomer, methanol allows a proximal interaction with the amine, leads to an opposite stereodifferentiation of the two diastereomeric intermediates during the final protodeauration step and results in the (R)-enantiomer.

}, keywords = {alkene, enantiodivergent catalysis, Gold, hydroamination, Silver}, doi = {10.3390/catal12111392}, author = {Dixit, Ruchi and Sharma, Himanshu and Agbossou-Niedercorn, Francine and Vanka, Kumar and Michon, Christophe} } @article {47834, title = {Silver-catalyzed [3 + 3]-annulation cascade of alkynyl alcohols and α,β-unsaturated ketones for the regioselective assembly of chromanes}, journal = {Organic Chemistry Frontiers}, volume = {9}, year = {2022}, month = {JAN}, pages = {802-809}, type = {Article}, abstract = {An unprecedented Ag(i)-catalyzed [3 + 3]-annulation of alkynyl alcohols (5-hexyn-1-ols) and α,β-unsaturated ketones is reported to construct simple to complex chromanes. This transformation begins with hydroalkoxylation of alkynol through C{\textendash}C triple bond activation to give cyclic-enol ether, followed by intermolecular 1,4-addition and intramolecular 1,2-addition of enol ethers onto the enone and oxidative aromatization or Grob-type elimination steps. Facile reaction conditions, broad substrate scope, good to excellent yields, and atom economy are the salient features of this protocol. Isolation of the active pyran-tethered cyclohexadiene reaction intermediate, additional supporting experiments, and DFT calculations strongly support the experimental findings and corroborate our proposed mechanism.}, issn = {2052-4129}, doi = {10.1039/D1QO01643A}, author = {Nakate, Ashwini K. and Thorat, Sagar S. and Jain, Shailja and Rama Krishna, Gamidi and Vanka, Kumar and Kontham, Ravindar} } @article {47998, title = {Single-step insertion of M-Nx moieties in commercial carbon for sustainable bifunctional electrocatalysis: mapping insertion capacity, mass loss, and carbon reconstruction}, journal = {Carbon}, volume = {196}, year = {2022}, month = {AUG}, pages = {1001-1011}, type = {Article}, abstract = {

Atomically dispersed earth-abundant metals in N-doped carbon (M-N-Cs) have emerged as a new class of electroactive materials that can match not only the performance of the precious metals but can catalyze both the cathodic and the anodic reactions due to their bifunctional behaviour. This inspires the development of simpler strategies for scale-up production since the existing ones rely on precursors whose commercial viability is not yet ascertained. Herein, we demonstrate the insertion prospects of M-Nx (M = Fe, Co, Ni) moieties, the electrocatalytic centers in the M-N-Cs, into commercial carbon to establish that a single-step heating of the inexpensive precursors is sufficient to generate bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with efficiencies that bypass the majority of the known catalysts. Further importantly, we quantify both the ORR and OER trends and the metal insertion limits for each metal while maintaining an atomic dispersion, without the formation of surface migration-induced clustering, because such clustering is inevitable in the existing processes to necessitate an extra acid-leaching step to remove them. We further quantify and explain for each metal a negative mass balance originating from anomalous mass loss of both metal and carbon content, and a massive reconstruction of the carbon backbone catalyzed by the very metal, an event documented for the first time though it ought to be associated with other M-N-C syntheses too. The study establishes an incredibly simple and inexpensive strategy for the realization of M-N-Cs and outlines the parameters to be considered during mass-production.

}, keywords = {Bifunctional catalysis, Carbon reconstruction, Commercial carbon, Metal insertion, Oxygen electrocatalysis}, issn = {0008-6223}, doi = {10.1016/j.carbon.2022.06.008}, author = {Garg, Reeya and Sahoo, Lipipuspa and Kaur, Komalpreet and Vinod, C. P. and Gautam, Ujjal K.} } @article {48223, title = {Stacking herbicide detoxification and resistant genes improves glyphosate tolerance and reduces phytotoxicity in tobacco (Nicotiana tabacum L.) and rice (Oryza sativa L.)}, journal = {Plant Physiology and Biochemistry}, volume = {189}, year = {2022}, month = {OCT}, pages = {126-138}, type = {Article}, abstract = {

Glyphosate residues retained in the growing meristematic tissues or in grains of glyphosate-resistant crops affect the plants physiological functions and crop yield. Removing glyphosate residues in the plants is desirable with no penalty on crop yield and quality. We report a new combination of scientific strategy to detoxify glyphosate that reduces the residual levels and improve crop resistance. The glyphosate detoxifying enzymes Aldo-keto reductase (AKR1) and mutated glycine oxidase (mGO) with different modes of action were co-expressed with modified EPSPS, which is insensitive to glyphosate in tobacco (Nicotiana tabacum L.) and rice (Oryza sativa L.). The transgenic tobacco plants expressing individual PsAKR1, mGO, CP4-EPSPS, combinations of PsAKR1:CP4EPSPS, PsAKR1:mGO, and multigene with PsAKR1: mGO: CP4EPSPS genes were developed. The bio-efficacy studies of in-vitro leaf regeneration on different concentrations of glyphosate, seedling bioassay, and spray on transgenic tobacco plants demonstrate that glyphosate detoxification with enhanced resistance. Comparative analysis of the transgenic tobacco plants reveals that double and multigene expressing transgenics had reduced accumulation of shikimic acid, glyphosate, and its primary residue AMPA, and increased levels of sarcosine were observed in all PsAKR1 expressing transgenics. The multigene expressing rice transgenics showed improved glyphosate resis-tance with yield maintenance. In summary, results suggest that stacking genes with two different detoxification mechanisms and insensitive EPSPS is a potential approach for developing glyphosate-resistant plants with less residual content.

}, keywords = {Detoxification, Gene stacking, Glyphosate, Herbicide, Multigene, Residual toxicity, Resistant, rice, Tobacco, Transgenics}, issn = {0981-9428}, doi = {10.1016/j.plaphy.2022.08.025}, author = {Vennapusa, Amaranatha Reddy and Agarwal, Subham and Hm, Hanumanth Rao and Aarthy, Thiagarayaselvam and Babitha, K. C. and Thulasiram, V. Hirekodathakallu and Kulkarni, Mahesh J. and Melmaiee, Kalpalatha and Sudhakar, Chinta and Udayakumar, M. and Vemanna, Ramu S.} } @article {47757, title = {Steroidal alkaloids defence metabolism and plant growth are modulated by the joint action of gibberellin and jasmonate signalling}, journal = {New Phytologist}, volume = {233}, year = {2022}, month = {FEB}, pages = {1220-1237}, type = {Article}, abstract = {Steroidal glycoalkaloids (SGAs) are protective metabolites constitutively produced by Solanaceae species. Genes and enzymes generating the vast structural diversity of SGAs have been largely identified. Yet, mechanisms of hormone pathways coordinating defence (jasmonate; JA) and growth (gibberellin; GA) controlling SGAs metabolism remain unclear. We used tomato to decipher the hormonal regulation of SGAs metabolism during growth vs defence tradeoff. This was performed by genetic and biochemical characterisation of different JA and GA pathways components, coupled with in vitro experiments to elucidate the crosstalk between these hormone pathways mediating SGAs metabolism. We discovered that reduced active JA results in decreased SGA production, while low levels of GA or its receptor led to elevated SGA accumulation. We showed that MYC1 and MYC2 transcription factors mediate the JA/GA crosstalk by transcriptional activation of SGA biosynthesis and GA catabolism genes. Furthermore, MYC1 and MYC2 transcriptionally regulate the GA signalling suppressor DELLA that by itself interferes in JA-mediated SGA control by modulating MYC activity through protein-protein interaction. Chemical and fungal pathogen treatments reinforced the concept of JA/GA crosstalk during SGA metabolism. These findings revealed the mechanism of JA/GA interplay in SGA biosynthesis to balance the cost of chemical defence with growth.}, keywords = {alpha-tomatine, defence, gibberellin (GA), growth, jasmonate (JA), steroidal glycoalkaloids (SGAs), Tomato}, issn = {0028-646X}, doi = {10.1111/nph.17845}, author = {Panda, Sayantan and Jozwiak, Adam and Sonawane, Prashant D. and Szymanski, Jedrzej and Kazachkova, Yana and Vainer, Andrii and Kilambi, Himabindu Vasuki and Almekias-Siegl, Efrat and Dikaya, Varvara and Bocobza, Samuel and Shohat, Hagai and Meir, Sagit and Wizler, Guy and Giri, Ashok P. and Schuurink, Robert and Weiss, David and Yasuor, Hagai and Kamble, Avinash and Aharoni, Asaph} } @article {48098, title = {Strain-enhanced phase transformation of iron oxide for higher alcohol production from CO2}, journal = {ACS Catalysis}, volume = {12}, year = {2022}, month = {SEP}, pages = {11118-11128}, type = {Article}, abstract = {

Conversion of CO2 to higher alcohols (HAs) and higher hydrocarbons (HCs) has a greater advantage compared to C1 products because of their high energy density and wide range of applications in daily life. Despite the immense potential of these chemicals, not much of scientific research has been focused on the conversion of CO2 to HAs. In the present work, we have introduced the concept of strain in designing the material to enhance the CO(2 )to HA performance. We introduced strain in a traditional iron-based catalyst, Fe2O3, by the introduction of indium (In), which facilitates the selective conversion of CO2 to HA. An optimum strain favored a 36.7\% CO2 conversion with a 42\% HA selectivity, and a record yield of 15.42\%. The strain has been tuned further with the introduction of K as a promoter. The introduced strain upon In substitution and K promotion favored the conversion of CO2, which is mapped by powder X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. Further, the change in the mechanism upon In incorporation and K promotion has been probed by in situ diffuse reflectance infrared fourier transform spectroscopy, and it is found that the OCHx intermediate, which produces HAs, is more prominent upon In substitution, which favored the enhancement of HA production compared to that of pristine Fe2O3.

}, keywords = {CO2 to HA, Fischer-Tropsch synthesis (FTS), Phase transformation, reverse water gas shift (RWGS) reaction, strain}, issn = {2155-5435}, doi = {10.1021/acscatal.2c0318311118}, author = {Goud, Devender and Churipard, Sathyapal R. and Bagchi, Debabrata and Singh, Ashutosh Kumar and Riyaz, Mohd and Vinod, C. P. and Peter, Sebastian C.} } @article {48088, title = {Structure-tailored surface oxide on Cu-Ga intermetallics enhances CO2 reduction selectivity to methanol at ultralow potential}, journal = {Advanced Materials}, volume = {34}, year = {2022}, month = {MAY}, pages = {2109426}, type = {Article}, abstract = {

Electrochemical CO2 reduction reaction (eCO(2)RR) is performed on two intermetallic compounds formed by copper and gallium metals (CuGa2 and Cu9Ga4). Among them, CuGa2 selectively converts CO2 to methanol with remarkable Faradaic efficiency of 77.26\% at an extremely low potential of -0.3 V vs RHE. The high performance of CuGa2 compared to Cu9Ga4 is driven by its unique 2D structure, which retains surface and subsurface oxide species (Ga2O3) even in the reduction atmosphere. The Ga2O3 species is mapped by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) techniques and electrochemical measurements. The eCO(2)RR selectivity to methanol are decreased at higher potential due to the lattice expansion caused by the reduction of the Ga2O3, which is probed by in situ XAFS, quasi in situ powder X-ray diffraction, and ex situ XPS measurements. The mechanism of the formation of methanol is visualized by in situ infrared (IR) spectroscopy and the source of the carbon of methanol at the molecular level is confirmed from the isotope-labeling experiments in presence of (CO2)-C-13. Finally, to minimize the mass transport limitations and improve the overall eCO(2)RR performance, a poly(tetrafluoroethylene)-based gas diffusion electrode is used in the flow cell configuration.

}, keywords = {(2) reduction, CO, Electrochemistry, Methanol}, issn = {0935-9648}, doi = {10.1002/adma.202109426}, author = {Bagchi, Debabrata and Raj, Jithu and Singh, Ashutosh Kumar and Cherevotan, Arjun and Roy, Soumyabrata and Manoj, Kaja Sai and Vinod, C. P. and Peter, Sebastian C.} } @article {48149, title = {Substitution at sp(3) boron of a six-membered NHC center dot BH3: convenient access to a dihydroxyborenium cation}, journal = {Chemical Communications}, volume = {58}, year = {2022}, month = {MAR }, pages = {3783-3786}, type = {Article}, abstract = {

Herein, we have undertaken the synthesis and investigated the reactivity of a 6-membered saturated NHC borane adduct (1). Direct electrophilic halogenation of 1 with a stoichiometric amount of I-2 led to NHC boryl iodides, 6-SIDipp center dot BH2I (2) and 6-SIDipp center dot BHI2 (3), which were further reacted with various nucleophiles to give novel 6-SIDipp based mono and disubstituted boranes with OTf (4 and 6) or ONO2 (5 and 7) functional groups. The addition of Br-2/H2O to 1 smoothly results in a dihydroxyborenium cation (8).

}, issn = {1359-7345}, doi = {10.1039/d1cc06816d}, author = {Kundu, Gargi and Ajithkumar, V. S. and Raj, K. Vipin and Vanka, Kumar and Tothadi, Srinu and Sen, Sakya S.} } @article {48183, title = {Synergistic electronic effects in AuCo nanoparticles stabilized in a triazine-based covalent organic framework: a catalyst for methyl orange and methylene blue reduction}, journal = {ACS Applied Nano Materials}, volume = {5}, year = {2022}, month = {APR }, pages = {4744-4753}, type = {Article}, abstract = {

Developing stable active catalysts for reducing water-soluble pollutants is a desirable target. In this pursuit, we have functionalized covalent organic frameworks (COFs) with gold (Au) and cobalt (Co) nanoparticles via a one-step aqueous synthesis process, and their catalytic activity in reducing methyl orange and methylene blue is examined. Operando absorbance measurements of methyl orange (anionic dye) reduction revealed AuCoCOF (1.3 Au/1.0 Co) to have superior kinetics over many other catalysts, which typically require additional external stimuli (e.g., photons) and higher catalyst loadings. After confirming the homogeneous dispersion of the nanoparticles on the COF support using three-dimensional (3D) tomography and material stability through powder X-ray diffraction (PXRD), infrared (IR), and thermal studies, we investigated their redox activity. Cyclic voltammetry (CV) confirmed the involvement of both metals in the redox process, while spectroelectrochemical measurements show that their activity and kinetics remain unaltered by an applied potential. Solid-state UV measurements reveal that the neat COF is a semiconductor with a large band gap (2.8 eV), which is substantially lowered when loaded with cobalt nanoparticles (2.2 eV for CoCOF). The electronic synergy between Au and Co nanoparticles further reduces the band gap of AuCoCOF (1.9 eV). Thus, there is a definite advantage in doping non-noble metal nanoparticles into a noble metal lattice and nanoconfining them into a porous COF support. Our study highlights the significance of bimetallic COF-supported nanocatalysts, wherein one can engage each component toward targeted applications that demand redox activity with favorable kinetics.

}, keywords = {AuCoCOF, band gaps, Covalent organic framework, methyl orange reduction, Nanoparticles, UV-vis spectroscopy}, doi = {10.1021/acsanm.1c04212}, author = {Devulapalli, Venkata Swaroopa Datta and Kushwaha, Rinku and Ovalle, Edwin and Singh, Himan Dev and Shekhar, Pragalbh and Chakraborty, Debanjan and Vinod, Chathakudath Prabhakaran and Vaidhyanathan, Ramanathan and Borguet, Eric} } @article {48217, title = {Synthesis and crystal structures of Mn(II) and Co(II) complexes as catalysts for oxidation of cyclohexanone}, journal = {Inorganics}, volume = {10}, year = {2022}, month = {JUL}, pages = {100}, type = {Article}, abstract = {

The global demand on adipic usage in the production of plasticizers and synthetic polyamide is increasing. In line with the search for an efficient and energy-conserving way to isolate adipic acid (AA) in good yields, this paper introduces the oxidization of cyclohexanone utilizing two new coordination compounds, [Mn(2,6-pydc)(2)](imi) (1) and [Co(H(2)pza)(2)(H2O)(2)(NO3)].NO3 (2), as catalysts. Compounds 1 and 2 were synthesized by room temperature and refluxing methods, and characterized by spectral analyses (IR and UV-Vis.), SEM, BET, TGA, elemental, and X-ray crystallography. The single crystal structure of compound 1 revealed that pyridinedicarboxylate (2,6-pydc) and imidazole (imi) moieties were coordinated to the Mn(II) atom through imine nitrogen and deprotonated oxygen atoms, to form an undistorted octahedral coordination geometry with the N2O4 donor set. The axial and equatorial planes containing O2, O4, O5, and O7 atoms were from two adjacent 2,6-pydc ligands which formed the unidendate donor ligand; imi, on the other hand, acted as a bidendate donor ligand. For compound 2, the Co(II) atom was being coordinated by two pyrazinamide (H(2)pza) moieties, which acted as an unidendate donor ligand; two water molecules occupying the axial position, and one nitrate molecule occupying the apical position, were within the coordination sphere; a nitrate molecule was disordered outside the coordination sphere. The distance, 4.658 angstrom, between the Co1 atom and the N8 atom of the uncoordinated nitrate molecule, was within the range reported elsewhere. Cyclohexanone peroxidation experiments revealed that compound 1 exhibited unique catalytic performance by giving a 72.8\% yield in adipic acid, in comparison to the 71.3\% yield obtained with compound 2. The yields in AA were maintained by way of recyclability evaluation. The reaction kinetics of compound 2 gave less activation energy, E-a 2938 J mol(-1), while the thermodynamic parameters indicated that the chemical reactivity of cyclohexanone on the active surfaces of compounds 1 and 2 was via monolayer physisorption.

}, keywords = {cobalt, Complexes, cyclohexanone, Imidazole, managanese, Oxidation, pyrazinamide, pyridinedicarboxylate}, doi = {10.3390/inorganics10070100}, author = {Tella, Adedibu C. and Isaac, Aaron Y. and Clayton, Hadley S. and Ogunlaja, Adeniyi S. and Venugopalan, Aswathy T. and Prabu, Marimuthu and Thirumalaiswamy, Raja} } @article {48151, title = {Tailored synthesis of ultra-stable Au@Pd nanoflowers with enhanced catalytic properties using cellulose nanocrystals}, journal = {Carbohydrate Polymers}, volume = {292}, year = {2022}, month = {SEP}, pages = {119723}, type = {Article}, abstract = {

A green strategy for the synthesis of bimetallic core-shell Au@Pd nanoflowers (NFs) employing banana pseudostem-derived TEMPO-oxidized cellulose nanocrystals (TCNC) as both capping and shape-directing agent via seed-mediated method is presented. Flower-like nanostructures of Au@Pd bound to TEMPO-oxidized cellulose nanocrystals (TCNC-Au@Pd) were decorated on amino-functionalized graphene (NH2-RGO) without losing their unique structure, allowing them to be deployed as an efficient, reusable and a green alternative heterogeneous catalyst. The decisive role of TCNC in the structural metamorphosis of nanoparticle morphology were inferred from the structural and morphology analyses. According to our study, the presence of -OH rich TCNC appears to play a pivotal role in the structured evolution of intricate nanostructure morphology. The feasibility of the bio-supported catalyst has been investigated in two concurrently prevalent model catalytic reactions, namely the oxygen reduction reaction (ORR) and the reduction of 4-nitrophenol, the best model reactions in fuel cell and industrial catalytic applications, respectively.

}, keywords = {Au@Pd, catalysis, Cellulose nanocrystals, Nanoflowers, oxygen reduction reaction}, issn = {0144-8617}, doi = {10.1016/j.carbpol.2022.119723}, author = {Hakkeem, Hasna M. Abdul and Babu, Aswathy and Shilpa, Nagaraju and Venugopal, Adithya A. and Mohamed, A. P. and Kurungot, Sreekumar and Pillai, Saju} } @article {48035, title = {Toxicity and preventive approaches of Fusarium derived mycotoxins using lactic acid bacteria: state of the art}, journal = {Biotechnology Letters}, volume = {44}, year = {2022}, month = {OCT}, pages = {1111-1126}, type = {Review}, abstract = {

Mycotoxin contamination of food and feed is a serious food safety issue and causes acute and chronic diseases in humans and livestock. Climatic and agronomic changes helps in the proliferation of fungal growth and mycotoxin production in food commodities. Mycotoxin contamination has attracted global attention due to its wide range of toxicity to humans and animals. However, physical and chemical management approaches in practice are unsafe for well-being due to their health-hazardous nature. Various antibiotics and preservatives are in use to reduce the microbial load and improve the shelf life of food products. In addition, the use of antibiotic growth promotors in livestock production may increase the risk of antimicrobial resistance, which is a global health concern. Due to their many uses, probiotics are helpful microbes that have a significant impact on food and nutrition. Furthermore, the probiotic potential of lactic acid bacteria (LAB) is employed in various food and feed preparations to neutralize mycotoxins, antimicrobial activities, balance the gut microbiome, and various immunomodulatory activities in both humans and livestock. In addition, LAB produces various antimicrobials, flavouring agents, peptides, and proteins linked to various food and health care applications. The LAB-based processes for mycotoxin management are more effective, eco-friendly, and low-cost than physical and chemical approaches. The toxicity, novel preventive measures, binding nature, and molecular mechanisms of mycotoxins{\textquoteright} detoxification using LAB have been highlighted in this review.

}, keywords = {Food safety, Fusarium species, Lactic acid bacteria, management, Mycotoxin}, issn = {0141-5492}, doi = {10.1007/s10529-022-03293-4}, author = {Navale, Vishwambar D. and Vamkudoth, Koteswara Rao} } @article {48051, title = {Tridentate NacNac stabilized tin and nickel complexes: access to a monomeric nickel hydride and its catalytic application}, journal = {Inorganic Chemistry}, volume = {61}, year = {2022}, month = {OCT}, pages = {17370-17377}, type = {Article}, abstract = {

The transmetalation reaction of picolyl-supported tridentate nacnac germylene monochloride [2,6-iPr2-C6H3NC-(Me)CHC(Me)NH(CH2py)]GeCl (1) (py = pyridine) with SnCl2 results in an analogous stannylene chloride (2). The three -coordinated stannylenium cation [{2,6-iPr2-C6H3NC(Me)CHC-(Me)NH(CH2py)}Sn]+ with SnCl3- as a counteranion (3) has been generated through the abstraction of chloride ligand from 2 using an additional equivalent of SnCl2. Instead of forming a donor-acceptor complex, 2 undergoes a facile redox trans-metalation reaction with Ni(COD)2 (COD = cyclooctadiene) and CuCl to afford analogous nickel and copper complexes [2,6-iPr2-C6H3NC(Me)CHC(Me)NH(CH2py)]MCl [M = Ni (4) and Cu (5)]. The reactions of 4 with potassium tri-sec-butylborohydride (commonly known as K-selectride) and AgSbF6 provide access to monomeric Ni(II) hydride, [2,6-iPr2-C6H3NC(Me)CHC(Me)NH(CH2py)]NiH (6) and a Ni(II) cation, [{2,6-iPr2- C6H3NC(Me)CHC(Me)NH(CH2py)}Ni][SbF6] (7), respectively. 6 was found to be an effective catalyst for the hydroboration of amides.

}, issn = {0020-1669}, doi = {10.1021/acs.inorgchem.2c03227}, author = {Pahar, Sanjukta and Sharma, Vishal and Mahata, Biplab and George, Christy P. and Sharma, Himanshu and Vanka, Kumar and Sen, Sakya S.} } @article {48047, title = {Tuning of work function of ZnO by doping and co-doping: an investigation using X-ray photoelectron spectroscopy}, journal = {Thin Solid Films}, volume = {761}, year = {2022}, month = {NOV}, pages = {139538}, type = {Article}, abstract = {

The shift in the work function of the ZnO thin film upon varying codoping ratio has been investigated by X-ray photoelectron spectroscopy. A notable shift of 0.2 eV in the work function was achieved in the films when the Al: In doping ratio was changed from 0:10 to 10:0. The elemental composition of the dopants obtained from XPS analysis showed the presence of more amount of In dopant than Al in codoped ZnO films. In this way a clear understanding of the variation in electrical properties on dopant ratio is obtained. A decrease in work function was also observed with the increase in free carrier concentration when the codopant ratio is changed. The effects of Burstein moss, band narrowing, and band renormalization observed in the bandgap were explained by an upward and downward shift of valence band maxima of the corresponding thin films. The controllable work function of the codoped ZnO films by varying the doping ratio offers excellent potential advantages in optoelectronic devices.

}, keywords = {Indium -Aluminum co -doping, Spray coating, thin film, Work function, X-ray photoelectron spectroscopy, Zinc oxide}, issn = {0040-6090}, doi = {10.1016/j.tsf.2022.139538}, author = {Soumya, K. and Selvam, I. Packia and Vinod, C. P. and Potty, S. N.} } @article {48181, title = {Tuning the hybridization and charge polarization in metal nanoparticles dispersed over Schiff base functionalized SBA-15 enhances CO2 capture and conversion to formic acid}, journal = {Journal of Materials Chemistry A}, volume = {10}, year = {2022}, month = {SEP}, pages = {18354-18362}, type = {Article}, abstract = {

Different Schiff base functionalized SBA-15 materials were synthesized through condensation reactions between 3-aminopropyltriethoxysilane (APTES) and different aldehydes (glutaraldehyde and butyraldehyde) over a mesoporous silica, SBA-15 (APTES-GLU/SBA-15 and APTES-BUT/SBA-15). Both static and dynamic experiments have been used for testing the CO2 capture efficiency of these materials. The hybridization of the N atom in APTES has been tuned from sp(3) to sp(2) upon condensation facilitating optimum CO2 capture in the direct synthesis of APTES-GLU/SBA-15. The undesirable oxides of nitrogen have been removed during the synthesis process to improve the CO2 capture efficiency. These materials were employed as supports for Pd-Ag and Pd-Ni bimetallic systems for the selective conversion of the captured CO2 to formic acid (FA) in 0.5 M KHCO3 solution. The Pd-Ni catalyst system exhibited enhanced CO2 to FA conversion activity compared to other heterogeneous systems, which is similar to 4 times better than that of the Pd-Ag system in this study. The X-ray absorption studies over the catalyst material confirmed that the relatively electron-deficient Ni in Pd-Ni compared to Ag in Pd-Ag favoured higher charge polarization between the metals in the Pd-Ni system enhancing the CO2 to FA conversion. The experimental observations are well supported by the DFT calculations.

}, issn = {2050-7488}, doi = {10.1039/d2ta03690h}, author = {Cherevotan, Arjun and Ray, Bitan and Yadav, Anish and Bagchi, Debabrata and Singh, Ashutosh Kumar and Riyaz, Mohd and Churipard, Sathyapal R. and Naral, Vinay and Kaur, Komalpreet and Gautam, Ujjal K. and Vinod, Chathakudath P. and Peter, Sebastian C.} } @article {47829, title = {Ultrathin twisty PdNi alloy nanowires as highly active ORR electrocatalysts exhibiting morphology-induced durability over 200 K cycles}, journal = {Nano Letters}, volume = {22}, year = {2022}, month = {JAN}, pages = {246-254}, type = {Article}, abstract = {Even though the anion exchange membrane fuel cells have many advantages, the stability of their electrocatalysts for oxygen reduction reaction (ORR) has remained remarkably poor. We report here on the ultrathin twisty PdNi-alloy nanowires (NWs) exhibiting a very low reaction overpotential with an E1/2 \~{} 0.95 V versus RHE in alkaline media maintained over 200 K cycles, the highest ever recorded for an electrocatalyst. The mass activity of the used NWs is >10 times higher than fresh commercial Pt/C. Therein, Ni improves the Pd d-band center for a more efficient ORR, and its leaching continuously regenerates the surface active sites. The twisty nanowire morphology imparts multiple anchor points on the electrode surface to arrest their detachment or coalescence and extra stability from self-entanglement. The significance of the NW morphology was further confirmed from the high-temperature durability studies. The study demonstrates that tailoring the number of contact points to the electrode-surface may help realize commercial-grade stability in the highly active electrocatalysts.}, doi = {10.1021/acs.nanolett.1c03704}, author = {Sahoo, Lipipuspa and Garg, Reeya and Kaur, Komalpreet and Vinod, C. P. and Gautam, Ujjal K.} } @article {47732, title = {Unraveling the reaction mechanism of selective C9 monomeric phenols formation from lignin using Pd-Al2O3-activated biochar catalyst}, journal = {Bioresource Technology}, volume = {344}, year = {2022}, month = {JAN}, pages = {126204}, type = {Article}, abstract = {The conversion of biomass-derived lignin to valuable monomeric phenols at high selectivity is of paramount importance for sustainable biorefineries. In this study, a novel Pd-Al2O3 supported on activated biochar catalyst is developed for lignin hydrogenolysis. The catalyst characterization revealed that the (1 1 1) planes of both of Pd-0 and Al2O3 were exposed to the surface. The maximum lignin conversion of 70.4\% along with high liquid yield (similar to 57 wt\%) was obtained at 240 degrees C, 3 h and 3 MPa H-2 pressure. The total monomeric phenols yield in the liquid was 51.6 wt\%, out of which C9 monomeric guaiacols constituted similar to 30.0 wt\% with 38.0\% selectivity to 4-propyl guaiacol. Using the reaction intermediate, coniferyl alcohol, chemoselective hydrogenation of C-alpha=C-beta is proved to occur over the Pd site, while dehydroxylation of C-gamma-OH is shown to occur over the alumina site. An impressive carbon atom economy of 60\% was achieved for the production of monomeric phenols.}, keywords = {Hydrogenolysis, lignin, Mechanism, Pd-Al/activated biochar, Propanol guaiacol, Propyl guaiacol}, issn = {0960-8524}, doi = {10.1016/j.biortech.2021.126204}, author = {Gurrala, L. and Kumar, M. M. and Yerrayya, Attada and Kandasamy, Prabu and Castano, Pedro and Raja, T. and Pilloni, Giovanni and Paek, C. and Vinu, R.} } @article {48200, title = {Unravelling faradaic electrochemical efficiencies over Fe/Co spinel metal oxides using surface spectroscopy and microscopy techniques}, journal = {Nanoscale}, volume = {14}, year = {2022}, month = {NOV }, pages = {15928-15941}, type = {Article}, abstract = {

Cobalt and iron metal-based oxide catalysts play a significant role in energy devices. To unravel some interesting parameters, we have synthesized metal oxides of cobalt and iron (i.e. Fe2O3, Co3O4, Co2FeO4 and CoFe2O4), and measured the effect of the valence band structure, morphology, size and defects in the nanoparticles towards the electrocatalytic hydrogen evolution reaction (HER), the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). The compositional variations in the cobalt and iron precursors significantly alter the particle size from 60 to \<10 nm and simultaneously the shape of the particles (cubic and spherical). The Tauc plot obtained from the solution phase ultraviolet (UV) spectra of the nanoparticles showed band gaps of 2.2, 2.3, 2.5 and 2.8 eV for Fe2O3, Co3O4, Co2FeO4 and CoFe2O4, respectively. Further, the valence band structure and work function analysis using ultraviolet photoelectron spectroscopy (UPS) and core level X-ray photoelectron spectroscopy (XPS) analyses provided better structural insight into metal oxide catalysts. In the Co3O4 system, the valence band structure favors the HER and Fe2O3 favors the OER. The composites Co2FeO4 and CoFe2O4 show a significant change in their core level (O 1s, Co 2p and Fe 2p spectra) and valence band structure. Co3O4 shows an overpotential of 370 mV against 416 mV for Fe2O3 at a current density of 2 mA cm(-2) for the HER. Similarly, Fe2O3 shows an overpotential of 410 mV against the 435 mV for Co3O4 at a current density of 10 mA cm(-2) for the OER. However, for the ORR, Co3O4 shows 70 mV improvement in the half-wave potential against Fe2O3. The composites (Co2FeO4 and CoFe2O4) display better performance compared to their respective parent oxide systems (i.e., Co3O4 and Fe2O3, respectively) in terms of the ORR half-wave potential, which can be attributed to the presence of the oxygen vacancies over the surface in these systems. This was further corroborated in density functional theory (DFT) simulations, wherein the oxygen vacancy formation on the surface of CoFe2O4(001) was calculated to be significantly lower (similar to 50 kJ mol(-1)) compared to Co3O4 (001). The band diagram of the nanoparticles constructed from the various spectroscopic measurements with work function and band gap provides in-depth understanding of the electrocatalytic process.

}, issn = {2040-3364}, doi = {10.1039/d2nr04170g}, author = {Kashyap, Varchaswal and Pandikassala, Ajmal and Singla, Gourav and Khan, Tuhin Suvra and Haider, M. Ali and Vinod, C. P. and Kurungot, Sreekumar} } @article {48162, title = {Versatile chemistry of six-membered NHC with boranes: bromination at sp(3) borane, activation of the B-H bond of HBpin, and ring expansion of NHC}, journal = {Dalton Transactions}, volume = {51}, year = {2022}, month = {OCT}, pages = {14452-14457}, type = {Article}, abstract = {

The NHC.borane chemistry has been majorly restricted to imidazol-2-ylidene classes of carbenes. In our previous communication, we reported the synthesis of 6-SIDipp center dot BH3 [6-SIDipp = 1,3-di(2,6-diisopropylphenyl) tetrahydropyrimidine-2-ylidene] and its electrophilic substitution reaction with iodine. Here, we have shown selective bromination of a 6-SIDipp stabilized sp(3) B-H bond. Treatment of 1.2 equivalents of N-bromosuccinamide with 6-SIDipp center dot BH3 gives a mixture of mono- and disubstituted products 6-SIDipp center dot BH2Br (1) and 6-SIDipp center dot BHBr2 (2). However, the reactions with alkyl bromides or carbon tetrabromide resulted in 6-SIDipp center dot BH2Br (1) selectively. Exploration of the chemistry of 6-SIDipp with BHCl2 and 9-BBN (9-borabicyclo[3.3.1]nonane) led to mono-6-SIDipp adducts 3 and 6a. Furthermore, 6a undergoes ring expansion to afford a seven-membered product, 6b, under mild conditions. Unlike BHCl2 or 9-BBN, the B-H bond of HBpin undergoes oxidative addition upon reaction with 6-SIDipp, epitomizing the first example (7) of a B-H bond insertion at NHCs. The analogous reactivity with HBcat led to a tetra-hydropyrimidinium salt with B(cat)(2) as a counteranion (8).

}, issn = {1477-9226}, doi = {10.1039/d2dt01707e}, author = {Kundu, Gargi and Dixit, Ruchi and Tothadi, Srinu and Vanka, Kumar and Sen, Sakya S.} } @article {48032, title = {Well-defined calcium compound catalyzes trimerization of arylisocyanates into 1,3,5-triarylisocyanurates}, journal = {ChemCatChem}, volume = {14}, year = {2022}, month = {JUN }, pages = {e202101788}, type = {Article}, abstract = {

We report the synthesis of a calcium complex (2) bearing a tetradentate monoanionic ligand with a diaminoethane core and phenolate and pyridine peripheral donors. Single crystal X-ray studies on 2 revealed that LiI was also co-crystallized, leading to a four-membered ring with four different elements. 2 was found to be an efficient catalyst for the cyclotrimerization of a variety of aromatic isocyanates under mild conditions.

}, keywords = {calcium, Cyclotrimerization, Isocyanurates, Tetradentate ligand}, issn = {1867-3880}, doi = {10.1002/cctc.202101788}, author = {Kumar, Rohit and Sharma, Vishal and Jain, Shailja and Sharma, Himanshu and Vanka, Kumar and Sen, Sakya S.} } @article {48335, title = {2D layered nanomaterials as fillers in polymer composite electrolytes for lithium batteries}, journal = {Advanced Energy Materials}, volume = {13}, year = {2023}, month = {APR}, type = {Review}, abstract = {

Polymer composite electrolytes (PCEs), i.e., materials combining the disciplines of polymer chemistry, inorganic chemistry, and electrochemistry, have received tremendous attention within academia and industry for lithium-based battery applications. While PCEs often comprise 3D micro- or nanoparticles, this review thoroughly summarizes the prospects of 2D layered inorganic, organic, and hybrid nanomaterials as active (ion conductive) or passive (nonion conductive) fillers in PCEs. The synthetic inorganic nanofillers covered here include graphene oxide, boron nitride, transition metal chalcogenides, phosphorene, and MXenes. Furthermore, the use of naturally occurring 2D layered clay minerals, such as layered double hydroxides and silicates, in PCEs is also thoroughly detailed considering their impact on battery cell performance. Despite the dominance of 2D layered inorganic materials, their organic and hybrid counterparts, such as 2D covalent organic frameworks and 2D metal-organic frameworks are also identified as tuneable nanofillers for use in PCE. Hence, this review gives an overview of the plethora of options available for the selective development of both the 2D layered nanofillers and resulting PCEs, which can revolutionize the field of polymer-based solid-state electrolytes and their implementation in lithium and post-lithium batteries.

}, keywords = {2D materials, clay minerals, covalent organic frameworks, metal-organic frameworks, MXene, polymer composite electrolyte, solid-state batteries}, issn = {1614-6832}, doi = {10.1002/aenm.202203326}, author = {Vijayakumar, Vidyanand and Ghosh, Meena and Asokan, Kiran and Sukumaran, Santhosh Babu and Kurungot, Sreekumar and Mindemark, Jonas and Brandell, Daniel and Winter, Martin and Nair, Jijeesh Ravi} } @article {48753, title = {Activation of the olefinic C-H bond of NHC and NHO by perimidine-based silicon and germanium compounds}, journal = {Organometallics}, volume = {42}, year = {2023}, month = {JUL}, pages = {1909-1917}, type = {Article}, abstract = {

In this manuscript, several backbonegermylene-functionalized zwitterioniccompounds were prepared conveniently from the corresponding N-heterocycliccarbenes or N-heterocyclic olefins in a single step through backboneC-H activation. Our initial motivation was to generate a silylenefrom C10H6(Me3SiN)(2)SiHCl(2) using ItBu [ItBu= (1,3-ditert-butyl)imidazol-2-ylidene], but instead, the reactionled to deprotonation from the imidazolium backbone of ItBu, forming the imidazolium salt with a silyl backbone at the C4position (3). We presumed that the reaction proceededthrough the generation of an ephemeral silylene. We subsequently preparedthe analogous germylene (4) and reacted it with IDipp[IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene], ItBu, and IDipp=CH2. Spectroscopic and crystallographicanalysis of these complexes revealed that, in all cases, there wasdeprotonation from the backbone and formation of zwitterionic products(5-7). When the hydrogen in the NHCbackbone was replaced with methyl groups such as IDipp(Me) (1,3-bis(2,6-diisopropylphenyl)-4,5-dimethylimidazol-2-ylidene),simple adduct formation occurred, exemplified by the isolation ofIDipp(Me)\& BULL;Ge(NSiMe3)(2)C10H6 (8).

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.3c00167}, author = {Gour, Kritika and Pramanik, Debjit and Dash, Soumya Ranjan and Tothadi, Srinu and Vanka, Kumar and Sen, Sakya S.} } @article {48935, title = {Active site engineering and theoretical aspects of {\textquoteleft}{\textquoteleft}Superhydrophilic{\textquoteright}{\textquoteright} nanostructure array enabling efficient overall water electrolysis}, journal = {Small}, volume = {19}, year = {2023}, month = {DEC}, type = {Article}, abstract = {

The rational design of noble metal-free electrocatalysts holds great promise for cost-effective green hydrogen generation through water electrolysis. In this context, here, the development of a superhydrophilic bifunctional electrocatalyst that facilitates both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline conditions is demonstrated. This is achieved through the in situ growth of hierarchical NiMoO4@CoMoO4 center dot xH(2)O nanostructure on nickel foam (NF) via a two-step hydrothermal synthesis method. NiMoO4@CoMoO4 center dot xH(2)O/NF facilitates OER and HER at the overpotentials of 180 and 220 mV, respectively, at the current density of 10 mA cm(-2). The NiMoO4@CoMoO4 center dot xH(2)O/NF parallel to NiMoO4@CoMoO4 center dot xH(2)O/NF cell can be operated at a potential of 1.60 V compared to 1.63 V displayed by the system based on the Pt/C@NF parallel to RuO2@NF standard electrode pair configuration at 10 mA cm(-2) for overall water splitting. The density functional theory calculations for the OER process elucidate that the lowest Delta G of NiMoO4@CoMoO4 compared to both Ni and NiMoO4 is due to the presence of Co in the OER catalytic site and its synergistic interaction with NiMoO4. The preparative strategy and mechanistic understanding make the windows open for the large-scale production of the robust and less expensive electrode material for the overall water electrolysis.

}, keywords = {density functional theory (DFT) study, hydrogen evolution reaction (HER), Hydrothermal synthesis, oxygen evolution reaction (OER), superhydrophilic nanostructures, synergistic interaction, water electrolysis}, issn = {1613-6810}, doi = {10.1002/smll.202304143}, author = {Barik, Sidharth and Kharabe, Geeta Pandurang and Illathvalappil, Rajith and Singh, Chandrodai Pratap and Kanheerampockil, Fayis and Walko, Priyanka S. and Bhat, Suresh K. and Devi, R. Nandini and Vinod, C. P. and Krishnamurty, Sailaja and Kurungot, Sreekumar} } @article {48749, title = {Biosynthesis of gold nanoparticles by Penicillium rubens and catalytic detoxification of ochratoxin A and organic dye pollutants}, journal = {International Microbiology}, volume = {26}, year = {2023}, month = {NOV}, pages = {765-780}, type = {Article}, abstract = {

The environmental pollution caused by chemical dyes is a growing concern nowadays. Limitations of traditional methods opened the route for nanotechnology; owing to the versatile properties of nanomaterials, gold nanoparticles (AuNPs) became a potential strategy for different applications. In the present study, biosynthesis of gold nanoparticles (BioAuNPs) was carried out by reacting chloroauric acid (HAuCl4) with cell-free filtrate of Penicillium rubens sp. nov. NCIM 1937. The AuNPs were then characterized by UV-visible spectroscopy, HR-TEM, FTIR, and DLS analysis to further examine their efficacious biosynthesis and morphological properties including size, shape, and stability. The biogenic AuNPs are polydisperse in nature, with a mean size of 14.92 +/- 5 nm. These AuNPs exhibited promising antimicrobial activity against Escherichia coli NCIM-2065, Bacillus subtilis NCIM-2010, and Penicillium verrucosum MTCC 4935. In vitro quantitative HPLC results revealed that BioAuNPs significantly inhibited the biosynthesis of ochratoxin A (OTA). Microbial fuel cells (MFCs) are intriguing for power generation and wastewater treatment since they can directly transform chemical energy stored in organic matter to electricity by extracellular electron transfer (EET) via membrane proteins. AuNPs also showed excellent potential for dye degradation of organic pollutants, viz., methylene blue (MB), phenol red (PR), bromothymol blue (BTB), Congo red (CR), and 4-nitrophenol (4-NP). All dye removal efficiencies were estimated and fitted to pseudo-first-order processes using kinetic rate constants (Ka).The present study reveals a simple, original, and eco-friendly method for the synthesis of multifunctional biogenic AuNPs that could be effective in OTA detoxification in food products and organic pollutant removal during wastewater treatment for a sustainable environment.

}, keywords = {Catalytic organic dye degradation, gold nanoparticles, Ochratoxin A, Penicillium rubens, Penicillium verrucosum}, issn = {1139-6709}, doi = {10.1007/s10123-023-00341-5}, author = {Bhandari, Yogesh and Varma, Sanjana and Sawant, Amol and Beemagani, Sreelatha and Jaiswal, Neha and Chaudhari, Bhushan P. and Vamkudoth, Koteswara Rao} } @article {48490, title = {Can Li atoms anchored on boron- and nitrogen-doped graphene catalyze dinitrogen molecules to ammonia? a DFT study}, journal = {ChemPhysChem}, volume = {24}, year = {2023}, month = {JUN}, type = {Article}, abstract = {

The most successful electrochemical conversion of ammonia from dinitrogen molecule reported to date is through a Li mediated mechanism. In the framework of the above fact and that Li anchored graphene is an experimentally feasible system, the present work is a computational experiment to identify the potential of Li anchored graphene as a catalyst for N-2 to NH3 conversion as a function of (a) minimum number of Li atoms needed for anchoring on graphene sheets and (b) the role of chemical modification of graphene surfaces. The studies bring forth an understanding that Li anchored graphene sheets are potential catalysts for ammonia conversion with preferential adsorption of N-2 through end-on configuration on Li atoms anchored on doped and pristine graphene surfaces. This mode of adsorption being characteristic of Nitrogen Reduction Reaction (NRR) through enzymatic pathway, examination of the same followed by analysis of electronic properties demonstrates that tri-Li atoms (Tri Atom Catalysts, TACs) are more efficient as catalysts for NRR as compared to two Li atoms (Di Atom Catalysts, DACs). Either way, the rate determining step was found to be *NH2 -\>*NH3 step (mixed pathway) with Delta G(max)=1.02 eV and *NH2-*NH3 -\>*NH2 step (enzymatic pathway) with Delta G(max)=1.11 eV for 1B doped TAC and DAC on graphene sheet, respectively. Consequently, this work identifies the viability of Li anchored graphene based 2-D sheets as hetero-atom catalyst for NRR.

}, keywords = {computational chemistry, Graphene Sheet, heterogeneous catalysis, Li Nanoparticles, Nitrogen Reduction Reaction}, issn = {1439-4235}, doi = {10.1002/cphc.202200750}, author = {Verma, Tushar Singh and Samal, Pragnya Paramita and Selvaraj, Kaliaperumal and Krishnamurty, Sailaja} } @article {48794, title = {Carbohydrate recognition using metal-ligand assemblies}, journal = {Organic \& Biomolecular Chemistry}, volume = {21}, year = {2023}, month = {JUL }, pages = {5492-5505}, type = {Review}, abstract = {

Carbohydrate-binding proteins, known as lectins, play a wide range of vital roles in cellular and pathological processes. Mimicking lectins to achieve specific molecular recognition of carbohydrates in organic and aqueous media using artificial receptors is challenging due to the synthetic hurdles of receptors and structural similarities between sugars. Carbohydrate recognition using non-covalent interactions remains a vast topic. This review summarises the recognition of carbohydrates using metal-ligand assemblies, including metallosupramolecules, macrocycles, and cages. It also highlights the challenges and future directions in the field.

}, issn = {1477-0520}, doi = {10.1039/d3ob00649b}, author = {Ahamed, Rafiq and Venkatesh, Jayashree and Srithar, Rakshantha and Gaikwad, Sudhakar and Pramanik, Susnata} } @article {48793, title = {Cocrystal approach to modulate the photoluminescent properties of a GFP chromophore analogue: role of halogen/hydrogen bonding in achieving a wide range of solid-state fluorescence emissions}, journal = {Crystal Growth \& Design}, volume = {23}, year = {2023}, month = {JUN }, pages = {5052-5065}, type = {Article}, abstract = {

Fine-tuning the photophysical properties of fluorescentorganicsolids is essential to attain multicolor displays and meet the demandfor futuristic light-emitting materials. Here, we report the tunableluminescence of a green fluorescent protein (GFP) chromophore analogue,3,4,5-TIA (A), based on the formation of two-component molecular cocrystalswith six different coformers. Coformers selected to synthesize thebinary cocrystals include 1,4-diiodotetrafluorobenzene (B), perfluoronaphthalene(C), 1,4-dibromotetrafluorobenzene (D), 2,3,5,6-tetrafluoroterephthalicacid (E), benzene-1,2,4,5-tetracarbonitrile (F), and benzene-1,2,4,5-tetracarboxylicacid (G). Interestingly, the cocrystals A center dot C and A center dot Fshowed molecular crystal polymorphism with a slight variation in fluorescence,revealing an aggregation-induced emission (AIE). A crystal structureanalysis showed the interplay of hydrogen bonding, halogen bonding,and aromatic pi-stacking interactions in associating neutralsolid components in the cocrystal. All of the novel cocrystals displayeda wide range of photoluminescence ranging from blue to dark orange.The time-dependent density functional theory (TD-DFT) calculationsindicate the changes in the energy level structures (HOMO to LUMO)in cocrystals that resulted in variations in fluorescence emission.The study aims to further understand the structure-propertyrelationship between molecular arrangement and photoluminescence. Cocrystals of a GFPc analogue with differentcoformers displayeda wide range of fluorescence emissions ranging from blue to dark orangewith varying quantum yields. With similar geometries of pi-stackinginteractions, hydrogen and halogen bonding have played a vital rolein fine-tuning the photoluminescence; halogen bonding leads to a blueshift, and hydrogen bonding results in a red shift.

}, issn = {1528-7483}, doi = {10.1021/acs.cgd.3c00307}, author = {Mali, Bhupendra P. and Dash, Soumya Ranjan and Annadhasan, Mari and Biswas, Anupam and Manoj, Kochunnoonny and Vanka, Kumar and Gonnade, Rajesh G.} } @article {48795, title = {COF-supported zirconium oxyhydroxide as a versatile heterogeneous catalyst for Knoevenagel condensation and nerve agent hydrolysis}, journal = {iScience}, volume = {26}, year = {2023}, month = {NOV}, pages = {108088}, type = {Article}, abstract = {

A composite of catalytic Lewis acidic zirconium oxyhydroxides (8 wt \%) and a covalent organic framework (COF) was synthesized. X-ray diffraction and infrared (IR) spectroscopy reveal that COF{\textquoteright}s structure is pre-served after loading with zirconium oxyhydroxides. Electron microscopy confirms a homogeneous distri-bution of nano-to sub-micron-sized zirconium clusters in the COF. 3D X-ray tomography captures the micron-sized channels connecting the well-dispersed zirconium clusters on the COF. The crystalline ZrOx(OH)(y)@COF{\textquoteright}s nanostructure was model-optimized via simulated annealing methods. Using 0.8 mol \% of the catalyst yielded a turnover number of 100-120 and a turnover frequency of 160-360 h(-1) for Knoevenagel condensation in aqueous medium. Additionally, 2.2 mol \% of catalyst catalyzes the hy-drolysis of dimethyl nitrophenyl phosphate, a simulant of nerve agent Soman, with a conversion rate of 37\% in 180 min. The hydrolytic detoxification of the live agent Soman is also achieved. Our study unveils COF-stabilized ZrOx(OH)(y) as a new class of zirconium-based Lewis + Bronsted-acid catalysts.

}, doi = {10.1016/j.isci.2023.108088}, author = {Shekhar, Pragalbh and Devulapalli, Venkata Swaroopa Datta and Reji, Reshma and Singh, Himan Dev and Jose, Aleena and Singh, Piyush and Torris, Arun and Vinod, Chatakudath P. and Tokarz III, John A. and Mahle, John J. and Peterson, Gregory W. and Borguet, Eric and Vaidhyanathan, Ramanathan} } @article {48687, title = {On the competition between six-membered and five-membered NHC towards alane centered ring expansion}, journal = {Chemical Communications}, volume = {59}, year = {2023}, month = {JUL}, pages = {8540-8543}, type = {Article}, abstract = {

The combination of 6-SIDipp center dot AlH3 (1) and 5-IDipp resulted in the ring expansion of 6-NHC, while the five-membered NHC remained unchanged, which was subsequently explained by DFT studies. Besides, the substitution chemistry of 1 was also studied with TMSOTf and I-2, which gave rise to the substitution of a hydride by triflate or iodide ligands.

}, issn = {1359-7345}, doi = {10.1039/d3cc02063k}, author = {Balayan, Kajal and Sharma, Himanshu and Vanka, Kumar and Ravindranathan, Sapna and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {48480, title = {Comprehensive analysis of physiological and metabolomic responses to drought reveals specific modulation of acquired tolerance mechanisms in rice}, journal = {Physiologia Plantarum}, volume = {175}, year = {2023}, month = {MAY}, pages = {e13917}, type = {Article}, abstract = {

Mild stresses induce {\textquoteleft}{\textquoteleft}acquired tolerance traits{\textquoteright}{\textquoteright} (ATTs) that provide tolerance when stress becomes severe. Here, we identified the genetic variability in ATTs among a panel of rice germplasm accessions and demonstrated their relevance in protecting growth and productivity under water-limited conditions. Diverse approaches, including physiological screens, association mapping and metabolomics, were adopted and revealed 43 significant marker-trait associations. Nontargeted metabolomic profiling of contrasting genotypes revealed 26 {\textquoteleft}{\textquoteleft}tolerance-related-induced{\textquoteright}{\textquoteright} primary and secondary metabolites in the tolerant genotypes (AC-39000 and AC-39020) compared to the susceptible one (BPT-5204) under water-limited condition. Metabolites that help maintain cellular functions, especially Calvin cycle processes, significantly accumulated more in tolerant genotypes, which resulted in superior photosynthetic capacity and hence water use efficiency. Upregulation of the glutathione cycle intermediates explains the ROS homeostasis among the tolerant genotypes, maintaining spikelet fertility, and grain yield under stress. Bioinformatic dissection of a major effect quantitative trait locus on chromosome 8 revealed genes controlling metabolic pathways leading to the production of osmolites and antioxidants, such as GABA and raffinose. The study also led to the identification of specific trait donor genotypes that can be effectively used in translational crop improvement activities.

}, issn = {0031-9317}, doi = {10.1111/ppl.13917}, author = {Doddaraju, Pushpa and Dharmappa, Prathibha M. and Thiagarayaselvam, Aarthy and Vijayaraghavareddy, Preethi and Bheemanahalli, Raju and Basavaraddi, Priyanka A. and Malagondanahalli, Mohan Kumar V. and Kambalimath, Sumanth and Thulasiram, Hirekodathakallu V. and Sreeman, Sheshshayee M.} } @article {48319, title = {Comprehensive molecular and clinical investigation of approved Anti-HCV drugs repurposing against SARS-CoV-2 infection: a glaring gap between benchside and bedside medicine}, journal = {Vaccines}, volume = {11}, year = {2023}, month = {MAR}, pages = {515}, type = {Article}, abstract = {

The limited availability of effective treatment against SARS-CoV-2 infection is a major challenge in managing COVID-19. This scenario has augmented the need for repurposing anti-virals for COVID-19 mitigation. In this report, the anti-SARS-CoV-2 potential of anti-HCV drugs such as daclatasvir (DCV) or ledipasvir (LDP) in combination with sofosbuvir (SOF) was evaluated. The binding mode and higher affinity of these molecules with RNA-dependent-RNA-polymerase of SARS-CoV-2 were apparent by computational analysis. In vitro anti-SARS-CoV-2 activity depicted that SOF/DCV and SOF/LDP combination has IC50 of 1.8 and 2.0 mu M, respectively, comparable to remdesivir, an approved drug for COVID-19. Furthermore, the clinical trial was conducted in 183 mild COVID-19 patients for 14 days to check the efficacy and safety of SOF/DCV and SOF/LDP compared to standard of care (SOC) in a parallel-group, hybrid, individually randomized, controlled clinical study. The primary outcomes of the study suggested no significant difference in negativity after 3, 7 and 14 days in both treatments. None of the patients displayed any worsening in the disease severity, and no mortality was observed in the study. Although, the post hoc exploratory analysis indicated significant normalization of the pulse rate showed in SOF/DCV and SOF/LDP treatment vs. SOC. The current study highlights the limitations of bench side models in predicting the clinical efficacy of drugs that are planned for repurposing.

}, keywords = {antiviral, COVID-19, daclatasvir, ledipasvir, SARS-CoV-2, sofosbuvir}, doi = {10.3390/vaccines11030515}, author = {Bansode, Sneha and Singh, Pawan Kumar and Tellis, Meenakshi and Chugh, Anita and Deshmukh, Narendra and Gupta, Mahesh and Verma, Savita and Giri, Ashok and Kulkarni, Mahesh and Joshi, Rakesh and Chaudhary, Dhruva} } @article {49130, title = {Comprehensive molecular docking and dynamic simulations for drug repurposing of clinical drugs against multiple cancer kinase targets}, journal = {Journal of Biomolecular Structure and Dynamics}, volume = {41}, year = {2023}, month = {NOV }, pages = {7735-7743}, type = {Article}, abstract = {

Drug repurposing is a method to identify novel therapeutic agents from the existing drugs and clinical compounds. In the present comprehensive work, molecular docking, virtual screening and dynamics simulations were carried out for ten cancer types viz breast, colon, central nervous system, leukaemia, melanoma, ovarian, prostate, renal and lung (non-small and small cell) against validated eighteen kinase targets. The study aims to understand the action of chemotherapy drugs mechanism through binding interactions against selected targets via comparative docking simulations with the state-art molecular modelling suits such as MOE, Cresset-Flare, AutoDock Vina, GOLD and GLIDE. Chemotherapeutic drugs (n = 112) were shortlisted from standard drug databases with appropriate chemoinformatic filters. Based on docking studies it was revealed that leucovorin, nilotinib, ellence, thalomid and carfilzomib drugs possessed potential against other cancer targets. A library was built to enumerate novel molecules based on the scaffold and functional groups extracted from known drugs and clinical compounds. Twenty novel molecules were prioritised further based on drug-like attributes. These were cross docked against 1MQ4 Aurora-A Protein Kinase for prostate cancer and 4UYA Mitogen-activated protein kinase for renal cancer. All docking programs yielded similar results but interestingly AutoDock Vina yielded the lowest RMSD with the native ligand. To further validate the final docking results at atomistic level, molecular dynamics simulations were performed to ascertain the stability of the protein-ligand complex. The study enables repurposing of drugs and lead identification by employing a host of structure and ligand based virtual screening tools and techniques. Communicated by Ramaswamy H. Sarma

}, keywords = {chemotherapeutic drugs, Drug repurposing, Molecular docking, molecular simulation (MD), structure-based drug designing (SBDD), virtual screening}, issn = {0739-1102}, doi = {10.1080/07391102.2022.2124453}, author = {Shaikh, Nilofer and Linthoi, R. K. and Swamy, V, K. and Karthikeyan, Muthukumarasamy and Vyas, Renu} } @article {48985, title = {Comprehensive study on solomonamides: total synthesis, stereochemical revision, and SAR studies toward identification of simplified lead}, journal = {Journal of Organic Chemistry}, volume = {88}, year = {2023}, month = {DEC }, pages = {17088-17133}, type = {Article}, abstract = {

Solomonamides, a pair of macrocyclic peptide natural products originating from marine sources, have garnered significant attention within the synthetic community owing to their marked anti-inflammatory efficacy and intricate molecular architectures. In this paper, we present a very detailed investigation into solomonamides, including the challenges associated with the total synthesis, the evolution of our synthetic strategies, structural reassignment, synthesis of all possible stereoisomeric macrocycles, biological assessment, structure-activity relationship (SAR) studies, etc. Within the ambit of this total synthesis, diverse strategies for macrocyclization were rigorously explored, encompassing the Friedel-Crafts acylation, cyclization involving the aniline NH2 moiety, macrolactamization utilizing Gly-NH2, and Heck macrocyclization methodologies. In addition, an array of intriguing chemical transformations were devised, including but not limited to photo-Fries rearrangement, Wacker oxidation, ligand-free Heck macrocyclization, oxidative cleavage of indole, synthesis of contiguous stereocenters via substrate/reagent-controlled protocols, and simultaneous making and breaking of olefinic moieties. The findings of this investigation revealed a structurally simplified lead compound. Remarkably, the lead compound, while possessing structural simplification in comparison to the intricate solomonamide counterparts, demonstrates equipotent in vivo anti-inflammatory efficacy.

}, issn = {0022-3263}, doi = {10.1021/acs.joc.3c01987}, author = {Jachak, Gorakhnath R. and Kashinath, K. and Vasudevan, N. and Athawale, Paresh R. and Choudhury, Rahul and Dange, Santoshkumar S. and Agarwal, Heena and Barthwal, Manoj Kumar and Reddy, D. Srinivasa} } @article {48283, title = {Computational insights into the iron-catalyze d magnesium-me diate d hydroformylation of alkynes}, journal = {Journal of Organometallic Chemistry}, volume = {986}, year = {2023}, month = {FEB}, pages = {122621}, type = {Article}, abstract = {

Iron is one of the most abundant transition metals in the earth{\textquoteright}s crust. It has attracted a lot of attention due to its low toxicity, bio-compatibility, and high natural abundance. Iron-catalyzed hydroamination, hydroalkoxylation, hydrocarboxylation, hydrosilylation, hydroboration, hydrophosphination, hydromagnesiation, and carbonylation reactions have therefore been developed over the past decades. However, despite many experimental and theoretical studies, a complete mechanistic understanding of iron-catalyzed hydrofunctionalisation at the molecular level has not yet been achieved. In this work, through density functional theory (DFT) calculations, we have shown the most feasible path for the hydroformylation of alkynes for an experimentally studied system. We have looked at the iron salt as a precatalyst without any external donor ligand, and the calculations revealed that hydrometalation followed by beta-hydride elimination was favorable over the direct migration of the beta-hydrogen to carbon. Furthermore, our calculations show that the solvent plays an important role in the hydromagnesiation reaction. Furthermore, we have employed an explicit solvent model, where the attachment of one molecule of solvent to the iron center was seen to stabilize the transition states significantly.(c) 2023 Elsevier B.V. All rights reserved.

}, keywords = {Computational study, Ethylene Assisted Catalysis, EtMgBr Assistance, Explicit Role of Solvent, Hydroformylation, Iron Catalyst}, issn = {0022-328X}, doi = {10.1016/j.jorganchem.2023.122621}, author = {Sharma, Himanshu and Tewari, Tanuja and Chikkali, Samir H. and Vanka, Kumar} } @article {48263, title = {Controlled reduction of isocyanates to formamides using monomeric magnesium}, journal = {Chemical Communications}, volume = {59}, year = {2023}, month = {FEB}, pages = {2255-2258}, type = {Article}, abstract = {

This work describes a transition metal-free methodology involving an efficient and controlled reduction of isocyanates to only formamide derivatives using pinacolborane (HBpin) as the hydrogenating agent and a bis(phosphino)carbazole ligand stabilized magnesium methyl complex (1) as the catalyst. A large number of substrates undergo selective hydroboration and give exclusively N-boryl formamides.

}, issn = {1359-7345}, doi = {10.1039/d3cc00036b}, author = {Kumar, Rohit and Sharma, Vishal and Banerjee, Subhrashis and Vanka, Kumar and Sen, Sakya S.} } @article {48833, title = {Covalent organic framework thin-film photodetectors from solution-processable porous nanospheres}, journal = {Journal of the American Chemical Society}, volume = {145}, year = {2023}, month = {JAN}, pages = {1649-1659}, type = {Article}, abstract = {

The synthesis of homogeneous covalent organic framework (COF) thin films on a desired substrate with decent crystallinity, porosity, and uniform thickness has great potential for optoelectronic applications. We have used a solution-processable sphere transmutation process to synthesize 300 +/- 20 nm uniform COF thin films on a 2 x 2 cm2 TiO2-coated fluorine-doped tin oxide (FTO) surface. This process controls the nucleation of COF crystallites and molecular morphology that helps the nanospheres to arrange periodically to form homogeneous COF thin films. We have synthesized four COF thin films (TpDPP, TpEtBt, TpTab, and TpTta) with different functional backbones. In a close agreement between the experiment and density functional theory, the TpEtBr COF film showed the lowest optical band gap (2.26 eV) and highest excited-state lifetime (8.52 ns) among all four COF films. Hence, the TpEtBr COF film can participate in efficient charge generation and separation. We constructed optoelectronic devices having a glass/FTO/TiO2/COF-film/Au architecture, which serves as a model system to study the optoelectronic charge transport properties of COF thin films under dark and illuminated conditions. Visible light with a calibrated intensity of 100 mW cm-2 was used for the excitation of COF thin films. All of the COF thin films exhibit significant photocurrent after illumination with visible light in comparison to the dark. Hence, all of the COF films behave as good photoactive substrates with minimal pinhole defects. The fabricated out-of-plane photodetector device based on the TpEtBr COF thin film exhibits high photocurrent density (2.65 +/- 0.24 mA cm-2 at 0.5 V) and hole mobility (8.15 +/- 0.64 x10-3 cm2 V-1 S-1) compared to other as synthesized films, indicating the best photoactive characteristics.

}, issn = {0002-7863}, doi = {10.1021/jacs.2c09838}, author = {Bag, Saikat and Sasmal, Himadri Sekhar and Chaudhary, Sonu Pratap and Dey, Kaushik and Blaette, Dominic and Guntermann, Roman and Zhang, Yingying and Poloz, Miroslav and Kuc, Agnieszka and Shelke, Ankita and Vijayaraghavan, Ratheesh K. and Ajithkumar, Thalasseril G. and Bhattacharyya, Sayan and Heine, Thomas and Bein, Thomas and Banerjee, Rahul} } @article {48261, title = {Covalently interconnected layers in g-C3N4: toward high mechanical stability, catalytic efficiency and sustainability}, journal = {Applied Catalysis B: Environmental}, volume = {322}, year = {2023}, month = {MAR}, pages = {122069}, type = {Article}, abstract = {

The grim prospects for the industrial utilization of g-C3N4 nanosheets arise from multi-step processing resulting in low material yields and poor visible light response due to quantum confinement. Herein, we introduce a strategy for linking the adjacent layers of g-C3N4 covalently to realize a high surface area without excess mass loss in a one-step process by introducing diethylene glycol as a precursor that produces-(CH2)2-O-(CH2)2-linkers in-situ. Their presence increases interlayer spacing and introduces surface curvatures, discouraging the stacking of a larger number of layers to produce nanosheets with-3 times higher surface area. Interestingly, unlike other layered materials, the linkers also provide extraordinary mechanical stability against exfoliating forces. In addition, the process instills sub-bandgap states and a considerable visible light response at 500 nm to slow down the picosecond exciton recombination dynamics, resulting in-5 times enhancement in H2 generation efficiency from photocatalytic water-splitting over the bulk sample.

}, keywords = {Layer-linkers, Sustainable synthesis, Transient absorption spectroscopy, water-splitting}, issn = {0926-3373}, doi = {10.1016/j.apcatb.2022.122069}, author = {Roy, Raj Sekhar and Mondal, Sanjit and Mishra, Samita and Banoo, Maqsuma and Sahoo, Lipipuspa and Kumar, Amit and Vinod, C. P. and De, Arijit K. and Gautam, Ujjal K.} } @article {48300, title = {Design and synthesis of 1,3-diynes as potent antifungal agents against aspergillus fumigatus}, journal = {ChemMedChem}, volume = {18}, year = {2023}, month = {MAY }, type = {Article}, abstract = {

Eugenol and isoeugenol, secondary metabolites isolated from the plant Myristica fragrans have displayed antifungal activities against Aspergillus fumigatus (IC50 1900 mu M). Compounds having conjugated unsaturation have been of great use as antifungals i. e. amphotericin B, nystatin and terbinafine etc. Hence, in the present study, we have designed and synthesised 1,3-diynes by utilizing Glaser-Hay and Cadiot-Chodkiewicz coupling reactions to furnish possible antifungal agents. Synthesis of 1,6-diphenoxyhexa-2,4-diyne derivatives was achieved by Cu(I) catalysed coupling of propargylated eugenol, isoeugenol, guaiacol, vanillin and dihydrogenated eugenol or eugenol in good to excellent yields. All the synthesized compounds were evaluated against pathogenic fungus A. fumigatus. Among all the synthesized compounds, one of the compounds was found to be exhibiting promising antifungal activity with IC50 value of 7.75 mu M thereby suggesting that this type of scaffold could pave the way for developing new antifungal agents. The most active compound was found to be low cytotoxic when assayed against L-132 cancer cell line. Effect of the most active compound on ergosterol biosynthesis has also been studied. Also, the most active compound exhibited significant anti-biofilm activity although the concentration was found to be higher than its anti-fungal activity. Morphological changes in the biofilm were remarkable under confocal laser scanning microscopy.

}, keywords = {1, 3-Diynes, Antifungal agents, Aspergillus fumigatus, Cadiot-Chodkiewicz, Glaser-Hay}, issn = {1860-7179}, doi = {10.1002/cmdc.202300013}, author = {Goswami, Lakshmi and Gupta, Lovely and Paul, Sayantan and Vijayaraghavan, Pooja and Bhattacharya, Asish K.} } @article {48951, title = {Distortion-induced interfacial charge transfer at single cobalt atom secured on ordered intermetallic surface enhances pure oxygen production}, journal = {ACS Nano}, volume = {17}, year = {2023}, month = {NOV }, pages = {23169-23180}, type = {Journal Article}, abstract = {

In this work, atomic cobalt (Co) incorporation into the Pd2Ge intermetallic lattice facilitates operando generation of a thin layer of CoO over Co-substituted Pd2Ge, with Co in the CoO surface layer functioning as single metal sites. Hence the catalyst has been titled Co-1-CoO-Pd2Ge. High-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy confirm the existence of CoO, with some of the Co bonded to Ge by substitution of Pd sites in the Pd2Ge lattice. The role of the CoO layer in the oxygen evolution reaction (OER) has been verified by its selective removal using argon sputtering and conducting the OER on the etched catalyst. In situ X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy demonstrate that CoO gets transformed to CoOOH (Co3+) in operando condition with faster charge transfer through Pd atoms in the core Pd2Ge lattice. In situ Raman spectroscopy depicts the emergence of a CoOOH phase on applying potential and shows that the phase is stable with increasing potential and time without getting converted to CoO2. Density functional theory calculations indicate that the Pd2Ge lattice induces distortion in the CoO phase and generates unpaired spins in a nonmagnetic CoOOH system resulting in an increase in the OER activity and durability. The existence of spin density even after electrocatalysis is verified from electron paramagnetic resonance spectroscopy. We have thus successfully synthesized intermetallic supported CoO during synthesis and rigorously verified the role played by an intermetallic Pd2Ge core in enhancing charge transfer, generating spin density, improving electrochemical durability, and imparting mechanical stability to a thin CoOOH overlayer. Differential electrochemical mass spectrometry has been explored to visualize the instantaneous generation of oxygen gas during the onset of the reaction.

}, keywords = {DEMS, interfacial charge transfer, Intermetallic, long-termstability, operando spectroscopic techniques, Oxygen Evolution Reaction, structuraldistortion}, issn = {1936-0851}, doi = {10.1021/acsnano.3c09680}, author = {Mondal, Soumi and Riyaz, Mohd and Bagchi, Debabrata and Dutta, Nilutpal and Singh, Ashutosh Kumar and Vinod, Chathakudath P. and Peter, Sebastian C.} } @article {48722, title = {Divergent synthesis of oxepino-phthalides and [5,5]-oxaspirolactones through [2+2+2]- and [2+3]-annulation of alkynyl alcohols with a-ynone-esters}, journal = {Journal of Organic Chemistry}, volume = {88}, year = {2023}, month = {AUG }, pages = {12597-12612}, type = {Article}, abstract = {

Unmasking the synthetic potential of alkyne functional group of alkynyl alcohols as surrogates of carbonyl compounds, herein we present the first Bronsted acid (TfOH)-catalyzed [2 + 2 + 2]-annulation of 4-pentyn-1-ols (possessing terminal alkyne) with a-ynone-esters to access tricyclic tetrahydro-oxepino-phthalides. Besides, an unprecedented synthesis of a-acetoaryl or a-alkynyl [5,5]-oxaspirolactones has been demonstrated by employing 4-pentyn-1-ols (possessing an internal alkyne) as an annulation partner, which proceeds through a divergent [2 + 3]-annulation pathway.

}, issn = {0022-3263}, doi = {10.1021/acs.joc.3c01301}, author = {Kambale, Digambar A. and Borade, Balasaheb R. and Vinodkumar, Ramavath and Kontham, Ravindar} } @article {48771, title = {Donor strapped perylene bisimide macrocycle and its lemniscate dimer with extended charge separation}, journal = {Inorganic Chemistry Frontiers}, volume = {10}, year = {2023}, month = {OCT }, pages = {5099-5107}, type = {Article}, abstract = {

Macrocyclic structures are fascinating due to their unique design and capability to place chromophores in specific orientations, resulting in exciting optoelectronic properties. However, the synthetic challenges limit the broad exploration of such systems. Herein, we report a thiophene-diacetylene-based ring strapped perylene bisimide macrocycle and its notably different electron transfer features. Single-crystal analysis of the macrocycle pointed to the nearly orthogonal placement of donor-acceptor units, facilitating better electronic communication between them. Interestingly, introduction of an alkyl substituent on the peripheral thiophene ring opened the possibility of forming a higher oligomer macrocycle consisting of two strapped perylene bisimide units. Diffusion and two-dimensional NMR experiments provided insight into the structure of the figure-eight-shaped lemniscate dimer. Transient absorption measurements showed faster electron transfer and extended stabilization of the charge-separated state. The thiophene-diacetylene-based ring is a better donor unit to facilitate rapid electron transfer and extended charge separation in the macrocycle and its lemniscate dimer. The new macrocycle design enables the formation of higher analogs equally capable of stabilizing the charge-separated state. Donor-acceptor (D-A) macrocycle designs position the respective units to achieve ultrafast electron transfer precisely and an extended charge-separated state. Here, we report a D-A macrocycle and its lemniscate dimer molecule with exciting electron transfer features.

}, issn = {2052-4129}, doi = {10.1039/d3qo01060k}, author = {Veer, Sairam Dnyaneshwar and Goswami, Tanmay and Ravindranathan, Sapna and Gonnade, Rajesh and Kharbanda, Nitika and Ghosh, Hirendra N. and Babu, Sukumaran Santhosh} } @article {48301, title = {Dual routes toward observation of a trans-H2/hydride complex in an iridium pincer system and hydrogenation catalytic activity}, journal = {Organometallics}, volume = {42}, year = {2023}, month = {MAR}, pages = {441-456}, type = {Article}, abstract = {

The Abstraction of chloride from a six- coordinate complex, trans-[ Ir(H)(Cl)((iPr)4)(POCOP)(PPh3)] (1) [((iPr)4)(POCOP) = 2,6-bis(di-iso-propylphosphinito)benzene,kappa(3)-C6H3-1,3-[OP(Pr-i)(2 )](2)], using NaBAr4f leads to the generation of a dinitrogen complex, trans-[Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)][BAr4f] (6). Addition of H-2 to [Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)](+) (6) under extremely mild conditions (1 bar, 298 K) resulted in the reversible coordination of H-2 to generate the cis-[Ir(H)(eta H-2-(2))((iPr)4)(POCOP)(PPh3)](+) (cis-11) complex. The cis-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) complex (cis-11) isomerized to a trans isomer, trans-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) (trans-11), at 253 K. The isomerization process has been studied and supported by computations. Employing an alternative route, protonation of the trans-[Ir(H)(2)((iPr)4)(POCOP)(PPh3)] complex (2) at 183 K resulted in the formation of an identical, trans-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) complex (trans-11); upon warming the sample, the trans-H-2/hydride complex isomerized to the cis isomer above 253 K. Two independent routes to obtain trans-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) (trans-11) species have been established. Reaction of trans-[Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)][BAr4f] (6) with C2H4 gave the cis-[Ir(H)(eta(2)-C2H4)((iPr)4)(POCOP)(PPh3)](+) complex (cis-15), which also undergoes isomerization to yield an equilibrium mixture of cis/trans-[Ir(H)(eta(2)-C2H4)((iPr)4)(POCOP)(PPh3)](+) complexes (cis-15 and trans-15) at 253 K. The trans-[Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)](+) complex (6) is an excellent catalyst for hydrogenation of ethylene to ethane under very mild conditions.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.2c00641}, author = {Agrawal, Nisha K. and Dash, Soumya R. and Vanka, Kumar and Jagirdar, Balaji R.} } @article {48762, title = {Effect of charge and solvation shell on non-radiative decay processes in s-block cationic metal ion water clusters}, journal = {Journal of Chemical Physics}, volume = {159}, year = {2023}, month = {AUG }, pages = {054304}, type = {Article}, abstract = {

Intermolecular Coulombic decay or electron transfer-mediated decay are the autoionization processes through which a molecule can relax. This relaxation is only possible if the inner valence{\textquoteright}s ionization potential (IP) exceeds the system{\textquoteright}s double ionization potential (DIP). To study the effects of charge and solvation shell, we have calculated the IP, DIP values, and lifetime of Na-2s and Mg-2s temporary bound states in various optimized structures of Na+-(H2O)(n) and Mg2+-(H2O)(n) (n = 1-5) micro-solvated clusters, where n water molecules are distributed in a way that some are directly bound to the metal ion and the rest to the water molecules. The first and second solvation shells are the names for the former and the latter water-binding positions, respectively. For a given n, the lifetime of decaying states is longer when water molecules are in the second solvation shell. We found that the Mg-2p state can decay for all n values in Mg2+-(H2O)(n) clusters, whereas the Na-2p state{\textquoteright}s decay is possible for n \>= 2 in Na+-(H2O)(n) clusters. Our findings highlight the influence of metal ions{\textquoteright} charge, different solvation shell structures, and the number of water molecules on the decay rate. These systems are relevant to the human body, which makes this study significant.

}, issn = {0021-9606}, doi = {10.1063/5.0153598}, author = {Kumar, Ravi and Ghosh, Aryya and Vaval, Nayana} } @article {48444, title = {Effect of protonation and deprotonation on electron transfer mediated decay and interatomic coulombic decay}, journal = {ChemPhysChem}, volume = {24}, year = {2023}, month = {JAN}, type = {Article}, abstract = {

Electronically excited atoms or molecules in an environment are often subject to interatomic/intermolecular Coulombic decay (ICD) and/or electron transfer mediated decay (ETMD) mechanisms. A few of the numerous variables that can impact these non-radiative decay mechanisms include bond distance, the number of nearby atoms or molecules, and the polarisation effect. In this paper, we have studied the effect of protonation and deprotonation on the ionization potential (IP), double ionization potential (DIP), and lifetime (or decay width) of the temporary bound state in these non-radiative decay processes. We have chosen LiH-NH3 and LiH-H2O as test systems. The equation of motion coupled cluster singles and doubles method augmented by complex absorbing potential (CAP-EOM-CCSD) has been used in calculating the energetic position of the decaying state and the system{\textquoteright}s decay rate. Deprotonation of LiH-NH3/LiH-H2O either from the metal center (LiH) or from ammonia/water lowers the IP and DIP compared to the neutral systems. In contrast, protonation increases these quantities compared to neutral systems. The protonation closes the inner valence state relaxation channels for ICD/ETMD. For example, the decay of the O-2s/N-2s state stops in protonated systems (LiH2+-H2O, LiH2+-NH3, and LiH-NH4+). Our study also shows that the efficiency, i. e., the rate of ICD/ETMD, can be altered by protonation and deprotonation. It is expected to have implications for chemical and biological systems.

}, issn = {1439-4235}, doi = {10.1002/cphc.202200340}, author = {Kumar, R. and Vaval, N.} } @article {48676, title = {Electrode|electrolyte interface enhancement in quasi-solid-state zinc-air batteries through an anion conducting polymer electrolyte interlayer by in situ polymerization}, journal = {Journal of Materials Chemistry A}, volume = {11}, year = {2023}, month = {JUL}, pages = {14776-14787}, type = {Article}, abstract = {

This work introduces a novel concept of electrode|electrolyte interface enhancement using an ultraviolet (UV) light-assisted in situ polymerization strategy to improve the performance of quasi-solid-state zinc-air batteries (ZABs). The suitability of the UV polymerization strategy to process a mechanically stable OH- conducting anion exchange polymer electrolyte membrane (AEPEM) reinforced by a glass fiber (GF) separator is also reported. The in situ polymerized ionomer-skin/interlayer (a thin anion-conducting polymer coating over the air-cathode of ZAB) acts as a buffer layer to narrow down the performance gap generally observed between ZABs possessing quasi-solid-state electrolytes and standard liquid electrolytes, respectively. For instance, when combined with the in situ polymerization strategy, a rechargeable ZAB (rZAB) based on an AEPEM-GF composite membrane delivered a high power density of 140 mW cm(-2), higher than that of the one without an in situ polymerized ionomer interlayer (120 mW cm(-2)). Notably, in a flexible rZAB configuration, this new strategy resulted in enhanced rate capability and cycling stability for 14 h at an operating current density of 2 mA cm(-2).

}, issn = {2050-7488}, doi = {10.1039/d3ta02320f}, author = {Kurian, Maria and Vijayakumar, Vidyanand and Manna, Narugopal and Kanheerampockil, Fayis and Bhat, Suresh and Kurungot, Sreekumar} } @article {48755, title = {Enhancing diradical character of chichibabin{\textquoteright}s hydrocarbon through fluoride substitution}, journal = {ChemPlusChem}, volume = {88}, year = {2023}, month = {AUG}, pages = {e202300273}, type = {Article}, abstract = {

In this work, 5-SIDipp [SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene] (1) derived Chichibabin{\textquoteright}s hydrocarbon with an octafluorobiphenylene spacer (3) has been reported. The addition of two equivalents of 5-SIDipp with decafluorobiphenyl in presence of BF3 gives the double C-F bond activated imidazolium salt with two tetrafluoroborate anions, 2. Further reduction of 2 gives the fluorine substituted 5-SIDipp based Chichibabin{\textquoteright}s hydrocarbon, 3. Quantum chemical calculations suggested a singlet state of 3 with a singlet-triplet energy gap (?ES-T) of 3.7 kcal mol(-1), which is substantially lower with respect to the hydrogen substituted NHC-based Chichibabin{\textquoteright}s hydrocarbons (10.7 kcal mol(-1), B3LYP). As a result, the diradical character (y) of 3 (y=0.62) is also noticeably higher than the hydrogen substituted CHs (y=0.41-0.43). The ?ES-T was found to be higher in CASSCF (22.24 kcal mol(-1)) and CASPT2 (11.17 kcal mol(-1)) for 3 and the diradical character (d) is 44.6 \%.

}, keywords = {C-F Bond Activation, Chichibabin \& PRIME, DFT, N-Heterocyclic carbene, s Hydrocarbon}, issn = {2192-6506}, doi = {10.1002/cplu.202300273}, author = {Kundu, Gargi and Dash, Soumya Ranjan and Kumar, Ravi and Vanka, Kumar and Ghosh, Aryya and Sen, Sakya S.} } @article {49140, title = { Ferroelectric aminophosphonium cyanoferrate with a large electrostrictive coefficient as a piezoelectric nanogenerator}, journal = {Angewandte Chemie-International Edition}, volume = {62}, year = {2023}, month = {JAN }, type = {Article}, abstract = {

Hybrid materials possessing piezo- and ferroelectric properties emerge as excellent alternatives to conventional piezoceramics due to their merits of facile synthesis, lightweight nature, ease of fabrication and mechanical flexibility. Inspired by the structural stability of aminophosphonium compounds, here we report the first A(3)BX(6) type cyanometallate [Ph-2((PrNH)-Pr-i)(2)P](3)[Fe(CN)(6)] (1), which shows a ferroelectric saturation polarization (P-s) of 3.71 mu C cm(-2). Compound 1 exhibits a high electrostrictive coefficient (Q(33)) of 0.73 m(4) C-2, far exceeding those of piezoceramics (0.034-0.096 m(4) C-2). Piezoresponse force microscopy (PFM) analysis demonstrates the polarization switching and domain structure of 1 further confirming its ferroelectric nature. Furthermore, thermoplastic polyurethane (TPU) polymer composite films of 1 were prepared and employed as piezoelectric nanogenerators. Notably, the 15 wt \% 1-TPU device gave a maximum output voltage of 13.57 V and a power density of 6.03 mu W cm(-2).

}, keywords = {Cyanometallates, energy conversion, H-bonding, hybrid composites, Phosphorus}, issn = {1433-7851}, doi = {10.1002/anie.202214984}, author = {Vijayakanth, Thangavel and Sahoo, Supriya and Kothavade, Premkumar and Sharma, Vijay Bhan and Kabra, Dinesh and Zareba, Jan K. K. and Shanmuganathan, Kadhiravan and Boomishankar, Ramamoorthy} } @article {48298, title = {Genetic diversity of toxigenic Fusarium verticillioides associated with maize grains, India}, journal = {Genetics and Molecular Biology}, volume = {46}, year = {2023}, month = {MAY}, pages = {e20220073}, type = {Article}, abstract = {

In the present investigation, prevalence, genetic diversity, and mycotoxin producing potential of Fusarium species associated with maize grain samples were studied from different geographical regions of India. The highest prevalence of Fusarium verticillioides was recorded as 88.52\%, followed by F. coffeatum, F. foetens, and F. euwallaceae, 6.55\%, 3.27\%, and 1.63\%, respectively. We isolated 54 strains of F. verticillioides, and their genetic diversity was studied by inter simple sequence repeats (ISSR). The ISSR fingerprints (AG) 8C and (AG) 8G showed 252 and 368 microsatellite sites in the genome of F. verticillioides and resulted in 99-100\% repeatability and reproducibility. The Simpson (SID) and Shannon (H) indices (0.78 and 2.36) suggest that F. verticillioides strains exhibit moderate to high diversity. Molecular detection of fumonisin B1 (FB1) biosynthetic genes (FUM1 and FUM13) involved in FB1 production in F. verticillioides was confirmed by polymerase chain reaction (PCR). Furthermore, 91\% of the strains were positive for FB1 production, which was affirmed by liquid chromatography with tandem mass spectrometry (LC-MS-MS). In-vitro appurtenance of F. verticillioides spores exhibited a high to moderate effect on the growth and development of the maize. The current finding demonstrated that most F. verticillioides strains showed a wide range of genetic diversity with varied toxigenic and pathogenic potentials. In conclusion, for the first time, F. coffeatum, F. foetens, and F. euwallaceae species were reported from maize grain samples in India. They were positive for FB1 and negatively affecting grain quality, which is a major concern in food safety.

}, keywords = {diversity, Food safety, Fusarium verticillioides, Mycotoxin, pathogenicity}, issn = {1415-4757}, doi = {10.1590/1678-4685-GMB-2022-0073}, author = {Navale, Vishwambar D. and Sawant, Amol M. and Vamkudoth, Koteswara Rao} } @article {48446, title = {Genomic determinants of entomopathogenic fungi and their involvement in pathogenesis}, journal = {Microbial Ecology}, volume = {85}, year = {2023}, month = {JAN}, pages = {49-60}, type = {Article}, abstract = {

Entomopathogenic fungi offer an effective and eco-friendly alternative to curb insect populations in biocontrol strategy. The evolutionary history of selected entomopathogenic fungi indicates their ancestral relationship with plant endophytes. During this host shifting, entomopathogenic fungi must have acquired multiple mechanisms, including a combination of various biomolecules that make them distinguishable from other fungi. In this review, we focus on understanding various biochemical and molecular mechanisms involved in entomopathogenesis. In particular, we attempt to explain the indispensable role of enlarged gene families of various virulent factors, viz. chitinases, proteases, lipases, specialized metabolites, and cytochrome P450, in entomopathogenesis. Our analysis suggests that entomopathogenic fungi recruit a different set of gene products during the progression of pathogenesis. Knowledge of these bio-molecular interactions between fungi and insect hosts will allow researchers to execute pointed efforts towards the development of improved entomopathogenic fungal strains.

}, keywords = {Biocontrol, Chitinases, Endophytic fungi, Entomopathogenic fungi, Hydrolytic enzymes, Insect pests}, issn = {0095-3628}, doi = {10.1007/s00248-021-01936-z}, author = {Vidhate, Ravindra P. and Dawkar, Vishal V. and Punekar, Sachin A. and Giri, Ashok P.} } @article {48791, title = {H-atom site exchange in an iridium trans-dihydrogen/hydride complex, trans-[Ir(H)(?2-H2)(iPr)4(POCOP)(DMAP)]+}, journal = {Dalton Transactions}, volume = {52}, year = {2023}, month = {OCT }, pages = {13858-13863}, type = {Article}, abstract = {

Treatment of trans-[Ir(H)(N)(2)((iPr)4)(POCOP)(DMAP)][BAr4f] (2) with H-2 (1 bar) under ambient conditions (298 K) results in the formation of a trans-[Ir(H)(?(2)-H-2)((iPr)4)(POCOP)(DMAP)][BAr4f] (3) complex. Complex 3 exhibits H-atom site exchange between the bound H-2 and the hydride ligands which are mutually trans to one another. A plausible mechanism of this exchange involves metal-ligand cooperativity as studied by computations.

}, issn = {1477-9226}, doi = {10.1039/d3dt02366d}, author = {Agrawal, Nisha K. and Gayathridevi, S. and Dash, Soumya R. and Vanka, Kumar and Jagirdar, Balaji R.} } @article {48271, title = {Hydrogenation of levulinic acid to gamma-valerolactone over nickel supported organoclay catalyst}, journal = {Catalysis Today}, volume = {408}, year = {2023}, month = {JAN }, pages = {36-49}, type = {Article}, abstract = {

In this work, a series of Ni/Organoclay catalysts with different Nickel loadings were prepared by the wetimpregnation method for the catalytic hydrogenation of levulinic acid (LA) to gamma-valerolactone (GVL). Reaction parameters such as reaction temperature, pressure, solvent effect, and wt\% of catalyst were optimized to get excellent conversion of levulinic acid selectively to gamma-valerolactone. Ni/Organoclay with 30\% Nickel loading exhibited 100\% conversion of LA with 100\% selectivity towards GVL at 140 degrees C and 3.0 MPa H2 pressure using 1,4-dioxane as a solvent in 5 h. Different bulk and surface characterization techniques such as XRD, BET, FE-SEM, HR-TEM, XPS, XRF, NH3-TPD, and H2-Chemisorption were used to characterize the Ni/Organoclay catalyst. BET and NH3-TPD analysis showed that the pre-treatment of bentonite with surfactant (CTAB) improved the pore volume, surface area, and acidity of Organoclay which assisted in improving the conversion and selectivity of LA and GVL respectively.

}, keywords = {?-Valerolactone (GVL), Bentonite, Hydrogenation, Levulinic acid (LA), Nickel, organoclay}, issn = {0920-5861}, doi = {10.1016/j.cattod.2022.10.004}, author = {Kamble, Paresh A. and Vinod, C. P. and Rathod, Virendra K. and Kantam, Mannepalli Lakshmi} } @article {48448, title = {Hydroxide ion-conducting viologen-bakelite organic frameworks for flexible solid-state zinc-air battery applications}, journal = {Nanoscale Horizons}, volume = {8}, year = {2023}, month = {JAN }, pages = {224-234}, type = {Article}, abstract = {

Adaptable polymer-based solid-state electrolytes can be a game-changer toward safe, lightweight flexible batteries. We present a robust Bakelite-type organic polymer covalently decked with viologen, triazine, and phenolic moieties. Its flexible structure with cationic viologen centers incorporates counter-balancing free hydroxide ions into the polymeric framework. By design, the aromatic groups and heteroatoms in the framework can be activated under an applied potential to prompt a push-pull drive, setting off the towing of hydroxide ions via weak electrostatic, van der Waals, and hydrogen-bond interactions. The frontier orbitals from a DFT-modeled structure certify this. The hydroxyl-polymer requires minimal KOH wetting to maintain a humid environment for Grotthuss-type transport. The hydroxide ion conductivity reaches a value of 1.4 x 10(-2) S cm(-1) at 80 degrees C and 95\% RH, which is retained for over 15 h. We enhanced its practical utility by coating it as a thin solid-state separator-cum-electrolyte on readily available filter paper. The composite exhibits a conductivity of 4.5 x 10(-3) S cm(-1) at 80 degrees C and 95\% RH. A zinc-air battery (ZAB) constructed using this polymer-coated paper as electrolyte yields a maximum power density of 115 mW cm(-2) and high specific capacitance of 435 mA h g(-1). The power density recorded for our ZAB is among the best reported for polymer electrolyte-based batteries. Subsequently, the flexible battery fabricated with IISERP-POF11_OH@FilterPaper exhibits an OCV of 1.44 V, and three batteries in series power a demo traffic signal. To underscore the efficiency of hydroxide ion transport through the complex multifunctional backbone of the polymer, we calculated the diffusion coefficient for OH- (Exp: 2.9 x 10(-5) cm(2) s(-1); Comp. 5.2 x 10(-6) cm(2) s(-1)) using electrochemical methods and MD simulations. Climbing-edge NEB calculations reveal a large energy barrier of 2.11 eV for Zn2+ to penetrate the polymer and identify hydroxide ions within the polymer, suggesting no undesirable Zn2+ crossover. Our findings assert the readily accessible C-C-linked cationic polymer{\textquoteright}s capacity as a solid-state electrolyte for ZABs and any anion-conducting membrane.

}, issn = {2055-6756}, doi = {10.1039/d2nh00455k}, author = {Rase, Deepak and Illathvalappil, Rajith and Singh, Himan Dev and Shekhar, Pragalbh and Leo, Liya S. and Chakraborty, Debanjan and Haldar, Sattwick and Shelke, Ankita and Ajithkumar, Thalasseril G. and Vaidhyanathan, Ramanathan} } @article {48458, title = {Imine oxidation catalyzed by zinc hydroxyapatite: kinetic studies}, journal = {ChemistrySelect}, volume = {8}, year = {2023}, month = {MAY}, pages = {e202203503}, type = {Article}, abstract = {

The synthesis of N,N-diphenylformamide from N-benzylideneaniline and urea hydrogen peroxide is investigated using a zinc hydroxyapatite (ZnHAP) catalyst. It was found that the catalyst resulted in the highest activity of 91 \% conversion and 40 \% selectivity at 130 degrees C in 2 h. A kinetic model was validated by Langmuir-Hinshelwood-Hougen-Watson (LHHW) at different temperatures and the absence of mass transfer resistance was proved by the Weisz Prater criterion. Effect of different catalysts, catalyst loading, temperature, mole-ratio, and speed of stirring was studied. The as-synthesized catalyst is characterized by FTIR, BET nitrogen adsorption-desorption, TEM, EDX, TPD-NH3, XPS, ICP-MS and XRD. ZnHAP catalyst was found to be stable up to three recycles with no loss in activity.

}, keywords = {heterogeneous catalysis, hydroxyapatite, imines, Oxidation, Reaction kinetics}, issn = {2365-6549}, doi = {10.1002/slct.202203503}, author = {Vishwakarma, Rakhi and Vinod, C. P. and Rathod, Virendra K. and Kantam, Mannepalli Lakshmi} } @article {48684, title = {Insights into adsorption of various gases on extra-framework cations of zeolite: a dispersion corrected DFT study on zeolite cluster models with Li plus , Na plus and K plus ions}, journal = {Microporous and Mesoporous Materials}, volume = {361}, year = {2023}, month = {Nov}, pages = {112739}, type = {Article}, abstract = {

Design of an economical and sustainable gas separation material is relevant in several industrial processes. Zeolites with tunable pore sizes are ideal molecular sieves of many gases. The adsorption centers of these molecular sieves are extra-framework Lewis acid centers. In this study, we attempt to delineate the electronic properties of such centers (Li+, Na+ and K+) and their sorption properties towards N2, O2, CO, CO2 and H2. Negative framework of zeolites are modeled using different cluster models that present distinct electronic environment and role of this environment on the Lewis acidity of the cation. The sorption property towards different gases is evaluated using dispersion corrected DFT studies. The results obtained are benchmarked for one of the studied model using CCSD calculations. The results indicate that while the local environment modulates the adsorption properties, the relative adsorption properties between different ions follow the same order irrespective of the type of negative framework modeled. This reveals that intrinsic atomic properties of the charge compensating cations drive the sorption properties of the zeolites. Adsorption energies compounded with the analysis of IR stretching frequencies of the adsorbed gases reveals that Li centers shows molecular adsorption (charge donation to the cationic centers) towards N2 as compared to O2 and towards CO2/CO as compared to H2, demonstrating the applicability of Li-Zeolites as ideal membranes for oxygen concentrators and syngas separation. These adsorption studies are ratified by the BOMD simulations at 300 K, where H2 and O2 desorbs while N2, CO and CO2 remains adsorbed to the cationic site.

}, keywords = {BOMD simulation, CO/CO2/H2 separation, Extra-framework cation, N2/O2 separation, zeolites}, issn = {1387-1811}, doi = {10.1016/j.micromeso.2023.112739}, author = {Devasia, George and Kumar, Ravi and Vaval, Nayana and Krishnamurty, Sailaja} } @article {48450, title = {Intrinsic charge polarization in Bi19S27Cl3 nanorods promotes selective C-C coupling reaction during photoreduction of CO2 to ethanol}, journal = {Advanced Materials}, volume = {35}, year = {2023}, month = {FEB}, type = {Article}, abstract = {

Obtaining multi-carbon products via CO2 photoreduction is a major catalytic challenge involving multielectron-mediated C-C bond formation. Complex design of multicomponent interfaces that are exploited to achieve this chemical transformation, often leads to untraceable deleterious changes in the interfacial chemical environment affecting CO2 conversion efficiency and product selectivity. Alternatively, robust metal centers having asymmetric charge distribution can effectuate C-C coupling reaction through the stabilization of intermediates, for desired product selectivity. However, generating inherent charge distribution in a single component catalyst is a difficult material design challenge. Here, a novel photocatalyst, Bi19S27Cl3, is presented which selectively converts CO2 to a C-2 product, ethanol, in high yield under visible light irradiation. Structural analysis through transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy reveals the presence of charge polarized bismuth centers in Bi19S27Cl3. The intrinsic electric field induced by charge polarized bismuth centers renders better separation efficiency of photogenerated electron-hole pair. Furthermore, charge polarized centers yield better adsorption of CO* intermediate and accelerate the rate determining C-C coupling step through the formation of OCCOH intermediate. Formation of these intermediates is experimentally mapped by in situ Fourier-transform infrared spectroscopy and further confirmed by theoretical calculation.

}, keywords = {C-C coupling, charge polarization, CO2 reduction, Ethanol, Photocatalysis}, issn = {0935-9648}, doi = {10.1002/adma.202205994}, author = {Das, Kousik and Das, Risov and Riyaz, Mohd and Parui, Arko and Bagchi, Debabrata and Singh, Ashutosh Kumar and Singh, Abhishek Kumar and Vinod, Chathakudath P. and Peter, Sebastian C.} } @article {48464, title = {Isolation and biochemical characterization of acid phytase from aspergillus niger and its applications in dephytinization of phytic acid in poultry feed ingredients}, journal = {Microbiology}, volume = {92}, year = {2023}, month = {APR}, pages = {221-229}, type = {Article}, abstract = {

Acidic phytase (PHY-B) was isolated from Aspergillus niger BIONCL8 strain, and assessed its application for the dephytinization of poultry feed ingredients. Aspergillus niger BIONCL8 strain was identified by precise molecular methods by targeting internal transcribed spacer (ITS) region of the fungi and molecular detection of PHY gene in the strain was confirmed by sequence analysis with respect to PHY production. The enzyme was isolated and purified by DEAE Sephadex A-50 and Bio-Gel P-60 Gel ion-exchange chromatography. The estimated molecular weight of the protein was 65 kDa on SDS-PAGE, it had a specific activity of 21.18 U/mg. The molecular weight of the protein was confirmed by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The peptide sequence of PHY-B was identified using high resolution-mass spectrometry (LC-HR-MS), and its physicochemical parameters were studied. The PHY was stable at acidic pH 2.1, most active at 40 degrees C and was stable up to 80 degrees C, retaining 30\% residual activity after 1 h of incubation. The PHY activity was enhanced in the presence of Mg2+ and EDTA, and activity was inhibited in the presence of Hg2+ and K+. The K-m and V-max of PHY were recorded as 3.35 mM and 1.27 U/mg, respectively. The PHY was shown to play a significant role in decreasing PA content in various poultry feed ingredients, ranging from 48.14 to 82.14\%. The novel features of the enzyme can be used to decrease the PA content in feed ingredients and increase the bioavailability of nutrients to non-ruminant animals.

}, keywords = {Aspergillus niger, dephytinization, high resolution-mass spectrometry, ion-exchange chromatography, matrix-assisted laser desorption ionization time-of-flight mass spectrometry, Phytase}, issn = {0026-2617}, doi = {10.1134/S0026261722601452}, author = {Bhandari, Y. and Sonwane, B. and Vamkudoth, K. R.} } @article {48717, title = {Isolation and molecular characterization of indigenous penicillium chrysogenum/rubens strain portfolio for penicillin V production}, journal = {Microorganisms}, volume = {11}, year = {2023}, month = {APR}, pages = {1132}, type = {Article}, abstract = {

Beta (beta)-lactam antibiotic is an industrially important molecule produced by Penicillium chrysogenum/rubens. Penicillin is a building block for 6-aminopenicillanic acid (6-APA), an important active pharmaceutical intermediate (API) used for semi-synthetic antibiotics biosynthesis. In this investigation, we isolated and identified Penicillium chrysogenum, P. rubens, P. brocae, P. citrinum, Aspergillus fumigatus, A. sydowii, Talaromyces tratensis, Scopulariopsis brevicaulis, P. oxalicum, and P. dipodomyicola using the internal transcribed spacer (ITS) region and the beta-tubulin (BenA) gene for precise species identification from Indian origin. Furthermore, the BenA gene distinguished between complex species of P. chrysogenum and P. rubens to a certain extent which partially failed by the ITS region. In addition, these species were distinguished by metabolic markers profiled by liquid chromatography-high resolution mass spectrometry (LC-HRMS). Secalonic acid, Meleagrin, and Roquefortine C were absent in P. rubens. The crude extract evaluated for PenV production by antibacterial activities by well diffusion method against Staphylococcus aureus NCIM-2079. A high-performance liquid chromatography (HPLC) method was developed for simultaneous detection of 6-APA, phenoxymethyl penicillin (PenV), and phenoxyacetic acid (POA). The pivotal objective was the development of an indigenous strain portfolio for PenV production. Here, a library of 80 strains of P. chrysogenum/rubens was screened for PenV production. Results showed 28 strains capable of producing PenV in a range from 10 to 120 mg/L when 80 strains were screened for its production. In addition, fermentation parameters, precursor concentration, incubation period, inoculum size, pH, and temperature were monitored for the improved PenV production using promising P. rubens strain BIONCL P45. In conclusion, P. chrysogenum/rubens strains can be explored for the industrial-scale PenV production.

}, keywords = {beta-tubulin gene, high-performance liquid chromatography, internal transcribed spacer region, Penicillium chrysogenum/rubens, phenoxymethyl penicillin}, doi = {10.3390/microorganisms11051132}, author = {Sawant, Amol M. and Navale, Vishwambar D. and Vamkudoth, Koteswara Rao} } @article {48735, title = {Made to measure squaramide COF cathode for zinc dual-ion battery with enriched storage via redox electrolyte}, journal = {Advanced Energy Materials}, volume = {13}, year = {2023}, month = {SEP}, type = {Article}, abstract = {

Aqueous rechargeable batteries are promising grid-scale energy storage devices because of their affordability, operational safety, and environmental benignity. Among these, Zn-ion batteries (ZIBs) have unfolded new horizons. Designing superior cathodes for ZIBs is crucial. Covalent organic frameworks (COFs) can be made redox active with a high storage surface. Here, for the first time, a chelating COF with redox-active ZnI2 in a ZnSO4(aq) electrolyte is combined. Including iodide harvests an approximately threefold enhancement in capacity from 208 to 690 mAh g(-1) at 1.5 A g(-1), the highest among all the COF-derived ZIBs. Remarkably, a charge-discharge curve at 1.3 V exhibits very limited dropout voltage and super-flat platform, with a remarkable capacity of 600 mAh g(-1) at 5 A g(-1) stable up to 6000 cycles, confirming that the polyiodide generation and storage are sustainable. The COF{\textquoteright}s dual-ion storage (Zn2+ and polyidode) delivers a ZIB with the highest energy density. Spectro-electrochemical measurements coupled with X-ray photoelectron spectroscopy unambiguously unveil the existence of multiple polyiodide species, with I-3(-) and IO3- ions as the prominent species. The latter gets reduced at the COF electrode under an applied potential, leaving I-3(-) as the major species stored on the COF. The prospect of COF-polyiodide((aq)) is a windfall for metal-ion batteries.

}, keywords = {covalent organic frameworks, flexible batteries, polyiodide, redox electrolytes, Zn ion batteries}, issn = {1614-6832}, doi = {10.1002/aenm.202301049}, author = {Kushwaha, Rinku and Jain, Chitvan and Shekhar, Pragalbh and Rase, Deepak and Illathvalappil, Rajith and Mekan, Deep and Camellus, Augastus and Vinod, Chathakudath Prabhakaran and Vaidhyanathan, Ramanathan} } @article {48775, title = {MeGen-generation of gallium metal clusters using reinforcement learning}, journal = {Machine Learning-Science and Technology}, volume = {4}, year = {2023}, month = {JUN }, pages = {025032}, type = {Article}, abstract = {

The generation of low-energy 3D structures of metal clusters depends on the efficiency of the search algorithm and the accuracy of inter-atomic interaction description. In this work, we formulate the search algorithm as a reinforcement learning (RL) problem. Concisely, we propose a novel actor-critic architecture that generates low-lying isomers of metal clusters at a fraction of computational cost than conventional methods. Our RL-based search algorithm uses a previously developed DART model as a reward function to describe the inter-atomic interactions to validate predicted structures. Using the DART model as a reward function incentivizes the RL model to generate low-energy structures and helps generate valid structures. We demonstrate the advantages of our approach over conventional methods for scanning local minima on potential energy surface. Our approach not only generates isomer of gallium clusters at a minimal computational cost but also predicts isomer families that were not discovered through previous density-functional theory (DFT)-based approaches.

}, keywords = {gallium clusters, reinforcement learning, structure generation}, doi = {10.1088/2632-2153/acdc03}, author = {Modee, Rohit and Verma, Ashwini and Joshi, Kavita and Priyakumar, U. Deva} } @article {48733, title = {Metabolites from lactococcus lactis subsp. lactis: isolation, structure elucidation, and antimicrobial activity}, journal = {ACS Omega}, volume = {8}, year = {2023}, month = {SEP}, pages = {36628-36635}, type = {Article}, abstract = {

Herein, we disclose the identification of novel metabolites from a potential probiotic strain, Lactococcus lactis subsp. lactis, obtained from traditional dairy milk samples collected in Maharashtra, India (in January 2021). Isolated metabolites include pyrazin-2-carboxamide [1, pyrazinamide, a potential antitubercular drug], 3,5-dihydroxy-6-methyl-2,3-dihydro-4H-pyran-4-one (2, DDMP), 2,4-di-tert-butylphenol (3), and hexadecanoic acid (4, palmitic acid). The chemical structures of these metabolites were elucidated through extensive 1D NMR (H-1 and C-13) and 2D NMR (HSQC, HMBC, and NOESY) analyses, high-resolution mass spectrometry, high-performance liquid chromatography, and single-crystal X-ray crystallography. Furthermore, these novel metabolites exhibited potent inhibitory activities against various bacteria, fungi, and yeast strains with minimum inhibitory concentrations ranging between 1.56 and 25 mu g/mL, and compounds 1 and 3 were found to be most active against a wide range of microbial strains tested.

}, issn = {2470-1343}, doi = {10.1021/acsomega.3c01662}, author = {Navale, Vishwambar D. and Borade, Balasaheb R. and Rama Krishna, Gamidi and Vamkudoth, Koteswara Rao and Kontham, Ravindar} } @article {48820, title = {Metal deficiency tailored by the 18-electron rule stabilizes metal-based inorganic compounds}, journal = {Chemistry of Materials}, volume = {35}, year = {2023}, month = {JUL}, pages = {6050-6058}, type = {Article}, abstract = {

The 18-electron (18-e(-)) rule is typicallyrestrictedto predicting the stability of transition-metal-based complexes. Herein,we report the use of the 18-e(-) to predict the stabilityin a family of intermetallics MNiSn (M = V, Cr, Fe, and Co) crystallizingin the Co1.75Ge structure type. Site deficiencies at theM site obtained from single-crystal X-ray diffraction are understoodas attaining a stable noble gas electronic configuration. The densityfunctional theory -based structure calculation confirms that the deficientstructure is more stable than the ideal occupation available at thecrystal lattice. MnNiSn, which crystallizes in the half-Heusler crystalstructure, depicts the role of covalent radii of the constituent elementsin determining the crystal structure. Using X-ray absorption spectroscopyand X-ray photoelectron spectroscopy, the local structure of the above-mentionedcompounds was also elucidated, supporting the role of deficiency tunedvalence fluctuation to attain a 18-e(-) configurationthat eventually leads to the formation of stable compounds.

}, issn = {0897-4756}, doi = {10.1021/acs.chemmater.3c01142}, author = {Singh, Ashutosh Kumar and Mumbaraddi, Dundappa and Mishra, Vidyanshu and Roy, Soumyabrata and Vinod, C. P. and Peter, Sebastian C.} } @article {48778, title = {Morphology-dependent catalysis by Co3O4 nanostructures in atmospheric pressure carbon dioxide hydrogenation}, journal = {Journal of Physical Chemistry C}, volume = {127}, year = {2023}, month = {JUL}, pages = {13055-13064}, type = {Article}, abstract = {

In this work, three Co3O4 nanostructureswith different morphologies (cubes, rods, and sheets) were synthesizedusing a hydrothermal method and tested for the CO2 hydrogenationreaction. The physicochemical properties of the structured Co3O4 were well characterized by X-ray diffraction(XRD), Raman spectroscopy, field-emission scanning electron microscopy(FESEM), transmission electron microscopy (TEM), high-resolution transmissionelectron microscopy (HRTEM), hydrogen temperature-programmed reduction(H-2-TPR), and X-ray photoelectron spectroscopy (XPS) techniques.Based on the characterization, cube, rod, and sheet Co3O4 nanostructures were found to expose the (100), (110),and (112) planes, respectively. The effect of cobalt oxide morphologieswith different exposed surfaces on the activity and selectivity towardCO(2) hydrogenation reaction in a plug-flow reactor operatedbetween 200 and 400 \& DEG;C under atmospheric pressure conditionswas explored. The results establish a correlation of the catalyticactivity with morphological structures in the order rods \> sheets\> cubes. H-2-TPR and XPS studies demonstrated that thehighreducibility of Co3O4 rod makes it an excellentcatalyst for CO2 hydrogenation.

}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.3c02857}, author = {Gupta, Sharad and Jain, Preeti and Jagadeesan, Dinesh and Vinod, C. P.} } @article {48828, title = {Non-Markov models of single-molecule dynamics from information-theoretical analysis of trajectories}, journal = {Journal of Chemical Physics}, volume = {159}, year = {2023}, month = {AUG }, pages = {064104}, type = {Article}, abstract = {

Whether single-molecule trajectories, observed experimentally or in molecular simulations, can be described using simple models such as biased diffusion is a subject of considerable debate. Memory effects and anomalous diffusion have been reported in a number of studies, but directly inferring such effects from trajectories, especially given limited temporal and/or spatial resolution, has been a challenge. Recently, we proposed that this can be achieved with information-theoretical analysis of trajectories, which is based on the general observation that non-Markov effects make trajectories more predictable and, thus, more {\textquoteleft}{\textquoteleft}compressible{\textquoteright}{\textquoteright} by lossless compression algorithms. Toy models where discrete molecular states evolve in time were shown to be amenable to such analysis, but its application to continuous trajectories presents a challenge: the trajectories need to be digitized first, and digitization itself introduces non-Markov effects that depend on the specifics of how trajectories are sampled. Here we develop a milestoning-based method for information-theoretical analysis of continuous trajectories and show its utility in application to Markov and non-Markov models and to trajectories obtained from molecular simulations.

}, issn = {0021-9606}, doi = {10.1063/5.0158930}, author = {Song, Kevin and Park, Raymond and Das, Atanu and Makarov, Dmitrii E. and Vouga, Etienne} } @article {48750, title = {Novel shear thickening fluids possessing high shear rates using monodispersed silica nanoparticles and PEG}, journal = {Polymer Bulletin}, volume = {80}, year = {2023}, month = {DEC}, pages = {13069-13098}, type = {Article}, abstract = {

Higher shear rate possessing homogeneous shear thickening fluids were synthesized using monodispersed silica nanoparticles and polyethylene glycol (PEG). Novel homogeneous methodology was developed for the synthesis of shear thickening fluids using monodispersed silica nanoparticles and PEG. Shear rate of shear thickening fluids (STF) was determined using rheometer at room temperature. The normal shear rate was observed in the range of 100 to 1200 s(-1), whereas higher shear rate 2000 s(-1) was obtained using monodispersed silica nanoparticles, PEG and shear rate enhancer. Monodispersed silica nanoparticles were synthesized in a typical one-pot using modified Stober{\textquoteright}s method at room temperature. Precursors were used for the synthesis of monodispersed silica nanoparticles such as tetraethyl orthosilicate (TEOS), ethanol, deionized water and ammonia as catalyst. Particle size of monodispersed silica nanoparticles was in the range of 100-1200 nm, and particle size distribution was varied from 0.000 to 0.221. Synthesis of monodispersed silica nanoparticles was studied by various parameters, namely effect of TEOS concentration, grade of ethyl alcohol, ammonia concentration and water concentration. TEOS concentration effect shows particle size and particle size distribution increases with increase in concentration of TEOS. Even though concentration of TEOS was increased up to 5 times the observation was same for all particle sizes such as 100, 300 and 500 nm. Particularly in the case of 300 nm monodispersed silica nanoparticle synthesis, as TEOS concentration was increased from 1 to 5X (5 times) the particle size was increased from 331.7, 447.8, 497.0, 512.0 and 531.7 nm and particle size distribution was 0.005, 0.000, 0.006, 0.007 and 0.089, respectively. The effect of grade of ethyl alcohol illustrates that Indian rectified spirit shows almost similar results with respect to China make ethyl alcohol. Comparative study of China and Indian rectified spirit shows silica nanoparticle size was 174.6 and 174.2 nm, and particle size distribution was 0.065 and 0.071, respectively. Ammonia concentration effect explains particle size and particle size distribution increases with increase in concentration of ammonia. Water concentration effect shows particle size and particle size distribution increases with increase in concentration of ammonia. Comparative data of water concentration effect for 1316 and 1974 mL shows particle size were 321.7 and 488.0 nm, and particle size distribution was 0.083 and 0.05, respectively, under similar conditions. Morphological studies displayed the shape of the silica nanoparticles was spherical, monodispersed and isolated. A typical TEM image of monodispersed silica nanoparticles for 500 nm was observed with extremely low polydispersity, i.e., 0.000. It is very difficult to get such a type of excellent photograph of monodispersity by Stober{\textquoteright}s method particularly on large scale. Rheology study of homogeneous shear thickening fluids studied by varying the parameters such as composition of silica nanoparticles with PEG, effect of amount of solvent, effect of refluxing time, effect of additive with respect to the mol. wt. of PEG and effect of additive such as Tannin. All these parameters of STF explored with respect to the shear rate and shear viscosity. Effect of ethanol amount on STF demonstrates the shear rate increases with increase in amount of solvent. Effect of refluxing time on STF exhibits the shear rate increases with increase in refluxing time. Effect of composition based on 500 nm monodispersed silica nanoparticles and PEG 200 with respect to 60:40, 65:35 and 70:30 composition was studied and the results predict that shear rate increases with increase in silica percentage in composition, i.e., 118, 265 and 1200 s(-1) for 60:40, 65:35 and 70:30 composition, respectively, whereas maximum viscosity decreases with increase in silica content, i.e., 2.559, 1.420 and 1.200 Pa.s for 60:40, 65:35 and 70:30 composition, respectively. Effect of additive on shear rate and shear viscosity illustrates that shear rate decreases with increase in additive percentage in composition, whereas maximum viscosity increases with increase in additive content. Effect of additives on shear rate and shear viscosity was performed using 65:35 composition with respect to PEG 200 along with PEG 6000 shows shear rate was decreased from 142 to 6.42 s(-1) and maximum viscosity was increased from 56.1 to 571.0 Pa.s when the quantity of PEG 6000 was doubled. In general, additive decreases shear rate and increases shear viscosity (maximum). But effect of Tannin as an additive on 500 nm monodispersed silica nanoparticles with PEG 200 using 70:30 composition showed enormous increase in shear rate, i.e., 2000 s(-1). This is anomalous behavior of additive was observed.

}, keywords = {Monodispersed silica nanoparticles, Nanocomposite, Polyethylene glycol, Shear rate, Shear thickening fluid}, issn = {0170-0839}, doi = {10.1007/s00289-023-04696-7}, author = {Chavan, Nayaku and Dhage, Atul and Wale, Apparav and Thorave, Asmita and Rajdeo, Kishor and Kamble, Sanjay and Ponrathnam, Surendra and Tambe, Sanjeev and Verma, Sanjeevkumar} } @article {48451, title = {Oligothiophene-ring-strapped perylene bisimides: functionalizable coaxial donor-acceptor macrocycles}, journal = {Angewandte Chemie-International Edition}, volume = {62}, year = {2023}, month = {JAN}, type = {Article}, abstract = {

Aesthetic designs from nature enable new knowledge to be gained and, at the same time, inspire scientific models. In this context, multicomponent macrocycles embody the advantage of precisely positioning the structural units to achieve efficient communication between them. However, the construction of a functionalizable macrocycle for ultrafast charge separation and stabilization has not been attempted. Herein, we report the synthesis, crystal structure, and transient absorption of a new functionalizable macrocycle consisting of an oligothiophene-ring-strapped perylene bisimide. Transient absorption results point to a sequential improvement in charge separation and stabilization from the macrocycle to the corresponding linear dimer and 2D polymer due to the unique design. Our macrocycle design with a supportive spatial arrangement of the donor and acceptor units will inspire the development of more complex synthetic systems with exciting electron-transfer and charge-separation features.

}, keywords = {Charge Separation, Donor-Acceptor Systems, Electron Transfer, Macrocycles, Perylene Bisimides}, issn = {1433-7851}, doi = {10.1002/anie.202212934}, author = {Dnyaneshwar Veer, Sairam and Chandrakant Wakchaure, Vivek and Asokan, Kiran and Dixit, Ruchi and Goswami, Tanmay and Saha, Ramchandra and Gonnade, Rajesh and Ghosh, Hirendra N. and Santhosh Babu, Sukumaran} } @article {48292, title = {Oxidation of ethylene by Cu/TiO2: reducibility of Cu2+ in TiO2 as a possible descriptor of catalytic efficiency}, journal = {Catalysis Science \& Technology}, volume = {13}, year = {2023}, month = {APR}, pages = {2330-2339}, type = {Article}, abstract = {

Catalytic oxidation using non-noble metal-based catalysts is a promising approach to mitigate pollution due to VOCs in the air. In this work, mesoporous Cu/TiO2 catalysts containing different concentrations of Cu2+ (0.2, 1, 3, and 4 wt\% Cu w.r.t. Ti) were synthesized using the sol-gel technique. The catalysts were characterized using inductively coupled plasma-optical emission spectrometry, XRD, Raman spectroscopy, N-2 physisorption, cyclic voltammetry, H-2-TPR and electron microscopy to understand the structure and composition. The thermal catalytic gas phase oxidation of ethylene was studied by heating a mixture of ethylene (1.5 vol\%) and air (5.9 vol\%) in the presence of the Cu/TiO2 samples in the temperature range of 298 to 773 K. Cu/TiO2 showed a higher catalytic activity compared to TiO2 for the thermal oxidation of ethylene, indicating a strong promotion by doped copper ions. A volcanic behaviour in the catalytic activity was observed with different concentrations of Cu doping, with 1\% Cu/TiO2 showing a 99.5\% ethylene conversion at 673 K and 100\% selectivity to CO2. The activity of 1\% Cu/TiO2 remained consistent without deactivation for 24 h. At low dopant concentrations of Cu (0.2 and 1\% Cu/TiO2), the reduction of Cu2+ to Cu+ was observed. An interplay of oxygen vacancies (O-V), Cu+, Cu2+ and Ti4+ may be involved in controlling the activity. DRIFT studies indicated the formation of surface bidendate carbonate as a possible intermediate.

}, issn = {2044-4753}, doi = {10.1039/d2cy02170f}, author = {Rajendran, K. and Sharma, Mandeep and Jaison, Augustine and Ankitha, Menon and Tiwari, Ankit D. and Vinod, C. P. and Jagadeesan, Dinesh} } @article {48270, title = {Palladium-catalyzed chemoselective oxygenation of C(sp2)-H and C(sp3)-H bonds in isatins}, journal = {Organic Letters}, volume = {25}, year = {2023}, month = {MAR}, pages = {1862-1867}, type = {Article}, abstract = {

The palladium-catalyzed chemoselective C(sp2)-H and C(sp3)-H bond oxygenation of substituted isatin derivatives is reported. This mild protocol exhibits the C5 C(sp2)-H oxygenation of isatins through electrophilic intermolecular C-H palladation in concentrated solutions using PhI(OAc)2 or Selectfluor as an oxidant, whereas it exhibits- N-CH3 C(sp3)-H oxygenation in dilute solutions via carbonyl-assisted intramolecular palladation in the presence of K2S2O8. This oxygenation reaction provides a direct and unified approach for synthesizing diverse oxygenated isatins with sensitive functionalities, including biorelevant compounds.

}, issn = {1523-7060}, doi = {10.1021/acs.orglett.3c00342}, author = {Vijaykumar, Muniyappa and Pradhan, Chandini and Gonnade, Rajesh G. and Punji, Benudhar} } @article {48723, title = {Pd nanoparticles supported on N-incorporated hybrid organosilica as an active and selective low-temperature phenol hydrogenation catalyst}, journal = {ACS Applied Nano Materials}, volume = {6}, year = {2023}, month = {JUN}, pages = {11500-11512}, type = {Article}, abstract = {

A heterogeneous Pd-NPMO hybrid-silicacatalyst is synthesized andits application for aqueous phase selective hydrogenation of phenolto cyclohexanone at near ambient temperature (40 degrees C) and underatmospheric hydrogen pressure is demonstrated. The homogeneously distributedPd nanoparticles on N-bridged hybrid mesoporous organosilica showedremarkable activity and selectivity for cyclohexanone compared tothe unmodified Pd-SBA-15 catalyst. Control experiments strongly claimthe role of nitrogen domains in the organic framework of hybrid silicasupport in stabilizing small Pd nanoparticles and possibly modifyingthe Pd sites responsible for catalysis to activate the substrate moleculesin water. The hybrid silica catalyst was stable and reused severaltimes without any significant drop-in activity, proving the heterogeneityof the bifunctional Pd catalyst. Based on the density functional theorystudy and experimental interventions, a possible reaction mechanismfor the low-temperature phenol hydrogenation explaining the role oforganic domains in the hybrid-silica framework is proposed.

}, keywords = {cyclohexanone, Hybrid silica, palladium nanoparticles, Periodic mesoporous organosilica, phenol hydrogenation}, doi = {10.1021/acsanm.3c01540}, author = {Betsy, K. J. and Bajpai, Priyam and Lazar, Anish and Vanka, Kumar and Vinod, C. P.} } @article {48919, title = {Polymerizable solvent-free organic liquids: a new approach for large area flexible and foldable luminescent films}, journal = { Angewandte chemie-international editon }, volume = {62}, year = {2023}, month = {AUG}, type = {Article}, abstract = {

The high demand for light-emitting and display devices made luminescent organic materials as attractive candidates. Solvent-free organic liquids are one of the promising emitters among them due to the salient features. However, the inherent limitations of forming sticky and noncurable surfaces must be addressed to become an alternate emitter for large-area device applications. Herein, we functionalized solvent-free organic liquids having monomeric emission in bulk with polymerizable groups to improve the processability. The polymerizable group on carbazole, naphthalene monoimide, and diketopyrrolopyrrole-based solvent-free liquid emitters enabled on-surface polymerization. These emitters alone and in combinations can be directly coated on a glass substrate without the help of solvents. Subsequent photo or thermal polymerization leads to stable, non-sticky, flexible, foldable, and free-standing large-area films with reasonably high quantum yield. Our demonstration of the tunable and white light-emitting films using polymerizable solvent-free liquids might be a potential candidate in flexible/foldable/stretchable electronics. The new concept of polymerizable liquid can be extended to other functional features suitable for futuristic applications.

}, keywords = {Energy Transfer, polymerization, Solvent-Free Organic Liquids, Thin-Film, White Light}, issn = {1433-7851}, doi = {10.1002/anie.202307381}, author = {Wakchaure, Vivek Chandrakant and Veer, Sairam Dnyaneshwar and Nidhankar, Aakash D. and Kumar, Viksit and Narayanan, Aswini and Babu, Sukumaran Santhosh} } @article {48470, title = {Potential role of lewis acid-base adducts in enhancing stereoselectivity in ziegler-natta catalysts: a DFT study}, journal = {Journal of Physical Chemistry C}, volume = {127}, year = {2023}, month = {APR}, pages = {7220-7229}, type = {Article}, abstract = {

Ziegler-Natta (Z-N) systems have been well established as heterogeneous catalysts that produce isotactic polypropylene and polyethylene with great efficiency. Such systems benefit considerably from donors (Lewis bases), whose addition significantly improves the stereoselectivity of polymerization. There is a consensus that the primary role of the external donors is to coordinate at the vacant site created by the extraction of internal donors and thus maintain the stereoselectivity. However, the bite difference between internal donors such as phthalates or succinate derivatives and external donors such as alkoxysilanes raises the question of how external donors can effectively replace internal donors. In order to investigate this, we have chosen four external alkoxysilane donors: (1) diisopropyl dimethoxysilane, (2) dicyclopentyl dimethoxysilane, (3) disec-butyl dimethoxysilane, and (4) sec-butyl(methyl) dimethoxysilane. DFT studies reveal that the bite difference problem can be overcome by the favorable formation of adducts between the alkoxysilane external donors and AlEt2Cl in the Z-N systems. These adducts tend to coordinate in the vicinity of the active site. Furthermore, our findings demonstrate the potential of these Lewis acid-base adducts to enhance the stereoselectivity of Z-N catalysts significantly.

}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.3c00814}, author = {Raj, K. Vipin and Gupta, Virendra Kumar and Vanka, Kumar} } @article {48740, title = {Quantum dot (Aun/Agn, n=3-8) capped single lipids: interactions and physicochemical properties}, journal = {Physical Chemistry Chemical Physics}, volume = {25}, year = {2023}, month = {AUG}, pages = {22294-22303}, type = {Article}, abstract = {

Realizing the potential of nano-hybrid biomaterials in various applications (nanoprobes to drug delivery), special attention has been devoted towards their synthesis and development. Nonetheless, several questions pertaining to the interface chemistry between the constituent entities (biomolecules and organic/inorganic part) of these hybrids, still remain unresolved. Keeping these unsolved issues in mind, the present theoretical investigation focuses on determining the electronic/physicochemical properties and interactions within gold and silver quantum dot-capped single lipid molecules. Quantum dots of varying sizes and shapes have been chosen and then coupled with lipid molecules (1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine (DMPE), 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol, sodium salt (DMPG)), at the choline/glycerol, carboxylate and phosphate site. It has been identified that Au Qds interact strongly as compared to Ag clusters. In addition to the type, the shape and size of the Qd also influences their attachment with lipids. Among various sites, the phosphate site provides a considerably stronger platform for the coupling of Qds. On the other hand, attachment at the choline site leads to significantly lower interaction energies. The trend noted in interaction energies coincides with the structure-electronic property analysis (interatomic bond distances, charge transfer, PO2- stretching frequencies), which further helps in deducing the nature of interactions. The molecular dynamics simulations performed on selected Qd-lipid complexes established that the Qd interacting with lipids at the phosphate site remains fairly stable at room temperature without undergoing fragmentation into individual components. On the other hand, at the choline site, the Qd-to-lipid coupling is unstable and therefore they experience disintegration at 300 K temperature. Additionally, a unique glycerol-to-phosphate site crossover is evidenced, which reaffirms that the phosphate site is selectively preferred by Qds for binding with lipid molecules.

}, issn = {1463-9076}, doi = {10.1039/d3cp01131c}, author = {Maneri, Asma H. H. and Varode, Shruti Suhas and Maibam, Ashakiran and Ranjan, Priyatosh and Krishnamurty, Sailaja and Joshi, Krati} } @article {48334, title = {Relativistic coupled-cluster study of SrF for low-energy precision tests of fundamental physics}, journal = {Theoretical Chemistry Accounts}, volume = {142}, year = {2023}, month = {FEB}, pages = {15}, type = {Article}, abstract = {

SrF, being a laser-coolable molecule, can be an interesting system for spectroscopic tests of fundamental physics. We present an electronic structure study of this molecule within the four-component relativistic coupled-cluster singles and doubles (RCCSD) framework and employ the RCCSD-based methods to compute its molecular-frame dipole moment and core properties such as hyperfine structure coupling constant and molecular P, T-odd electronic structure parameters that are of great importance for the high-precision tests of fundamental physics. The impact of basis set size, Hamiltonian and nuclear model on the property calculation of SrF is also investigated. The computed results are in good agreement with the available experimental values. The present study shows that the SrF molecule could be useful for high-precision molecular experiments to explore physics beyond the Standard Model of elementary particles.

}, keywords = {Coupled cluster theory, CP violation, Hyperfine structure, Molecular spectroscopy, Relativistic effects}, issn = {1432-881X}, doi = {10.1007/s00214-023-02953-6}, author = {Talukdar, Kaushik and Buragohain, Haimyapriya and Nayak, Malaya K. K. and Vaval, Nayana and Pal, Sourav} } @article {48814, title = {Response of cardiac pulse parameters in humans at various inclinations via 360{\textdegree} rotating platform for simulated microgravity perspective}, journal = {NPJ Microgravity}, volume = {9}, year = {2023}, month = {JUL}, pages = {54}, type = {Article}, abstract = {

On the Earth, the human body is designed and adapted to function under uniform gravitational acceleration. However, exposure to microgravity or weightlessness as experienced by astronauts in space causes significant alterations in the functioning of the human cardiovascular system. Due to limitations in using real microgravity platforms, researchers opted for various ground-based microgravity analogs including head-down tilt (HDT) at fixed inclination. However, in the present study, an investigation of response of various cardiac parameters and their circulatory adaptation in 18 healthy male subjects was undertaken by using an indigenously developed 360 \& DEG; rotating platform. Cardiac pulse was recorded from 0 \& DEG; to 360 \& DEG; in steps of 30 \& DEG; inclination using piezoelectric pulse sensor (MLT1010) and associated cardiac parameters were analyzed. The results showed significant changes in the pulse shape while an interesting oscillating pattern was observed in associated cardiac parameters when rotated from 0 \& DEG; to 360 \& DEG;. The response of cardiac parameters became normal after returning to supine posture indicating the ability of the cardiovascular system to reversibly adapt to the postural changes. The observed changes in cardiac parameters at an inclination of 270 \& DEG;, in particular, were found to be comparable with spaceflight studies. Based on the obtained results and the proposed extended version of fluid redistribution mechanism, we herewith hypothesize that the rotation of a subject to head down tilt inclination (270 \& DEG;) along with other inclinations could represent a better microgravity analog for understanding the cumulative cardiac response of astronauts in space, particularly for short duration space missions.

}, doi = {10.1038/s41526-023-00301-3}, author = {Jagtap, Sagar and Kumar, Ajay and Mahale, Bhoopesh and Dixit, Jyotsana and Kalange, Ashok E. and Kanawade, Rajesh and Gangal, Shashikala and Vidyasagar, Pandit} } @article {48472, title = {Rivaroxaban eutectics with improved solubility, dissolution rates, bioavailability and stability}, journal = {Crystengcomm}, volume = {25}, year = {2023}, month = {JUN }, pages = {3253-3263}, type = {Article}, abstract = {

Rivaroxaban (RXB) is a direct factor Xa inhibitor used for the treatment of deep vein thrombosis (DVT, a blood clot in the leg) and pulmonary embolism (PE, a blood clot in the lung) and to prevent blood clots in atrial fibrillation following hip or knee surgery. However, RXB suffers from poor solubility that hinders its broader application. Although its cocrystals are reported for solubility enhancement, the methodology used to prepare multi-component crystals is complex. Also, it uses hazardous solvents to develop cocrystals. We have prepared eutectics of RXB with caffeic acid (CAA), coumaric acid (CA), fumaric acid (FA), succinic acid (SA), mandelic acid (MA) and trimesic acid (TA) and analyzed them using hot stage microscopy (HSM), differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and fourier transform infrared spectroscopy (FTIR) techniques. The saturation solubility and dissolution rate profiles were also obtained to investigate the effect of eutectics on these parameters. Amongst all the coformers tested, coformers CAA, CA, and FA showed significant enhancement in the solubility of RXB. The powder dissolution rate of the eutectics showed considerable enhancement compared to that of RXB. In vivo pharmacokinetic study was carried out for RXB-CAA, RXB-CA and RXB-FA in rats and compared with RXB, which showed 1.5 and 1.4 times enhancement in relative bioavailability for RXB-CAA and RXB-CA, respectively. Stability studies were carried out as per ICH guidelines for all the eutectics, which revealed excellent stability over six months under accelerated (40 degrees C and 75\%) conditions and twelve months under long-term (30 degrees C and 60\% RH) conditions. The DFT studies carried out using the B3LYP/TZVP level of theory revealed higher Gibbs free interaction energy (Delta G(int)) for homosynthons (drugMIDLINE HORIZONTAL ELLIPSISdrug and coformerMIDLINE HORIZONTAL ELLIPSIScoformer) than heterosynthons (drugMIDLINE HORIZONTAL ELLIPSIScoformer).

}, doi = {10.1039/d3ce00261f}, author = {Shaligram, Parth S. and George, Christy P. and Sharma, Himanshu and Mahadik, Kakasaheb R. and Patil, Sharvil and Vanka, Kumar and Arulmozhi, S. and Gonnade, Rajesh G.} } @article {48738, title = {Six-membered NHC stabilized monomeric zinc complexes}, journal = {European Journal of Inorganic Chemistry}, volume = {26}, year = {2023}, month = {JUL}, pages = {e202300167}, type = {Article}, abstract = {

This paper describes the rare use of a 6-membered saturated N-heterocyclic carbene (NHC) known as 1,3-di(2,6-diisopropylphenyl) tetrahydropyrimidine-2-ylidene (abbreviated as 6-SI-Dipp) as a ligand in zinc chemistry. We report on the investigation of the reactions between 6-SI-Dipp and ZnX2, which resulted in a range of new monomeric 6-SIDipp center dot ZnX2 complexes (X=Et (1), Cl (2), Br (3), and I (4)). We also prepared a new NHC zinc complex where the two substituents of the zinc atom are different, 6-SIDipp center dot Zn(Et)Br (7) through the reaction of the proligand [6-SIDippH]Br with ZnEt2. We have observed that the reactions of complex 1 with sulfur and HBpin led to the removal of the ZnEt2 moiety, resulting in the formation of a C=S double bond and a B H activation product, respectively. Lastly, the reaction of 1 with five-membered NHCs led to the exchange of carbene and the formation of either 5-IDipp center dot ZnEt2 (8) or 5-SIDipp center dot ZnEt2 (9).

}, keywords = {Lewis adduct, NHC, X-ray diffraction, zinc}, issn = {1434-1948}, doi = {10.1002/ejic.202300167}, author = {Gour, Kritika and Kundu, Gargi and Dash, Soumya Ranjan and Vanka, Kumar and Tothadi, Srinu and Sen, Sakya S.} } @article {48452, title = {Speed breeding opportunities and challenges for crop improvement}, journal = {Journal of Plant Growth Regulation}, volume = {42}, year = {2023}, month = {JAN}, pages = {46-59}, type = {Article}, abstract = {

Crop improvement in light of the rapidly changing climate and the increasing human population continues to be one of the primary concerns for researchers across the globe. The rate at which current crop improvement programs are progressing is essentially inadequate to meet the food demand. There is an urgent need for redesigning the crops for climate resilience and sustainable yield and nutrition. The rate of crop improvement is largely impeded owing to the long generation time taken by crop plants during the breeding process. As a solution in this direction, speed breeding is now being practiced at a large scale to reduce generation time to accommodate multiple generations of crops per year. To enhance the efficiency of breeding, researchers are now adopting an integrated approach where speed breeding is used along with modern plant breeding and genetic engineering technologies. In the present review, we have summarized the technological aspects, opportunities, and limitations associated with speed breeding. The application of speed breeding such as mapping population development, haplotype-based breeding, transgenic breeding, and genome-edited line advancement has also been discussed. Speed breeding is a promising technology that expedites the goals of food and industrial crop improvement by reducing the breeding cycles for establishing nutritional security and sustainable agriculture.

}, keywords = {Genome editing, Genomic selection, Haplotype breeding, Speed breeding, Transgenic breeding}, issn = {0721-7595}, doi = {10.1007/s00344-021-10551-8}, author = {Sharma, Shivani and Kumar, Amit and Dhakte, Priyanka and Raturi, Gaurav and Vishwakarma, Gautam and Barbadikar, Kalyani M. and Das, B. K. and Shivaraj, S. M. and Sonah, Humira and Deshmukh, Rupesh} } @article {48984, title = {Sulfonated zinc phthalocyanine coating as an efficient and ecofriendly corrosion inhibitor for copper surfaces: an in silico led design and its experimental validation}, journal = {Langmuir}, volume = {39}, year = {2023}, month = {NOV }, pages = {17295-17307}, type = {Article}, abstract = {

The current study highlights the successful integration of an in silico design with experimental validation to create a highly effective corrosion inhibitor for copper (Cu) surfaces. The synthesized sulfonated zinc phthalocyanine (Zn-Pc) is electrochemically characterized and demonstrates an impressive 97\% inhibition efficiency, comparable to the widely used industrial corrosion inhibitor, BTA, for Cu surfaces. The corrosion inhibition is comprehensively analyzed through potentiodynamic polarization and impedance spectroscopy techniques, supported by their respective equivalent circuits. Furthermore, the sample undergoes thorough characterization using scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, contact angle measurements, and atomic force microscopy. Density functional theory calculations reveal that sulfonated Zn-Pc exhibits the highest interaction energy, underscoring its exceptional inhibition properties. These results open possibilities for utilizing computational methods to design and optimize corrosion inhibitors for protection of Cu surfaces.

}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.3c02393}, author = {Dekshinamoorthy, Amuthan and Samal, Pragnya Paramita and Krishnamurty, Sailaja and Khatri, Praveen K. and Jain, Suman Lata and Ray, Anjan and Vijayaraghavan, Saranyan} } @article {48826, title = {Synthesis, biological evaluation and docking studies of silicon incorporated diarylpyrroles as MmpL3 inhibitors: an effective strategy towards development of potent anti-tubercular agents}, journal = {European Journal of Medicinal Chemistry}, volume = {259}, year = {2023}, month = {NOV }, pages = {115633}, type = {Article}, abstract = {

Growing global demand for new molecules to treat tuberculosis has created an urgent need to develop novel strategies to combat the menace. BM212 related compounds were found to be potent anti-TB agents and they inhibit mycolic acid transporter, MmpL3, a known potent drug target from Mycobacterium tuberculosis. In order to enhance their inhibitory potency, several silicon analogues of diarylpyrroles related to BM212 were designed, synthesized, and evaluated for anti-tubercular activities. In Alamar blue assay, most of the silicon-incorporated compounds were found to be more potent than the parent compound (BM212), against Mycobacterium tuberculosis (MIC = 1.7 \& mu;M, H37Rv). Docking results from the crystal structure of MmpL3 and silicon analogues as pharmacophore model also strongly correlate with the biological assays and suggest that the incorporation of silicon in the inhibitor scaffold could enhance their potency by stabilizing the hydrophobic residues at the binding pocket. The best docking hit, compound 12 showed an MIC of 0.1 \& mu;M against H37Rv with an acceptable in vitro ADME profile and excellent selectivity index. Overall, the present study indicates that, the designed silicon analogues, especially compound 12 could be a good inhibitor for an intrinsically flexible drug-binding pocket of MmpL3 and has potential for further development as anti-tubercular agents.

}, keywords = {antibiotic, BM212, docking studies, MmpL3 inhibitor, Silicon analogue, tuberculosis}, issn = {0223-5234}, doi = {10.1016/j.ejmech.2023.115633}, author = {Vasudevan, N. and Motiwala, Zenia and Ramesh, Remya and Wagh, Sachin B. and Shingare, Rahul D. and Katte, Revansiddha and Anand, Amitesh and Choudhary, Sushil and Kumar, Ajay and Gokhale, Rajesh S. and Kulkarni, Kiran A. and Reddy, D. Srinivasa} } @article {48832, title = {Synthesis, characterization, crystal structure, in silico and computational studies on a novel Schiff base derived from α-chlorocinnamaldehyde and 4-aminoantipyrine}, journal = {Journal of Molecular Structure}, volume = {1289}, year = {2023}, month = {OCT}, pages = {135928}, type = {Article}, abstract = {

Schiff base, 4-(((1E,2Z)-2-chloro-3-phenylallylidene)amino)-1,5-dimethyl-2-phenyl-1,2 -dihydro-3H-pyrazol-3-one (1) was synthesized by condensation reaction of 4-aminoantipyrine and \& alpha;-chlorocinnamaldehyde. The compound was characterized using Fourier-transform infrared spectroscopy (FT-IR), ultraviolet (UV)-visible spectroscopy, proton and carbon nuclear magnetic resonance spectroscopy (1H/13C NMR) and single-crystal X-ray diffraction analysis (SC-XRD). Density functional theory (DFT) was used to compute molecular parameters and also compared them with experimental data. The X-ray diffraction data revealed that the compound crys-tallizes as a monoclinic crystal system with a space group of C2/c and Z = 8, and is stabilized by C12-H12MIDLINE HORIZONTAL ELLIPSISO1, and C8-H8AMIDLINE HORIZONTAL ELLIPSISO1 intramolecular hydrogen bonds. The presence of a distinctive azomethine C = N bond length N3-C12 of 1.283(3) \& ANGS;, and 1640 cm-1 stretching vibration in the FT-IR spectrum are evidence of the formation of a Schiff base. The computational result indicates that the ionization energy (IE), and electron affinity (EA) values for the molecule are 4.025 and 2.110 eV, respectively. The positive value of EA suggests that the addition of an electron to the molecule would be an exothermic process. The evaluated energy is relatively low and is an expression of the ease of electron transfer from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). Hirsfeld surface map over dnorm and curvedness surface indicated the presence of 7C-7C stacking while the shape factor index suggests donor and acceptor intermolecular C-H-7C. Analysis of Hirsfeld surfaces concerning the fingerprint indicated a minimal contribution from the de -di pair and reveals H{\textendash}H as a major contribution to the Hirsfeld surface. However, the molecular packing did not confirm H{\textendash}H as a significant contributor the packing. Docking calculations on the compound showed average theoretical binding energies toward aromatase (-5.99 \& PLUSMN; 0.34 kcal/mol) and fibroblast growth factor receptor (FGFR) (-17.57 \& PLUSMN; 6.85 kcal/mol), indicating binding interactions with both protein targets.

}, keywords = {Computational studies, molecular modeling, Schiff base, X-ray crystallography}, issn = {0022-2860}, doi = {10.1016/j.molstruc.2023.135928}, author = {Adimudo, Hillary Chijioke and Agu, Chidike Justus and Okenyeka, Obinna U. and Eddy, Nnabuk O. and Dim, Ebubechukwu Nnamdi and Dege, Necmi and Bonardd, Sebastian and Vanka, Kumar and Ibezim, Akachukwu and Idika, Digbo Iku and Diaz, David Diaz and Obasi, Nnamdi Lawrence} } @article {49138, title = {Synthesis of advanced asbestos-free material using rice husk ash and marble waste for thermal insulation applications}, journal = {Biomass Conversion and Biorefinery}, volume = {13}, year = {2023}, month = {JUL}, pages = {8985-8998}, type = {Article}, abstract = {

The importance and utilization of advanced thermal insulating materials increase due to their broad and irreplaceable energy conservation role. This paper describes the novel way of achieving insulating material. In two waste by-products, namely rice husk ash (RHA), agriculture waste, and marble waste powder (MWP), industrial waste has been utilized to make asbestos-free advanced material for thermal insulation. A novel method for making asbestos-free advanced material for thermal insulation using RHA and marble waste{\textquoteright}s inherent characteristics has developed mechano-chemical for appropriate physico-chemical consolidation, densification, and ceramic processing route. The Si and Ca sources undergo a series of chemical transformations accompanied by mass transfer and thermal reactions during the synthesis process. The formation of this silicate compound occurs due to the presence of higher contents of CaO in marble waste powder (MWP) and silica in rice husk ash (RHA), resulting in thermal insulating characteristics in the advanced thermal insulation material (ATIM). Raman spectra of ATIM after heating at 1100 degrees C were mainly amorphous, which had a broad peak at 1072 cm(-1). This shows thermal transformation occurs after the heating process, the admixture of tailored powder, and fly ash (FA). The density of the ATIM is found to be 1150 kg/m(3). The phase transformation (glass transition temperature) was found in all the samples between 600 and 800 degrees C. The mechanical properties, namely the compressive strength and impact strength evaluation test, showed that the material meets the standard specifications for ceramic tiles. The thermal conductivity (W/mK) was calculated from different temperature 30, 50, 100,150, and 200 degrees C and found to be 0.571, 0.541, 0.516, 0.498, and 0.477, respectively. According to the test results, it is concluded that ATIM from MWP, RHA, and FA were excellent insulating components. The novel feature of the reported process is the development of non-toxic and asbestos-free thermal insulating low-cost material wherein chemically designed and mineralogically formulating desired phases lead to the homogeneous and effective thermal insulating matrix. The process is feasible, simple, cheap, and highly energy-efficient, increases production efficiency, and is environmentally friendly. The widespread use of advanced material for a broad application spectrum ranges from aerospace, automobile, electronics, transportation, construction, to other industries.

}, keywords = {Asbestos, Fly ash, Marble waste, Material, Rice husk ash, Thermal insulation}, issn = {2190-6815}, doi = {10.1007/s13399-021-01950-8}, author = {Verma, Sarika and Bajpai, Harsh and Suresh, S. and Mili, Medha and Gupta, Ritesh Kumar and Shetty, Rohit and Kamble, Sanjay and Khan, Mohd. Akram and Hashmi, S. A. R. and Srivastava, A. K.} } @article {48720, title = {Synthesis of Si(IV)- and Ge(II)-substituted amines, hydrazone, and hydrazine from hypersilyl germylene}, journal = {Organometallics}, volume = {42}, year = {2023}, month = {OCT}, pages = {2983-2990}, type = {Article}, abstract = {

This study investigates the reactivity of a hypersilyl germylene [PhC-(NtBu)(2)GeSi-(SiMe3)(3)] (1) with various organic compounds including azides, diazoalkanes, 1,2-diphenylhydrazine, and trifluoroacetophenone. The reactivity observed in these reactions is driven by the insertion of the organic fragment between a silicon and germanium bond. This leads to the formation of novel compounds, including an amine featuring three different substituents from three different elements of group 14. When reacting with Me3SiCHN2, we observed the insertion of the diazoalkane fragment in an end-on fashion into the Ge-Si bond. An analogous trend was observed in reactions with 1,2-diphenylhydrazine and trifluoroacetophenone, where the N-N and C-O fragments were inserted into the Ge-Si bond. Multinuclear NMR and single-crystal X-ray diffraction analyses were conducted to characterize the newly synthesized compounds.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.3c00318}, author = {Ajithkumar, V. S. and Ghanwat, Pratiksha B. and Raj, K. Vipin and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {48953, title = {Tailoring COFs: transforming nonconducting 2D layered COF into a conducting quasi-3D architecture via interlayer knitting with polypyrrole}, journal = {Journal of the American Chemical Society}, volume = {146}, year = {2023}, month = {DEC}, pages = {487-499}, type = {Journal Article}, abstract = {

Improving the electronic conductivity and the structural robustness of covalent organic frameworks (COFs) is paramount. Here, we covalently cross-link a 2D COF with polypyrrole (Ppy) chains to form a quasi-3D COF. The 3D COF shows well-defined reflections in the SAED patterns distinctly indexed to its modeled crystal structure. This knitting of 2D COF layers with conjugated polypyrrole units improves electronic conductivity from 10(-9) to 10(-2 )S m(-1). This conductivity boost is affirmed by the presence of density of states near the Fermi level in the 3D COF, and this elevates the COF{\textquoteright}s valence band maximum by 0.52 eV with respect to the parent 2D pyrrole-functionalized COF, which agrees well with the opto-electro band gaps. The extent of HOMO elevation suggests the predominant existence of a polaron state (radical cation), giving rise to a strong EPR signal, most likely sourced from the cross-linking polypyrrole chains. A supercapacitor devised with COF20-Ppy records a high areal capacitance of 377.6 mF cm(-2), higher than that of the COF loaded with noncovalently linked polypyrrole chains. Thus, the polypyrrole acts as a {\textquoteleft}{\textquoteleft}conjugation bridge{\textquoteright}{\textquoteright} across the layers, lowering the band gap and providing polarons and additional conduction pathways. This marks a far-reaching approach to converting many 2D COFs into highly ordered and conducting 3D ones.

}, keywords = {covalent organic frameworks, Electrical conductivity}, issn = {0002-7863}, doi = {10.1021/jacs.3c09937}, author = {Jain, Chitvan and Kushwaha, Rinku and Rase, Deepak and Shekhar, Pragalbh and Shelke, Ankita and Sonwani, Disha and Ajithkumar, Thalasseril G. and Vinod, Chathakudath Prabhakaran and Vaidhyanathan, Ramanathan} } @article {48769, title = {Taming the parent oxoborane}, journal = {Chemical Science}, volume = {14}, year = {2023}, month = {JUN}, pages = {5894-5898}, type = {Article}, abstract = {

Despite recent advancements in the chemistry of multiply bound boron compounds, the laboratory isolation of the parent oxoborane moiety, HBO has long remained an unsolved and well-recognized challenge. The reaction of 6-SIDipp(.)BH3 [6-SIDipp = 1,3-di(2,6-diisopropylphenyl)tetrahydropyrimidine2-ylidene] with GaCl3 afforded an unusual boron-gallium 3c-2e compound (1). The addition of water to 1 resulted in the release of H-2 and the formation of a rare acid stabilized neutral parent oxoborane, LB(H)]O (2). Crystallographic and density functional theory (DFT) analyses support the presence of a terminal B=O double bond. Subsequent addition of another equivalent of water molecule led to hydrolysis of the B-H bond to the B-OH bond, but the {\textquoteleft}B=O{\textquoteright} moiety remained intact, resulting in the formation of the hydroxy oxoborane compound (3), which can be classified as a monomeric form of metaboric acid.

}, issn = {2041-6520}, doi = {10.1039/d3sc01544k}, author = {Kundu, Gargi and Amrutha, P. R. and Raj, K. Vipin and Tothadi, Srinu and Vanka, Kumar and Sen, Sakya S.} } @article {48758, title = {Thermally activated delayed fluorescent solvent-free organic liquid hybrids for tunable emission applications}, journal = {Chemistry-An Asian Journal}, volume = {18}, year = {2023}, month = {JUL }, type = {Article}, abstract = {

The synthetic feasibility and excellent luminescence features of organic molecules attracted much attention and were eventually found useful in lighting applications. In this context, a solvent-free organic liquid having attractive thermally activated delayed fluorescence features in bulk along with high processability has prime importance. Herein, we report a series of naphthalene monoimide-based solvent-free organic liquids exhibiting cyan to red thermally activated delayed fluorescence with luminescence quantum yields up to 80\% and lifetimes between 10 to 45 mu s. An effective approach explored energy transfer between liquid donors with various emitters exhibiting tunable emission colors, including white. The high processability of liquid emitters improved the compatibility with polylactic acid and was used for developing multicolor emissive objects using 3D printing. Our demonstration of the thermally activated delayed fluorescence liquid will be much appreciated as a processable alternate emissive material suitable for large-area lighting, display, and related applications.

}, keywords = {3D printing, Energy Transfer, OLED, Organic Liquids, TADF}, issn = {1861-4728}, doi = {10.1002/asia.202300276}, author = {Nidhankar, Aakash D. D. and Goudappagouda and Kothavade, Premkumar D. and Dongre, Sangram D. and Veer, Sairam Dnyaneshwar and Dash, Soumya Ranjan and Rajeev, Kavya and Unni, K. N. Narayanan and Shanmuganathan, Kadhiravan and Babu, Sukumaran Santhosh} } @article {48342, title = {Titanium trisulfide nanosheets and nanoribbons for field emission- based nanodevices}, journal = {ACS Applied Nano Materials}, volume = {6}, year = {2023}, month = {JAN}, pages = {44-49}, type = {Article}, abstract = {

The field emission (FE) properties of TiS3 nanosheets and nanoribbons, synthesized by direct sulfuration of bulk titanium, are investigated. The nanosheets show an enhanced FE behavior with a low turn-on field of similar to 0.3 V/ mu m, required for drawing an emission current density of similar to 10 mu A/cm2. Interestingly, the TiS3 nanosheet emitter delivered a large emission current density of similar to 0.9 mA/ cm2 at a relatively low applied electric field of similar to 0.4 V/mu m. We have estimated the values of the field enhancement factor (beta), which are found to be similar to 5 x 104 for the TiS3 nanosheet emitter and similar to 4 x 103 for the nanoribbon emitter. We attribute the superior FE performance to the presence of atomically sharp edges and the reduced thickness of TiS3, as reflected in the high value of beta. In fact, the nanosheet sample presents a higher density of ultrathin layers (similar to 12 nm-thick), and thus, they have a larger edge to volume ratio than the nanoribbon samples (which are similar to 19 nm-thick). The superior FE behavior of TiS3 nanosheets over nanoribbons makes them a propitious field emitter and can be utilized for various FE-based applications, demanding large emission currents and lower operational voltages. Moreover, the FE current stability recorded on these samples confirms their promising performance. Thus, the present investigation brings out a great promise of TiS3 nanosheets and nanoribbons as field emitters for vacuum nanoelectronics devices.

}, keywords = {Current stability, field emission, nanoribbon, nanosheets, TiS3}, doi = {10.1021/acsanm.2c03460}, author = {Pawbake, Amit S. and Khare, Ruchita T. and Island, Joshua O. and Flores, Eduardo and Ares, Jose R. and Sanchez, Carlos and Ferrer, Isabel J. and Pawar, Mahendra and Frank, Otakar and More, Mahendra A. and van der Zant, Herre S. J. and Castellanos-Gomez, Andres and Late, Dattatray J.} } @article {48773, title = {Topological phases in nanoparticle monolayers: can crystalline, hexatic, and isotropic-fluid phases coexist in the same monolayer?}, journal = {Soft Matter}, volume = {19}, year = {2023}, month = {OCT }, pages = {7271-7280}, type = {Article}, abstract = {

Topological phases are stable configurations of matter in 2-dimensions (2D) formed via spontaneous symmetry breaking. These play a crucial role in determining the system properties. Though a number of fundamental studies on topological phase transitions and topological defect dynamics have been conducted with model colloidal systems (typically microns in size), the same is lacking on nanoparticle monolayers (NPMLs, typically made of ligand-coated sub-ten nanometer particles). Here, we show that in an evaporation-driven self-assembly process, the three topological phases, namely crystalline, hexatic, and isotropic-fluid phases, can coexist within the same NPML. We associate this coexistence with the local variation in particle size, which can be described by a unique frequency parameter (p(25)), quantifying the fraction of NPs that has size deviation greater than or equal to 25\% of the mean size (where the deviation,f is defined as f = ((|Size-mean|)/mean)). The p(25)-values for the three phases are distinctly different: crystalline arrangement occurs when p(25) \< similar to 0.02, while a hexatic phase exists for 0.02 \<= p(25) \<= 0.1. For p(25) Z 0.1, the isotropic-fluid phase occurs. Following KTHNY-theory, we further numerically extrapolate the occurrence of each phase to the accumulated excess planar strain in the NPML due to the presence of various topological defects in the structures.

}, issn = {1744-683X}, doi = {10.1039/d3sm00290j}, author = {Bhattacharjee, Kaustav and Vaidya, Salil S. and Pathak, Tushar and Shimpi, Jayesh R. and Prasad, Bhagavatula L. V.} } @article {48668, title = {Total synthesis, structure elucidation and expanded bioactivity of icosalide A: effect of lipophilicity and ester to amide substitution on its bioactivity}, journal = {Organic \& Biomolecular Chemistry}, volume = {21}, year = {2023}, month = {JUL}, pages = {5725-5731}, type = {Article}, abstract = {

The first total synthesis of icosalide A, an antibacterial depsipeptide that is unique in that it contains two lipophilic beta-hydroxy acids, has been achieved by following Fmoc solid-phase peptide synthesis in combination with solution-phase synthesis. The ambiguity in the absolute stereochemistry of icosalide A has been resolved by synthesizing the reported structures and other relevant diastereomers of icosalides and comparing their NMR data. NMR-based structure elucidation of icosalide A revealed a well-folded structure with cross-strand hydrogen bonds similar to the anti-parallel beta-sheet conformation in peptides and displayed a synergistic juxtaposition of the aliphatic sidechains. 12 analogues of icosalide A were synthesized by varying the constituent lipophilic beta-hydroxy acid residues, and their biological activities against Bacillus thuringiensis and Paenibacillus dendritiformis were explored. Most of these icosalide analogues showed an MIC of 12.5 \& mu;g mL(-1) against both bacteria. Swarming inhibition by icosalides was least in B. thuringiensis (8.3\%) compared to that in P. dendritiformis (33\%). Furthermore, this is the first report of icosalides showing assured inhibitory action (MIC between 2 and 10 \& mu;g mL(-1)) against the active stage of Mycobacterium tuberculosis and cancer cell lines such as HeLa and ThP1. This study could help optimize icosalides for anti-TB, antibacterial, and anti-cancer activities.

}, issn = {1477-0520}, doi = {10.1039/d3ob00809f}, author = {Dangi, Abha and Pande, Bharat and Agrawal, Sonia and Sarkar, Dhiman and Vamkudoth, Koteswara Rao and Marelli, Udaya Kiran} } @article {48835, title = {Unprecedented energy storage in metal-organic complexes via constitutional isomerism}, journal = {Chemical Science}, volume = {14}, year = {2023}, month = {JUN}, pages = {6383-6392}, type = {Article}, abstract = {

The essence of any electrochemical system is engraved in its electrical double layer (EDL), and we report its unprecedented reorganization by the structural isomerism of molecules, with a direct consequence on their energy storage capability. Electrochemical and spectroscopic analyses in combination with computational and modelling studies demonstrate that an attractive field-effect due to the molecule{\textquoteright}s structural-isomerism, in contrast to a repulsive field-effect, spatially screens the ion-ion coulombic repulsions in the EDL and reconfigures the local density of anions. In a laboratory-level prototype supercapacitor, those with beta-structural isomerism exhibit nearly 6-times elevated energy storage compared to the state-of-the-art electrodes, by delivering similar to 535 F g(-1) at 1 A g(-1) while maintaining high performance metrics even at a rate as high as 50 A g(-1). The elucidation of the decisive role of structural isomerism in reconfiguring the electrified interface represents a major step forward in understanding the electrodics of molecular platforms.

}, issn = {2041-6520}, doi = {10.1039/d3sc01692g}, author = {Kottaichamy, Alagar Raja and Deebansok, Siraprapha and Deng, Jie and Nazrulla, Mohammed Azeezulla and Zhu, Yachao and Bhat, Zahid Manzoor and Devendrachari, Mruthyunjayachari Chattanahalli and Vinod, Chathakudath Prabhakaran and Kotresh, Harish Makri Nimbegondi and Fontaine, Olivier and Thotiyl, Musthafa Ottakam} } @article {49136, title = {Unusual ligand assistance in molecular electrocatalysis via interfacial proton charge assembly}, journal = {Journal of Physical Chemistry Letters }, volume = {14}, year = {2023}, month = {JUN }, pages = {5377-5385}, type = {Article}, abstract = {

We show that the ability of the ligand to reorganizethe electricdouble layer (EDL) often dominates the electrocatalysis contrary totheir inductive effect in the spectrochemical series, leading to counterintuitiveelectrocatalysis. With water oxidation and chlorine evolution as theprobe reactions, the same catalytic entity with carboxy functionalizedligand exhibited surprisingly higher electrochemical activity in comparisonto the aggressively electron-withdrawing nitro functionalized ligands,which is contrary to their actual location in the spectrochemicalseries. Spectroscopic and electrochemical analyses suggest the enrichmentof catalytically active species in the carboxy substituted ligandvia proton charge assembly in the EDL that in turn enhances the kineticsof the overall electrochemical process. This demonstration of lessobvious ligands becoming indispensable in electrocatalysis suggestsa blind designing of ligands solely based on their inductive effectshould be reconsidered as it will prevent the utilization of the maximumpotential of the molecule in electrocatalysis.

}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.3c01262}, author = {Mukhopadhyay, Sanchayita and Kottaichamy, Alagar Raja and Chame, Pallavi Vyankuram and Ghosh, Prasenjit and Vinod, Chathakudath Prabhakaran and Makri Nimbegondi Kotresh, Harish and Kanade, Sandeep C. and Thotiyl, Musthafa Ottakam} } @article {48746, title = {Visible-light-active unsymmetrical squaraine dyes with 1 V of open-circuit voltage for dye-sensitized solar cells}, journal = {ChemPhotoChem}, volume = {7}, year = {2023}, month = {MAY}, type = {Article}, abstract = {

A series of alkyl-group-functionalized, aniline- and indoline-donor-based, unsymmetrical visible-light-active squaraine dyes, AM1-3, were designed and synthesized. Dye-sensitized solar cell (DSSC) devices were fabricated with both I-/I-3(-) and [Cu(tmby)(2)](+/2+) electrolytes. DSSC devices sensitized with the AM1 and AM2 dyes showed relatively high-power conversion efficiency of 7.44 \% and 7.22 \%, respectively with I-/I-3(-) in the absence of chenodeoxycholic acid (CDCA) than those of the AM3 dye (5.41 \%). The [Cu(tmby)(2)](+/2+) electrolyte along with poly(3,4-ethylenedioxythiophene) (PEDOT) as cathode material showed excellent open-circuit potentials (V-OC) of 1030, 1025, and 1001 mV with the DSSC efficiency of 8.05 \%, 7.96 \%, and 5.84 \%, respectively, for the AM1, AM2, and AM3 dyes in the absence of CDCA. Here, the AM1 dye exhibited the maximum DSSC efficiency of 8.05 \% and V-OC of 1030 mV, which is the highest obtained efficiency and V-OC for the visible-light active zwitterionic unsymmetrical-squaraine dye with copper-based electrolyte.

}, keywords = {Cu electrolytes, dihedral angle, Dye-sensitized solar cells, open circuit voltage, squaraine dyes}, issn = {2367-0932}, doi = {10.1002/cptc.202200328}, author = {Singh, Amrita and Kumar Singh, Ambarish and Dixit, Ruchi and Vanka, Kumar and Krishnamoorthy, Kothandam and Nithyanandhan, Jayaraj} } @article {48491, title = {Wadsworth-emmons reaction by using the fluorapatite catalyst: kinetic studies}, journal = {Industrial \& Engineering Chemistry Research}, volume = {62}, year = {2023}, month = {MAY }, pages = {7901-7911}, type = {Article}, abstract = {

Wadsworth-Emmons reaction was successfully carriedout byusing the fluorapatite (FAP) catalyst. The reaction of 2-methoxybenzaldehydeand triethylphosphonoacetate using FAP afforded \& alpha;,\& beta;-unsaturatedester with 100\% conversion and 80\% selectivity. A kinetic model wasvalidated at different temperatures by Langmuir-Hinshelwood-Hougen-Watson(LHHW), and the absence of mass transfer resistance was verified bythe Weisz Prater criterion. The effect of different catalysts, temperature,catalyst loading, solvent, mole ratio, and speed of stirring was studied.The FAP catalyst was characterized by Fourier transform infrared spectroscopy,Brunauer-Emmett-Teller method, nitrogen adsorption-desorption,transmission electron microscopy, energy-dispersive X-ray spectroscopy,temperature programmed desorption (TPD-NH3), X-ray diffraction,and X-ray photoelectron spectroscopy. The FAP catalyst was found tobe stable up to three recycles with no loss in activity.

}, issn = {0888-5885}, doi = {10.1021/acs.iecr.3c00407}, author = {Vishwakarma, Rakhi and Vinod, Chathakudath P. and Rathod, Virendra and Kantam, Mannepalli Lakshmi} } @article {48714, title = {"Weak" C-H{\textbullet}{\textbullet}{\textbullet}S interaction drives enantioselectivity in cinchona alkaloid complex catalyzed thiocyanation}, journal = {Chemistry-An Asian Journal}, volume = {18}, year = {2023}, month = {JUL}, pages = {e202300321}, type = {Article}, abstract = {

The great success of asymmetric organocatalysis has made it one of the most important advancements made in chemistry in the past two decades. A significant achievement in this context is the asymmetric organocatalysis of the thiocyanation reaction. In the current study, computational studies with density functional theory have been done in order to understand an interesting experimental finding: the reversal of enantioselectivity from R to S when the electrophile is changed from beta-keto ester to oxindole for the thiocyanation reaction with the cinchona alkaloid complex catalyst. The calculations reveal an unusual fact - the principal reason for the reversal is the presence of the C-H center dot center dot center dot S noncovalent interaction, which is present only in the major transition states in each of the two nucleophile cases. Only recently has it been realized that the supposedly weak C-H center dot center dot center dot S noncovalent interaction has the properties of a hydrogen bond, and the fact that this interaction is the cause of enantioselectivity has relevance, because of the large number of asymmetric transformations involving the sulphur heteroatom.

}, keywords = {Density functional calculations, Enantioselectivity, noncovalent interactions, organocatalysis, reaction mechanisms}, issn = {1861-4728}, doi = {10.1002/asia.202300321}, author = {Banerjee, Subhrashis and Vanka, Kumar} } @article {48962, title = {Wurtzite CuGaS2 with an in-situ-formed CuO layer photocatalyzes CO2 conversion to ethylene with high selectivity}, journal = {Angewandte chemie-international edition}, volume = {62}, year = {2023}, month = {FEB 20}, type = {Article}, abstract = {

We present surface reconstruction-induced C-C coupling whereby CO2 is converted into ethylene. The wurtzite phase of CuGaS2. undergoes in situ surface reconstruction, leading to the formation of a thin CuO layer over the pristine catalyst, which facilitates selective conversion of CO2 to ethylene (C2H4). Upon illumination, the catalyst efficiently converts CO2 to C2H4 with 75.1 \% selectivity (92.7 \% selectivity in terms of R-electron) and a 20.6 mu mol g(-1) h(-1) evolution rate. Subsequent spectroscopic and microscopic studies supported by theoretical analysis revealed operando-generated Cu2+, with the assistance of existing Cu+, functioning as an anchor for the generated *CO and thereby facilitating C-C coupling. This study demonstrates strain-induced in situ surface reconstruction leading to heterojunction formation, which finetunes the oxidation state of Cu and modulates the CO2 reduction reaction pathway to selective formation of ethylene.

}, keywords = {C-C coupling, charge polarization, CO2 reduction, Photocatalysis}, issn = {1433-7851}, doi = {10.1002/anie.202216613}, author = {Chakraborty, Subhajit and Das, Risov and Riyaz, Mohd and Das, Kousik and Singh, Ashutosh Kumar and Bagchi, Debabrata and Vinod, Chathakudath P. and Peter, Sebastian C.} } @article {48690, title = {Zwitterionic disilanylium from an unsymmetrical disilene}, journal = {Chemical Communications}, volume = {59}, year = {2023}, month = {FEB }, pages = {1669-1672}, type = {Article}, abstract = {

The reaction of PhC(NtBu)2SiSi(SiMe3)(3) (1) with Me3SiCH(2)Cl afforded an unsymmetrical sp(2)-sp(3) disilene, 2, with concomitant elimination of Me3SiCl. The analogous reaction with PhC(NtBu)2SiCl resulted in the oxidative addition of the C-Cl bond at the Si(II) atom (3). The reactions of 2 with sulfur and selenium led to compounds with Si=E (E=S (4) and Se (5)) double bonds. Tellurium reacted differently with 2 and furnished a zwitterionic compound, 6.

}, issn = {1359-7345}, doi = {10.1039/d2cc06954g}, author = {Bisai, Milan Kumar and Ajithkumar, V. S. and Raj, K. Vipin and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {49139, title = {Zwitterionic tetrastanna(II) cyclic crown}, journal = {European Journal of Inorganic Chemistry}, volume = {26}, year = {2023}, month = {OCT }, type = {Article}, abstract = {

A 12-membered zwitterionic tetrastanna(II) cycle 1 having a crown ether-like topology has been isolated from the deprotonation of 1,1 \& PRIME;-methylenediimidazole (B) with two equivalents of Sn[N(SiMe3)(2)](2) (A). The solid-state structure and NMR analysis confirms the tetrastanna(II) cycle 1 to be comprised of two stannate(II) and two stannyliumylidene ion pairs in alternating positions of the heterocycle. Computational analysis shows greater nucleophilicity at the proximally located stannate(II) centers. Nonetheless, the tetrastanna(II) cycle 1 remains poorly reactive due to engagement of Sn-II lone pair electrons in intramolecular donor-acceptor interactions. Simple deprotonation reaction between Sn[N(SiMe3)(2)](2) (A) and N-(diisopropylphenyl)imidazole (C) in equimolar ratio has led to a stannylene 2, involving the formation of a Sn-C covalent bond with the anionic imidazol-2-yl carbon center along with the release of NH(SiMe3)(2). Compound 2 exists as a dimer, where the unsubstituted ring nitrogen atom coordinated intermolecularly to the other stannylene center.

}, keywords = {Deprotonation, Imidazole, Macrocycle, Sn-II cation, stannylene}, issn = {1434-1948}, doi = {10.1002/ejic.202300249}, author = {Sahoo, Padmini and Chibde, Purva and Das, Satyabrata and Banerjee, Subhrashis and Mali, Bhupendra P. and Vanka, Kumar and Gonnade, Rajesh G. and Yildiz, Cem. B. and Majumdar, Moumita} } @article {49393, title = {Activation of carbon disulfide by a hypersilyl germylene}, journal = {Dalton Transactions}, volume = {53}, year = {2024}, month = {JUL}, type = {Article}, abstract = {

In this work, the insertion of CS2 into the Ge-Si bond of PhC(NtBu)2Ge-Si(SiMe3)3 (1) has been investigated, resulting in the formation of PhC(NtBu)2Ge-C( 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 S)-S-Si(SiMe3)3 (2). Interestingly, the addition of NHC to 2 allows the release of NHCCS2 with concomitant regeneration of 1. Addition of another equivalent of 1 or an analogous hypersilyl silylene, [PhC(NtBu)2Si-Si(SiMe3)3], to 2 led to the formation of compounds with a GeS (3) or a SiS (4) bond. In this work, the insertion of CS2 into the Ge-Si bond of PhC(NtBu)2Ge-Si(SiMe3)3 (1) has been investigated, resulting in the formation of PhC(NtBu)2Ge-C(S)-S-Si(SiMe3)3 (2).

}, issn = {1477-9226}, doi = {10.1039/d4dt01573h}, author = {Ajithkumar, V. S. and Khilari, Nripen and Ghanwat, Pratiksha B. and Venugopal, Geethu and Koley, Debasis and Sen, Sakya S.} } @article {49367, title = {Aluminium, nitrogen-dual-doped reduced graphene oxide Co-existing with cobalt-encapsulated graphitic carbon nanotube as an activity modulated electrocatalyst for oxygen electrocatalyst for oxygen electrochemistry applications}, journal = {Small}, volume = {20}, year = {2024}, month = {AUG}, type = {Article}, abstract = {

There is a rising need to create high-performing, affordable electrocatalysts in the new field of oxygen electrochemistry. Here, a cost-effective, activity-modulated electrocatalyst with the capacity to trigger both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in an alkaline environment is presented. The catalyst (Al, Co/N-rGCNT) is made up of aluminium, nitrogen-dual-doped reduced graphene oxide sheets co-existing with cobalt-encapsulated carbon nanotube units. Based on X-ray Absorption Spectroscopy (XAS) studies, it is established that the superior reaction kinetics in Al, Co/N-rGCNT over their bulk counterparts can be attributed to their electronic regulation. The Al, Co/N-rGCNT performs as a versatile bifunctional electrocatalyst for zinc-air battery (ZAB), delivering an open circuit potential approximate to 1.35 V and peak power density of 106.3 mW cm-2, which are comparable to the system based on Pt/C. The Al, Co/N-rGCNT-based system showed a specific capacity of 737 mAh gZn-1 compared to 696 mAh gZn-1 delivered by the system based on Pt/C. The DFT calculations indicate that the adsorption of Co in the presence of Al doping in NGr improves the electronic properties favoring ORR. Thus, the Al, Co/N-rGCNT-based rechargeable ZAB (RZAB) emerges as a highly viable and affordable option for the development of RZAB for practical applications. This manuscript reports the development of a new bifunctional catalyst that exhibits high activity and stability under practical operating conditions. The catalyst (Al, Co/N-rGCNT) is made up of aluminium, nitrogen-dual-doped reduced graphene oxide sheets co-existing with the in situ formed cobalt-encapsulated CNT units is synthesized by a scalable pyrolysis method in an inert Ar atmosphere. The developed electrocatalyst achieved enhanced the oxygen reduction reaction (ORR) and the oxygen evolution reaction OER activity as a result of the favorable synergistic modulations and the system can serve as a process-friendly air-electrode for rechargeable zinc-air battery (RZAB). image

}, keywords = {Al, Bifunctional catalyst, DFT study, encapsulated structure, N-dual doping, Oxygen Evolution Reaction, oxygen reduction reaction, rechargeable zinc-air battery, X-ray absorption spectroscopy}, issn = {1613-6810}, doi = {10.1002/smll.202400012}, author = {Kharabe, Geeta Pandurang and Barik, Sidharth and Veeranmaril, Sudheesh Kumar and Nair, Aathira and Illathvalappil, Rajith and Yoyakki, Athira and Joshi, Kavita and Vinod, Chathakudath Prabhakaran and Kurungot, Sreekumar} } @article {49062, title = {architecturally rational hemostat for rapid stopping of massive bleeding on anticoagulation therapy}, journal = {Proceedings of the National Academy of Sciences of the United States of America}, volume = {121}, year = {2024}, month = {JAN}, pages = {e2316170121}, type = {Article}, abstract = {

Hemostatic devices are critical for managing emergent severe bleeding. With the increased use of anticoagulant therapy, there is a need for next- generation hemostats. We rationalized that a hemostat with an architecture designed to increase contact with blood, and engineered from a material that activates a distinct and undrugged coagulation pathway can address the emerging need. Inspired by lung alveolar architecture, here, we describe the engineering of a next- generation single - phase chitosan hemostat with a tortuous spherical microporous design that enables rapid blood absorption and concentrated platelets and fibrin microthrombi in localized regions, a phenomenon less observed with other classical hemostats without structural optimization. The interaction between blood components and the porous hemostat was further amplified based on the charged surface of chitosan. Contrary to the dogma that chitosan does not directly affect physiological clotting mechanism, the hemostat induced coagulation via a direct activation of platelet Toll - like receptor 2. Our engineered porous hemostat effectively stopped the bleeding from murine liver wounds, swine liver and carotid artery injuries, and the human radial artery puncture site within a few minutes with significantly reduced blood loss, even under the anticoagulant treatment. The integration of engineering design principles with an understanding of the molecular mechanisms can lead to hemostats with improved functions to address emerging medical needs.

}, keywords = {biomaterial, clotting, hemostasis, hemostat, trauma}, issn = {0027-8424}, doi = {10.1073/pnas.2316170121}, author = {Lee, Vivian K. and Lee, Taewoo and Ghosh, Amrit and Saha, Tanmoy and Bais, V. Manish and Bharani, Kala Kumar and Chag, Milan and Parikh, Keyur and Bhatt, Parloop and Namgung, Bumseok and Venkataramanan, Geethapriya and Agrawal, Animesh and Sonaje, Kiran and Mavely, Leo and Sengupta, Shiladitya and Mashelkar, Raghunath Anant and Jang, Hae Lin} } @article {49406, title = {Aroma Alchemy: uridine diphosphate-dependent glycosyltransferases mediated regulation of fruit aroma and flavor biosynthesis}, journal = {Phytochemistry Reviews}, year = {2024}, month = {DEC}, type = {Review; Early Access}, abstract = {

The aroma compounds contribute to fruits flavor, taste, and nutritional value. These compounds include various chemical classes such as terpenoids, lactones, ketones, esters, acids, alcohols, and their derivatives. Uridine diphosphate-dependent glycosyltransferases (UGTs) modify these compounds by covalently adding one or multiple sugar molecules. This glycosylation process converts volatile, unstable, and hydrophobic aroma compounds into hydrophilic, stable, and slow-releasing reservoirs of fruit flavor. The diversity and spatio-temporal expression patterns of UGTs play a crucial role in forming a wide range of glycosylated aroma compounds. This review focuses on aroma-related compounds in both free and glycosylated-bound forms found in commercial vital fruits. We discuss various fruit-specific UGTs and their role in the glycosylation of aroma compounds. Based on structural and functional information on UGTs, we have assessed sugar donor specificity and the residues responsible for the same. Moreover, phylogenetic analysis of characterized UGTs provides insights into their substrate preferences. We also surveyed the expression dynamics of UGTs during fruit ripening, as the switching between aglycon and glycosylated-bound forms of aroma compounds significantly impacts fruit quality. Potential applications of UGTs in the food and fragrance industry have been discussed. The information reviewed could be beneficial for developing novel methods for flavor manipulation of commercially important glycosides derived from natural resources.

}, keywords = {Aroma, Flavor, Fruit, Glycoconjugates, Glycosyltransferase, Volatile compounds}, issn = {1568-7767}, doi = {10.1007/s11101-024-10049-7}, author = {Vare, Tejas B. and Joshi, Rakesh S. and Giri, Ashok P.} } @article {49391, title = {Atmospheric-pressure continuous-flow methane oxidation to methanol and acetic acid using H2O2 over the Au-Fe catalyst}, journal = {ACS SUSTAINABLE CHEMISTRY \& ENGINEERING}, volume = {12}, year = {2024}, month = {MAY }, pages = {8958-8967}, type = {Journal Article}, keywords = {CO oxidation, HIGHLY SELECTIVE OXIDATION, metal-organic frameworks}, issn = {2168-0485}, doi = {10.1021/acssuschemeng.4c02993}, author = {Jagtap, Anuradha V. and Kumar, Pawan and Gupta, Sharad and Nagendra, Abharana and Jha, Shambhu Nath and Bhattacharyya, D. and Ajithkumar, Thalasseril G. and Vinod, C. P.} } @article {49382, title = {Biexciton emission in CsPbBr3 nanocrystals: polar facet matters}, journal = {Nano Letters}, volume = {24}, year = {2024}, month = {AUG }, pages = {10434-10442}, type = {Article}, abstract = {

The metal halide perovskite nanocrystals exhibit a remarkable tolerance to midgap defect states, resulting in high photoluminescence quantum yields. However, the potential of these nanocrystals for applications in display devices is hindered by the suppression of biexcitonic emission due to various Auger recombination processes. By adopting single-particle photoluminescence spectroscopy, herein, we establish that the biexcitonic quantum efficiency increases with the increase in the number of facets on cesium lead bromide perovskite nanocrystals, progressing from cube to rhombic dodecahedron to rhombicuboctahedron nanostructures. The observed enhancement is attributed mainly to an increase in their surface polarity as the number of facets increases, which reduces the Coulomb interaction of charge carriers, thereby suppressing Auger recombination. Moreover, Auger recombination rate constants obtained from the time-gated photon correlation studies exhibited a discernible decrease as the number of facets increased. These findings underscore the significance of facet engineering in fine-tuning biexciton emission in metal halide perovskite nanocrystals.

}, keywords = {Auger recombination, biexciton emission, Cs-133 MAS NMR spectroscopy, Perovskites, time-gatedphoton correlation}, issn = {1530-6984}, doi = {10.1021/acs.nanolett.4c01186}, author = {Titus, Timi and Vishnu, E. Krishnan and Garai, Arghyadeep and Dutta, Sumit Kumar and Sandeep, Kuttysankaran and Shelke, Ankita and Ajithkumar, Thalasseril G. and Shaji, Anil and Pradhan, Narayan and Thomas, K. George} } @article {49419, title = {Bimetallic and plasmonic Ag and Cu integrated TiO2 thin films for enhanced solar hydrogen production in direct sunlight}, journal = {Energy Advances}, volume = {3}, year = {2024}, month = {APR}, pages = {829-840}, type = {Article}, abstract = {
Plasmonic metal nanoparticle-integrated mesoporous TiO2\ nanocomposites (Ag/TiO2, Cu/TiO2\ and Ag{\textendash}Cu/TiO2), prepared by a simple chemical reduction method, have been demonstrated to show superior activity in thin-film form for solar H2\ generation in sunlight. Integration of Ag + Cu on TiO2\ significantly enhances the solar H2\ production due to the combined SPR effect of both metal species and the possible synergistic interaction among Cu + Ag in Ag{\textendash}Cu/TiO2. TiAgCu-1 (0.75 wt\% Ag and 0.25 wt\% Cu on TiO2) showed the highest H2\ yield of 6.67 mmol h-1\ g-1\ and it is 43 times higher than that of bare TiO2. The thin-film form of TiAgCu-1 shows 5 times higher solar H2\ production than its powder counterpart. 1 wt\% of Ag or Cu on TiO2\ shows a H2\ yield of 4.6 or 2 mmol h-1\ g-1, respectively, which underscores the importance of combined or synergistic effects. The increase in solar H2\ generation in Ag{\textendash}Cu/TiO2\ is attributed to factors such as the SPR effect of Cu and Ag, and strong interaction between Ag and Cu. The high photocatalytic efficiency of the TiAgCu-1 thin film is attributed to the large dispersion of metallic species with relatively high Ag/Cu surface atomic ratio, enhanced light absorption, a heterogeneous distribution of Ag and Cu species, and high double layer capacitance. The inter particle mesoporous network increases the interfacial charge transfer and reduces the mass transfer limitations. The plausible photocatalytic reaction mechanism could involve the combination of direct electron transfer from metal (Cu/Ag) to TiO2\ as well as the significant field effect due to the Ag{\textendash}Cu alloy, which is expected to increase the electron excitation locally.
Plasmonic metal nanoparticle integrated mesoporous TiO2\ nanocomposites (Ag/TiO2, Cu/TiO2\ and Ag{\textendash}Cu/TiO2), prepared by a simple chemical reduction method, have been demonstrated to show superior activity in thin-film form for solar H2\ generation.

}, doi = {https://doi.org/10.1039/d4ya00056k}, author = {Mani, Sunesh S. and Rajendran, Sivaraj and Arun, Pushkaran S. and Vijaykumar, Aparna and Mathew, Thomas and Gopinath, Chinnakonda S.} } @article {49100, title = {Boron- and oxygen-doped π-extended helical nanographene with circularly polarised thermally activated delayed fluorescence}, journal = {Chemistry-A European Journal}, volume = {30}, year = {2024}, month = {APR }, type = {Article}, abstract = {

Helical nanographenes have garnered substantial attention owing to their finely adjustable optical and semiconducting properties. The strategic integration of both helicity and heteroatoms into the nanographene structure, facilitated by a boron-oxygen-based multiple resonance (MR) thermally activated delayed fluorescence (TADF), elevates its photophysical and chiroptical features. This signifies the introduction of an elegant category of helical nanographene that combines optical (TADF) and chiroptical (CPL) features. In this direction, we report the synthesis, optical, and chiroptical properties of boron, oxygen-doped pi-extended helical nanographene. The pi-extension induces distortion in the DOBNA-incorporated nanographene, endowing a pair of helicenes, (P)-B2NG, and (M)-B2NG exhibiting circularly polarized luminescence with glum of -2.3x10-3 and +2.5x10-3, respectively. B2NG exhibited MR-TADF with a lifetime below 5 mu s, and a reasonably high fluorescence quantum yield (50 \%). Our molecular design enriches the optical and chiroptical properties of nanographenes and opens up new opportunities in multidisciplinary fields. B, O-doped pi-extended helical nanographene has been explored for its optical and chiroptical properties. The presence of helical and nanographene segments stabilize the helicity and imparts tunable optical properties. Helical nanographene display circularly polarized thermally activated delayed fluorescence. image

}, keywords = {circularly polarized luminescence, DOBNA, dual emission, nanographene, TADF}, issn = {0947-6539}, doi = {10.1002/chem.202304169}, author = {Venugopal, Geethu and Kumar, Viksit and Jadhav, Ashok Badrinarayan and Dongre, Sangram D. and Khan, Abujunaid and Gonnade, Rajesh and Kumar, Jatish and Santhosh Babu, Sukumaran} } @article {49360, title = {Breaking the Pt electron symmetry and OH spillover towards ptir active center for performance modulation in direct ammonia fuel cell}, journal = {Small}, volume = {20}, year = {2024}, month = {DEC}, type = {Article}, abstract = {

The growing interest in low-temperature direct ammonia fuel cells (DAFCs) arises from the utilization of a carbon-neutral ammonia source; however, DAFCs encounter significant electrode overpotentials due to the substantial energy barrier of the *NH2 to *NH dehydrogenation, compounded by the facile deactivation by *N on the Pt surface. In this work, a unique catalyst, Pt4Ir@AlOOH/NGr i.e., Pt4Ir/ANGr, is introduced composed of PtIr alloy nanoparticles controllably decorated on the pseudo-boehmite phase of AlOOH-supported nitrogen-doped reduced graphene (AlOOH/NGr) composite, synthesized via the polyol reduction method. The detailed studies on the structural and electronic properties of the catalyst by XAS and VB-XPS reveal the possible electronic modulations. The optimized Pt4Ir/ANGr composition exhibits a significantly improved onset potential and mass activity for AOR. The DFT study confirms the OHad species spillover by AlOOH and Pt4Ir (100) facilitates the conversion of the *NH2 to *NH with minimal energy barriers. Finally, testing of DAFC at the system level using a membrane electrode assembly (MEA) with Pt4Ir/ANGr as the anode catalyst, demonstrating the suitability of the catalyst for its practical applications. This study thus uncovers the potential of the Pt4Ir catalyst in synergy with ANGr, largely addressing the challenges in hydrogen transportation, storage, and safety within DAFCs. In this article, a versatile catalyst, Pt4Ir/ANGr, is introduced composed of PtIr alloy nanoparticles decorated on AlOOH/NGr composite. The AlOOH provides an -OH-rich surface conducive to the facile adsorption and decoration of the PtIr alloy nanoparticles and OHad species spillover from AlOOH to the Pt4Ir active center during AOR, further validating the higher experimental activity obtained in Pt4Ir/ANGr. image

}, keywords = {ammonia oxidation reaction (AOR), d-band center, density functional theory (DFT) study, direct ammonia fuel cells, hydroxyl spillover effect, XAS analysis}, issn = {1613-6810}, doi = {10.1002/smll.202406589}, author = {Barik, Sidharth and Kharabe, Geeta Pandurang and Samal, Pragnya Paramita and Urkude, Rajashri R. and Kumar, Sachin and Yoyakki, Athira and Vinod, C. P. and Krishnamurty, Sailaja and Kurungot, Sreekumar} } @article {49024, title = {Bronsted acid-promoted cyclodimerization of α,β-unsaturated γ-ketoesters: construction of fused pyrano-ketal-lactones and γ-ylidene-butenolides}, journal = {ACS Omega}, volume = {9}, year = {2024}, month = {APR }, pages = {19859-19878}, type = {Article}, abstract = {

Unprecedented MsOH-promoted diastereoselective cascade dimerization and intramolecular lactonization of readily accessible alpha,beta-unsaturated gamma-ketoesters are presented. The results obtained in this work, control experiments, and density functional theory (DFT) calculations suggested that the initial enolization and E to Z isomerization/equilibration of olefin (C=C) of substrate alpha,beta-unsaturated gamma-ketoesters give a Z-isomer preferentially over an E-isomer. Subsequently, the Z-isomer undergoes intermolecular annulation with alpha,beta-unsaturated gamma-ketoesters via domino Michael addition/ketalization/lactonization steps to furnish fused tetracyclic pyrano-ketal-lactone. However, the Z-isomer prefers intramolecular trans-esterification in a competing pathway and gives bicyclic gamma-ylidene-butenolide. The key features of this work include simple Br \& oslash;nsted acid catalysis, the formation of three bonds, two rings, and three contiguous stereogenic centers in a single step, DFT calculations, and the assignment of relative stereochemistry through X-ray diffraction (XRD) and two-dimensional (2D) nuclear magnetic resonance (NMR) analyses.

}, issn = {2470-1343}, doi = {10.1021/acsomega.3c08873}, author = {Vinodkumar, Ramavath and Nakate, Ashwini K. and Sharma, Himanshu and Vanka, Kumar and Rama Krishna, Gamidi and Kontham, Ravindar} } @article {49092, title = {Br{\o}nsted acid- and Ni(ii)-catalyzed C-H oxidation/rearrangement of cyclotriveratrylenes (CTVs) to cyclic and acyclic quinones as potential anti-cancer agents}, journal = {Organic and biomolecular chemistry}, volume = {22}, year = {2024}, month = {JAN }, pages = {1038-1046}, type = {Article}, abstract = {

This paper describes a simple and practical protocol for the direct synthesis of acyclic and cyclic quinone derivatives via an acid-promoted nickel(ii)-catalyzed inner rim C-H oxidation of cyclotriveratrylene (CTV) and its analogues. The cyclic quinone derivatives resulted from trimethoxy-cyclotriveratrylene (TCTV) through C-C bond formation via intramolecular ipso substitution followed by subsequent anionic rearrangement containing stereo-vicinal quaternary centers. The DFT calculations strongly support the experimental findings and reveal the role of Bronsted acids in the C-H bond activation of CTV. All the newly synthesized compounds were screened for their in vitro anti-cancer activity using colorimetric SRB assay analysis. Among them, compounds 3a, 3d, 3h, 4a, 4b, 4c and 4e exhibited moderate anticancer activity against A549, HCT-116, PC-3, MDA-MB-231, HEK-293 and SW620 human cancer cell lines.

}, issn = {1477-0520}, doi = {10.1039/d3ob01428b}, author = {Darole, Ratanamala S. and Choudhary, Shailendra Singh and Sharma, Himanshu and Mali, Bhupendra P. and Gopu, Booblan and Vanka, Kumar and Senthilkumar, Beeran} } @article {49199, title = {Chelation-assisted and steric-controlled selectivity in the Pd-catalyzed C-H/C-H oxidative coupling of indoles}, journal = {Chemical Communications}, volume = {60}, year = {2024}, month = {NOV }, pages = {13028-13031}, type = {Article}, abstract = {

We report the first regioselective C2-C7 oxidative coupling of indoles using a palladium catalyst upon the strategic installation of N-pyridinyl and C3-carbonyl, which delivers 2,7-biindoles with a broad scope (25 examples; up to 93\% yield). Isolation of the catalytic intermediate reveals the initial activation of the C(7)-H bond, followed by the C(2)-H bond in indoles, and the reaction proceeds via a Pd(ii)/Pd(0) pathway. This manuscript describes the first regioselective C2-C7 oxidative coupling of indoles using a palladium catalyst through the strategic installation of N-pyridinyl and C3-carbonyl, which delivers diverse biorelevant 2-7-biindoles.

}, issn = {1359-7345}, doi = {10.1039/d4cc03835e}, author = {Vijaykumar, Muniyappa and Pradhan, Chandini and Gonnade, Rajesh G. and Punji, Benudhar} } @article {49215, title = {Circulatory levels of lysophosphatidylcholine species in obese adolescents: Findings from cross-sectional and prospective lipidomics analyses}, journal = {NUTRITION METABOLISM AND CARDIOVASCULAR DISEASES}, volume = {34}, year = {2024}, month = {JUL}, pages = {1807-1816}, type = {Journal Article}, keywords = {Adolescent obesity, Asian Indians, biomarker, Lipidomics, Lysophosphatidyl- choline}, issn = {0939-4753}, doi = {10.1016/j.numecd.2024.02.009}, author = {Sharma, Sapna and Subrahmanyam, Yalamanchili Venkata and Ranjani, Harish and Sidra, Sidra and Parmar, Dharmeshkumar and Vadivel, Sangeetha and Kannan, Shanthini and Grallert, Harald and Usharani, Dandamudi and Anjana, Ranjit Mohan and Balasubramanyam, Muthuswamy and Mohan, Viswanathan and Jerzy, Adamski and Panchagnula, Venkateswarlu and Gokulakrishnan, Kuppan} } @article {49634, title = {Comparative proteomics of sugarcane smut fungus- Sporisorium scitamineum unravels dynamic proteomic alterations during the dimorphic transition}, journal = {Journal of Proteomics}, volume = {304}, year = {2024}, month = {JUL }, pages = {105230}, type = {Article}, abstract = {

Life cycle of the dimorphic sugarcane smut fungi, Sporisorium scitamineum , involves recognition and mating of compatible saprophytic yeast -like haploid sporidia (MAT -1 and MAT -2) that upon fusion, develop into infective dikaryotic mycelia. Although the dimorphic transition is intrinsically linked with the pathogenicity and virulence of S. scitamineum , it has never been studied using a proteomic approach. In the present study, an iTRAQ-based comparative proteomic analysis of three distinct stages was carried out. The stages were: the dimorphic transition period - haploid sporidial stage (MAT -1 and MAT -2); the transition phase (24 h post co -culturing (hpc)) and the dikaryotic mycelial stage (48 hpc). Functional categorization of differentially abundant proteins showed that the most altered biological processes were energy production, primary metabolism, especially, carbohydrate, amino acid, fatty acid, followed by translation, post -translation and protein turnover. Several differentially abundant proteins (DAPs), especially in the dikaryotic mycelial stage were predicted as effectors. Taken together, key molecular mechanisms underpinning the dimorphic transition in S. scitamineum at the proteome level were highlighted. The catalogue of stage -specific and dimorphic transition -associated -proteins and potential effectors identified herein represents a list of potential candidates for defective mutant screening to elucidate their functional role in the dimorphic transition and pathogenicity in S. scitamineum . Biological significance: Being the first comparative proteomics analysis of S. scitamineum , this study comprehensively examined three pivotal life cycle stages of the pathogen: the non-pathogenic haploid phase, the transition phase, and the pathogenic dikaryotic mycelial stage. While previous studies have reported the sugarcane and S. scitamineum interactions, this study endeavored to specifically identify the proteins responsible for pathogenicity. By analyzing the proteomic alterations between the haploid and dikaryotic mycelial phases, the study revealed significant changes in metabolic pathway -associated proteins linked to energy production, notably oxidative phosphorylation, and the citrate cycle. Furthermore, this study successfully identified key metabolic pathways that undergo reprogramming during the transition from the non-pathogenic to the pathogenic stage. The study also deciphered the underlying mechanisms driving the morphological and physiological alterations crucial for the S. scitamineum virulence. By studying its life cycle stages, identifying the key metabolic pathways and stage -specific proteins, it provides unprecedented insights into the pathogenicity and potential avenues for intervention. As proteomics continues to advance, such studies pave the way for a deeper understanding of plantpathogen interactions and the development of innovative strategies to mitigate the impact of devastating pathogens like S. scitamineum.

}, keywords = {dimorphism, fungi, iTRAQ, Smut, Sugarcane, Virulence}, issn = {1874-3919}, doi = {10.1016/j.jprot.2024.105230}, author = {Kumaravel, Nalayeni and Ebinezer, Leonard Barnabas and Ashwin, N. M. R. and Franchin, Cinzia and Battisti, Ilaria and Carletti, Paolo and Sundar, Amalraj Ramesh and Masi, Antonio and Malathi, Palaniyandi and Viswanathan, Rasappa and Arrigoni, Giorgio} } @article {49055, title = {Computational identification of most potent atom pair catalysts for electrocatalytic nitrogen reduction reaction over hydrogen evolution reaction}, journal = {Inter.}, volume = {58}, year = {2024}, month = {MAR }, pages = {1345-1358}, type = {Article}, abstract = {

Robust electrocatalytic atom pair compositions (APCs) where Nitrogen Reduction Reaction (NRR) is more enhanced over competing Hydrogen Evolution Reaction (HER) is searched for using computational studies based on Density Functional Theory based methods. Atomic pairs are anchored on mechanically and thermally stable graphene surfaces. A wide range of transition metal based atom pair compositions from 3d, 4d, and 5d groups are systematically investigated for reduction of dinitrogen molecule with lower reduction barrier as compared to HER. APR compositions of Ni-Rh with an overall limiting potential of -0.22 V, Fe-W with an overall limiting potential of -0.26 V and Co-Pt with an overall limiting potential of -0.28 V are identified as the most potent atomic pairs for enhanced nitrogen reduction reaction over the HER. Finally, the performance of most potent composition, viz., Ni-Rh is validated to be consistent with respect to their thermodynamic stability and performance within the solvent effects.

}, keywords = {Atom pair catalysts, Density Functional Theory (DFT), Electrochemical nitrogen reduction reaction (eNRR), hydrogen evolution reaction (HER), IR stretching frequencies, N-N bond length}, issn = {0360-3199}, doi = {10.1016/j.ijhydene.2024.01.203}, author = {Verma, Tushar Singh and Dar, Afshana Hassan and Dar, Manzoor Ahmad and Selvaraj, Kaliaperumal and Krishnamurty, Sailaja} } @article {49032, title = {Copper-catalyzed regioselective C-H alkylation of phenol derivatives with unactivated alkyl chlorides: manifesting a Cu(I)/Cu(III) pathway}, journal = {Journal of Catalysis }, volume = {430}, year = {2024}, month = {FEB}, type = {Article}, abstract = {

The use of unactivated alkyl chlorides in regioselective C -H alkylation is a highly challenging process with diverse applications of alkylation strategy in drug discovery and agrochemistry. In this work, we report an efficient and cost-effective copper -catalyzed protocol for the coupling of unactivated alkyl chlorides with the C -H bond of phenol derivatives via 2-pyridinyl chelation assistance. The reaction shows a high level of regioselectivity, leading to an exclusive ortho alkylation and providing a broad scope with the endurance of numerous functionalities such as silyl, ether, thioether, pyrrolyl, indolyl, carbazolyl groups, including alkyl bearing fatty alcohol, nonylphenol, and vitamin E. Detailed mechanistic investigations suggest that the alkylation occurs through a two -electron oxidative addition of alkyl chloride to an active Cu(I) species. Deuterium labeling and kinetics experiments indicate a facile and reversible C -H bond activation process. Overall, the alkylation follows a Cu(I)/Cu(III) pathway involving chelation-assisted smooth C -H metalation and rate -limiting C-Cl oxidative addition of alkyl chloride.

}, issn = {0021-9517}, doi = {10.1016/j.jcat.2024.115351}, author = {Verma, Suryadev K. and Punji, Benudhar} } @article {49258, title = {Crystal engineering for intramolecular π-π stacking: effect of substitution of electron-donating and electron-withdrawing groups on the molecular geometry in conformationally flexible Sulfoesters and sulfonamides}, journal = {CrystEngComm}, volume = {26}, year = {2024}, month = {JUL}, pages = {3557-3573}, type = {Article}, abstract = {

A series of 21 sulfoester and sulfonamide derivatives comprising two aromatic rings was synthesized to investigate the effect of the presence of either electron-donating (ED) or electron-withdrawing (EW) groups on the intramolecular pi-stacking assembly. The positioning of ED or EW moieties was carried out directly on one of the aromatic rings linked to the sulfonyl or sulfonamide moieties. In contrast, the other aromatic ring (phenyl or pyridine) was connected by a -CH2-CH2- spacer with the sulfonyl or sulfonamide moiety. The purpose of having an ethyl spacer between the two aromatic rings was to achieve conformational flexibility, facilitating the intramolecular pi-stacking assembly between the two aromatic rings. The use of sulfoester/sulfonamide groups allowed more conformational flexibility to attain desired orientations in solids with the interplay of the hydrogen-bonding interactions. Between the two functional groups, sulfonamides offered a more hydrogen-rich environment due to the amine moiety and may exhibit higher H-bonding propensity than the sulfoester moiety. The central idea here was to study the interplay between the hydrogen-bonding and pi \& ctdot;pi interactions. The substituent groups chosen were categorized as strong electron-withdrawing (-CF3 and -CN), weak electron-withdrawing (-Cl and -Br), neutral (-H), and good electron-donating (-CH3 and -OCH3) groups. Crystal structure analysis revealed the syn conformation for all the derivatives, enabling intramolecular pi \& ctdot;pi interactions between the two aromatic rings, whereas in the sulfonamide derivatives, the molecule takes either midway or anti conformations, except for one pyridine sulfonamide derivative, which showed the syn orientation but lacked intramolecular pi-stacking interactions. The absence of any conventional H-bond forming functional groups in the sulfoester derivatives may have resulted in the syn geometry facilitated by intramolecular pi-stacking interactions. Conversely, H-bond-forming functional groups in the sulfonamide derivatives could have prevented the syn conformation. The conformational analysis carried out employing density functional theory (DFT) calculations confirmed the higher stability of the syn conformation over the midway and anti orientations. The placing of electron-withdrawing and electron-donating groups at the para position of the benzene revealed sulfoesters preferably adopts a syn geometry facilitating the intramolecular pi-stacking, but sulphonamides takes midway or anti-geometry.

}, doi = {10.1039/d4ce00309h}, author = {Shaikh, Samir R. and Gawade, Rupesh L. and Dabke, Niteen B. and Dash, Soumya R. and Vanka, Kumar and Gonnade, Rajesh G.} } @article {49341, title = {Cu-catalyzed multicomponent reaction of arylhydrazines with β-ketoesters and TBN: one-pot access to N 2-aryl 1,2,3-triazole-1-oxides}, journal = {Journal of Organic Chemistry}, volume = {89}, year = {2024}, month = {NOV }, pages = {16990-16998}, type = {Article}, abstract = {

We report a copper-catalyzed one-pot, multicomponent strategy for the convenient synthesis of N 2-aryl 1,2,3-triazole-1-oxides using arylhydrazines, beta-ketoesters, and tert-butyl nitrite. This mild and simple reaction proceeds in an atom-economic manner with broad substrate scope, affording a variety of N 2-aryl 1,2,3-triazole-1-oxide derivatives. Other salient features of the reaction are good functional group tolerance, scalability, and product diversification.

}, issn = {0022-3263}, doi = {10.1021/acs.joc.4c00298}, author = {Mujahid, Mohammad and Vara, Vijay and Arshad, Usman and Gamidi, Rama Krishna and Muthukrishnan, M.} } @article {49194, title = {Dehydrogenative coupling of alcohols with internal alkynes under nickel catalysis: an access to β-deuterated branched ketones}, journal = {ACS Catalysis}, volume = {14}, year = {2024}, month = {MAY}, pages = {8294-8309}, type = {Article}, abstract = {

In synthetic organic chemistry, unconventional strategies for advanced chemical synthesis pose interesting and challenging problems. Alcohols act as alkylating agents in the C-C and C-N bond-forming reactions via the dehydrogenative borrowing hydrogen strategy in traditional transition metal catalysis; however, as an acylating agent in the C-C bond-forming reactions is challenging and rarely reported. Here, we report the dehydrogenative coupling of benzylic alcohols with internal alkynes under nickel(II) catalysis, wherein alcohol is used as an acylating agent. This reaction system affords a wide range of alpha-branched aryl ketone derivatives with zero waste generation through the umpolung borrowing hydrogen strategy. Moreover, we have demonstrated the chemodivergent applications of the alpha-disubstituted ketones to other valuable building blocks, including large-scale synthesis of beta-deuterated branched ketones. Several spectroscopic studies, intermediate identification, and density functional theory calculations were performed to elucidate the reaction mechanism.

}, keywords = {Alcohols, alpha-branched aryl ketones, dehydrogenative coupling, internal alkynes, nickel catalysis, pseudoumpolung}, issn = {2155-5435}, doi = {10.1021/acscatal.3c06091}, author = {Subaramanian, Murugan and Gouda, Chandrakant and Roy, Triptesh Kumar and Ganesan, Sivakumar and Banerjee, Subhrashis and Vanka, Kumar and Balaraman, Ekambaram} } @article {49417, title = {Designing of imine thiophene-ligated metal-complexes and implication in ethylene polymerization}, journal = {Journal of Macromolecular Science Part A-Pure and Applied Chemistry}, year = {2024}, month = {SEP}, type = {Article; Early Access}, abstract = {

Polyethylene is the single largest volume polymer produced globally using Ziegler-type catalysts. Numerous modifications have been reported in search of a better catalyst that can control molecular weight, polydispersity, and branching. In our attempts to identify a suitable imine thiophene-ligated chromium complex, we examined 9 different titanium complexes computationally. The DFT investigations considered barriers for insertion, propagation, and termination by beta-H elimination or chain transfer, and identified N-(4-methoxyphenyl)-2-phenyl-1-(thiophen-2-yl)ethan-1-imine(L9) as the most suitable ligand. Subsequently, L9 was prepared in good yield (70\%) by condensing 2-phenyl-1-(thiophen-2-yl)ethan-1-one with 4-methoxyaniline. Ligand L9 was treated with early transition metal precursors (Ti, Cr, Zr) to generate a homogenous catalyst. The identity of these catalysts was unambiguously ascertained using a combination of NMR, ICP, FT-IR, UV-Vis spectroscopy, and ESI-MS. The performance of L9-ligated titanium complex [Cat.1] was examined in ethylene polymerization using MMAO as a co-catalyst. Insertion of ethylene was tracked using high-pressure NMR experiments and Cat.1 was found to be active in the polymerization. Ethylene polymerization conditions were optimized to obtain high activity and molecular weight polyethylene. The chromium complex [Cat.2] outperformed the Ti and Zr-derived catalysts with the highest TOF of 6294 mol of PE/mol of Cr/h. Cat.2 produced high molecular weight, high-density polyethylene.

}, keywords = {Cr-complexes, DFT, high-density polyethylene, Imine thiophene ligand, Polyethylene}, issn = {1060-1325}, doi = {10.1080/10601325.2024.2409753}, author = {Shaikh, Maulali H. and Ramekar, V. Rohan and Jawoor, Shailaja and Dash, Soumya R. and Birajadar, Rajkumar S. and Pawal, Sandip B. and Thenmani, Nandakumar and Vanka, Kumar and Chikkali, Samir H.} } @article {49612, title = {Dietary supplementation of lactococcus lactis subsp. lactis BIONCL17752 on growth performance, and gut microbiota of broiler chickens}, journal = {Probiotics and Antimicrobial Proteins}, year = {2024}, month = {JUN}, type = {Article}, abstract = {

The rapid rise of antimicrobial resistance (AMR) is a global concern, being triggered by the overuse or misuse of antibiotics in poultry farming sector. We evaluated Lactococcus lactis subsp. lactis BIONCL17752 strain, and characterized its probiotic potential to endure hostile gastrointestinal conditions. Genome sequencing analysis revealed probiotics traits, and gene clusters involved in bacteriocins, lactococcin A, and sactipeptides production. The absence of genes for antibiotic resistance, virulence, and biogenic amine production indicates the potential of probiotic strain. The BIONCL17752 strain was explored for antibiotic-free feed supplement for growth promotor in broiler chicken. The feed supplemented with 4 x 109 CFU/kg of probiotic strain, in combination with various concentrations of fructooligosaccharides (FOS) 1.0, 2.5, and 5.0 kg/tonne in starter, grower, and finisher diets, respectively. A significant improvement of body weight 152 to 171 g/bird (p \< 0.05), and a low feed conversion ratio (FCR) of 1.62, was achieved without using synthetic antibiotics for growth promotion. The results of biochemical, hematological, and histological examinations showed normal features, indicating that the treatment had no harmful effects on the bird{\textquoteright}s health. Reduced levels of cholesterol, triglycerides, high-density lipoprotein (HDL), and low-density lipoprotein (LDL) in serum are an indication of the health benefits for the treated birds. Microbial community analysis of fecal samples of poultry birds exhibited a higher abundance of Bacteroidetes, Firmicutes, Proteobacteria, Actinobacteria, and Fusobacteria. Probiotic treatment resulted in reduced Firmicutes and increased Bacteroidetes (F/B ratio) in the broiler{\textquoteright}s gut which highlights the benefits of probiotic dietary supplements. Importantly, the probiotic-fed group exhibited a high abundance of carbohydrate-active enzymes (CAZyme) such as glycoside hydrolases (GH), glycoside transferases (GT), and carbohydrate-binding module (CBM) hydrolases which are essential for the degradation of complex sugar molecules. The probiotic potential of the BIONCL17752 strain contributes to broilers{\textquoteright} health by positively affecting intestinal microbiota, achieving optimal growth, and lowering mortality, demonstrating the economic benefits of probiotic treatment in organic poultry farming.

}, keywords = {Antibiotic growth promotor, Broiler chickens, Functional genome analysis, Growth performance, Gut microbiota, Lactococcus lactis subsp. lactis}, issn = {1867-1306}, doi = {10.1007/s12602-024-10313-4}, author = {Navale, Vishwambar D. and Yadav, Rakeshkumar and Khilari, Ajinkya and Dharne, Mahesh and Shanmugam, Dhanasekaran and Vamkudoth, Koteswara Rao} } @article {49037, title = {Effect of position of donor units and alkyl groups on dye-sensitized solar cell device performance: indoline-aniline donor-based visible light active unsymmetrical squaraine dyes}, journal = {ACS Om.}, volume = {9}, year = {2024}, month = {MAR}, pages = {16429-16442}, type = {Article}, abstract = {

Indoline (In) and aniline (An) donor-based visible light active unsymmetrical squaraine (SQ) dyes were synthesized for dye-sensitized solar cells (DSSCs), where the position of An and In units was changed with respect to the anchoring group (carboxylic acid) to have In-SQ-An-CO2H and An-SQ-In-CO2H sensitizers, AS1-AS5. Linear or branched alkyl groups were functionalized with the N atom of either In or An units to control the aggregation of the dyes on TiO2. AS1-AS5 exhibit an isomeric pi-framework where the squaric acid unit is placed in the middle, where AS2 and AS5 dyes possess the anchoring group connected with the An donor, and AS1, AS3, and AS4 dyes having the anchoring group connected with the In donor. Hence, the conjugation between the middle squaric acid acceptor unit and the anchoring -CO2H group is short for AS2, AS5, and AK2 and longer for AS1, AS3, and AS4 dyes. AS dyes showed absorption between 501 and 535 nm with extinction coefficients of 1.46-1.61 x 10(5) M-1 cm(-1). Further, the isomeric pi-framework of An-SQ-In-CO2H and In-SQ-An-CO2H exhibited by means of changing the position of In and An units a bathochromic shift in the absorption properties of AS2 and AS5 compared to the AS1, AS3, and AS4 dyes. The DSSC device fabricated with the dyes contains short acceptor-anchoring group distance (AS2 and AS5) showed high photovoltaic performances compared to the dyes having longer distance (AS1, AS3, and AS4) with the iodolyte (I-/I-3(-)) electrolyte. DSSC device efficiencies of 5.49, 6.34, 6.16, and 5.57\% have been achieved for AS1, AS2, AS3, and AS4 dyes, respectively; without chenodeoxycholic acid (CDCA), small changes have been observed in the device performance of the AS dyes with CDCA. Significant changes have been noted in the DSSC parameters (open-circuit voltage V-OC, short-circuit current J(SC), fill factor ff, and efficiency eta) for the AS5 dye while sensitized with CDCA and showed highest DSSC efficiency of 8.01\% in the AS dye series. This study revealed the potential of shorter SQ acceptor-anchoring group distance over the longer one and the importance of alkyl groups on the overall DSSC device performance for the unsymmetrical squaraine dyes.

}, issn = {2470-1343}, doi = {10.1021/acsomega.4c00123}, author = {Singh, Amrita and Singh, Ambarish Kumar and Dixit, Ruchi and Vanka, Kumar and Krishnamoorthy, Kothandam and Nithyanandhan, Jayaraj} } @article {49312, title = {An effective, facile, and rapid synthesis of nanosized Mn3O4 using a microwave route}, journal = {Journal of Nanoparticle Research}, volume = {26}, year = {2024}, month = {OCT}, pages = {239}, type = {Article}, abstract = {

Microwave-assisted one-pot, one-step, calcination-free synthesis of nanosized Mn3O4 is reported using only benzylamine and manganese acetate. Benzylamine in this protocol plays a vital role for efficient microwave synthesis. This microwave method enables the synthesis of nanosized Mn3O4 in just few hours only in a single step eliminating the need of calcinations of any intermediate. The synthesized nanosized Mn3O4 was analyzed by XRD, HRTEM, EDAX, and Raman spectroscopy. The catalytic and electrochemical properties of as-synthesized Mn3O4 were investigated. In galvanostatic charge-discharge experiments, after 800 cycles, more than 89\% capacitance was retained for electrodes made by as synthesized Mn3O4 nanomaterials indicating its very good stability. In the catalytic conversion of cinnamyl alcohol to cinnamaldehyde via oxidation, using as prepared nanosized Mn3O4 as a catalyst, it displays effective catalytic properties. A probable mechanical study of its formation was also envisaged. This synthesis protocol is additive-free, occurs in a short time, is facile, is energy efficient, and eliminates the use of many chemicals. These silent features make these reported protocols economically viable and environmentally benign which adhere to the principles of Green Chemistry.

}, keywords = {Calcination free, Electrochemical and catalytic properties, Nanosized Mn3O4, Single-step synthesis}, issn = {1388-0764}, doi = {10.1007/s11051-024-06148-3}, author = {Yadav, Akash and Jha, Ratnesh and Bhatkar, Akash and Kamble, Aditi and Vaishnav, Vishal and Bogalera, Shivamurthy P. and Manikandan, Marimuthu and Nayaka, Girish Praveen and Umbarkar, Shubhangi and Raja, Thirumalaiswamy and Bhatte, Kushal D.} } @article {49413, title = {Electrocatalytic and selective oxidation of glycerol to formate on 2D 3d-metal phosphate nanosheets and carbon-negative hydrogen generation}, journal = {ACS Materials Au}, volume = {4}, year = {2024}, month = {JUN}, pages = {500-511}, type = {Article}, abstract = {

In the landscape of green hydrogen production, alkaline water electrolysis is a well-established, yet not-so-cost-effective, technique due to the high overpotential requirement for the oxygen evolution reaction (OER). A low-voltage approach is proposed to overcome not only the OER challenge by favorably oxidizing abundant feedstock molecules with an earth-abundant catalyst but also to reduce the energy input required for hydrogen production. This alternative process not only generates carbon-negative green H2\ but also yields concurrent value-added products (VAPs), thereby maximizing economic advantages and transforming waste into valuable resources. The essence of this study lies in a novel electrocatalyst material. In the present study, unique and two-dimensional (2D) ultrathin nanosheet phosphates featuring first-row transition metals are synthesized by a one-step solvothermal method, and evaluated for the electrocatalytic glycerol oxidation reaction (GLYOR) in an alkaline medium and simultaneous H2\ production. Co3(PO4)2\ (CoP), Cu3(PO4)2\ (CuP), and Ni3(PO4)2\ (NiP) exhibit 2D sheet morphologies, while FePO4\ (FeP) displays an entirely different snowflake-like morphology. The 2D nanosheet morphology provides a large surface area and a high density of active sites. As a GLYOR catalyst, CoP ultrathin (\~{}5 nm) nanosheets exhibit remarkably low onset potential at 1.12 V (vs RHE), outperforming that of NiP, FeP, and CuP around 1.25 V (vs RHE). CoP displays 82\% selective formate production, indicating a superior capacity for C{\textendash}C cleavage and concurrent oxidation; this property could be utilized to valorize larger molecules. CoP also exhibits highly sustainable electrochemical stability for a continuous 200 h GLYOR operation, yielding 6.5 L of H2\ production with a 4 cm2\ electrode and 98 {\textpm} 0.5\% Faradaic efficiency. The present study advances our understanding of efficient GLYOR catalysts and underscores the potential of sustainable and economically viable green hydrogen production methodologies.

}, doi = {https://doi.org/10.1021/acsmaterialsau.4c00024}, author = {Chauhan, Inderjeet and Vijay, Pothoppurathu M. and Ranjan, Ravi and Patra, Kshirodra Kumar and Gopinath, Chinnakonda S.} } @article {48992, title = {Electrochemical energy storage in an organic supercapacitor via a non-electrochemical proton charge assembly}, journal = {Chemical Science}, volume = {15}, year = {2024}, month = {JAN }, pages = {1726-1735}, type = {Article}, abstract = {

Contrary to conventional beliefs, we show how a functional ligand that does not exhibit any redox activity elevates the charge storage capability of an electric double layer via a proton charge assembly. Compared to an unsubstituted ligand, a non-redox active carboxy ligand demonstrated nearly a 4-fold increase in charge storage, impressive capacitive retention even at a rate of 900C, and approximately a 2-fold decrease in leakage currents with an enhancement in energy density up to approximately 70\% via a non-electrochemical route of proton charge assembly. Generalizability of these findings is presented with various non-redox active functional units that can undergo proton charge assembly in the ligand. This demonstration of non-redox active functional units enriching supercapacitive charge storage via proton charge assembly contributes to the rational design of ligands for energy storage applications.

}, issn = {2041-6520}, doi = {10.1039/d3sc05639b}, author = {Mukhopadhyay, Sanchayita and Kottaichamy, Alagar Raja and Devendrachari, Mruthyunjayachari Chattanahalli and Mendhe, Rahul Mahadeo and Kotresh, Harish Makri Nimbegondi and Vinod, Chathakudath Prabhakaran and Thotiyl, Musthafa Ottakam} } @article {49121, title = {Enhanced catalytic conversion of disaccharides to propylene glycol using metal-supported graphitic carbon nitride}, journal = {Energy and Fuels}, volume = {38}, year = {2024}, month = {MAR }, pages = {7005-7017}, type = {Article}, abstract = {

Propylene glycol (or) 1,2-propanediol (1,2-PD) is an important polyol widely used for pharmaceuticals, polyester resins, paints, cosmetics, antifreeze, etc. Sucrose has emerged as a promising feedstock to produce 1,2-PD, as indicated by recent research findings. Graphitic carbon nitride (g-C3N4/gCN) was synthesized by using different crucibles. Ni-Mo was loaded on different g-C3N4 supports via the wetness impregnation method for sucrose hydrogenolysis. Effects of different g-C3N4 supports were studied. Catalysts with varying Ni (x = 0-8 wt \%) and Mo (y = 0-15 wt \%) contents were characterized using XRD, BET, XPS, FE-SEM, Py-FTIR, HR-TEM, TPD (CO2)and Raman spectroscopy. An attempt was made on sucrose conversion into 1,2-PD using a Ni-Mo/g-C3N4 catalyst. The catalyst containing 8\% Ni and 10\% Mo on Gr-gCN exhibited the best performance, achieving complete sucrose conversion with a 76\% yield of 1,2-PD under mild reaction conditions. The presence of highly dispersed nanoparticles and the nature of graphitic carbon nitride help improve the reactions{\textquoteright} yield by allowing reactions at lower temperatures, reducing the occurrence of side reactions, and increasing recycling rates. A straightforward approach to material preparation, coupled with the exceptional dispersion of metal nanoparticles, paves the way for a novel platform for biomass conversion.

}, issn = {0887-0624}, doi = {10.1021/acs.energyfuels.3c05087}, author = {Kirali, Arun Arunima Balachandran and Narayanan, Hariprasad and Viswanathan, Balasubramanian and Yadav, Parmeshwar and Marimuthu, Banu} } @article {48956, title = {Enhancing the Catalytic Activity of Pd Nanocrystals towards Suzuki Cross-Coupling by g-C3N4 Photosensitization}, journal = {Chemnanomat}, volume = {10}, year = {2024}, month = {JAN}, type = {Journal Article}, abstract = {

Developing renewable means of activating molecules over traditional catalysts for C-C bond formation is desirable for industrial applications. Herein, we report a strategy to improve the efficiency of Pd nanoparticles (NPs) for the Suzuki cross-coupling reactions by visible-light irradiation using g-C3N4 nanosheets (NSs) as photosensitizer. Pd NPs mounted on g-C3N4 become electron-rich under visible-light due to generation of excited electrons in g-C3N4 and thereby accelerate the rate-determining step. Remarkable photocatalytic activity was accomplished utilizing Pd/g-C3N4 for the Suzuki cross-coupling reaction in environmentally benign aqueous settings under room temperature conditions. The activity remarkably improves (similar to 2.5 times) upon light irradiation, yielding one of the highest known turnover frequencies (TOF) of 1858 h(-1) and confirming the photosensitizer role of g-C3N4. The TOF for coupling of aryl bromides is also significantly high (similar to 356 h(-1)). We establish that the low-energy/long-lived excitons preferencially transfer to Pd, paving a way for rational designing photocatalysts for various C-C coupling reactions.

}, keywords = {2D graphitic carbon nitride, C-C cross-coupling, exciton transfer, heterogeneous photocatalyst, Photosensitization}, issn = {2199-692X}, doi = {10.1002/cnma.202300451}, author = {Mondal, Sanjit and Sahoo, Lipipuspa and Banoo, Maqsuma and Vaishnav, Yuvraj and Prabhakaran Vinod, Chathakudath and Gautam, Ujjal} } @article {49014, title = {Experimental and kinetic modelling studies for the design of fixed bed methanol reactor over CuZA catalyst}, journal = {Chemical Engineering Research Design }, volume = {205}, year = {2024}, month = {MAY}, pages = {79-90}, type = {Article}, abstract = {

Direct conversion of CO 2 via hydrogenation to value-added chemicals is a vital approach for utilising CO 2 emitted into the atmosphere. In this paper, a critical analysis of reaction kinetic modelling studies is explored in a fixed bed reactor to improve methanol yield for different H 2 to CO 2 ratios by simulating a lab-scale reactor for adiabatic and isothermal conditions. The feed inlet temperature and pressure variations are applied to study the effect of both configurations on methanol production. The results show that the isothermal configuration yields 2.76\% more methanol yield compared to the adiabatic reactor. The effect of H 2 to CO 2 molar ratios of 3, 6 and 9 on the performance of the catalyst and the influence of CO and CO 2 hydrogenation is investigated with model simulations. The overall methanol yield is increased from 19.03\% to 36.41\% with increase in H 2 to CO 2 molar ratio from 3 to 9. Experiments are performed using commercial copper-based catalyst for different temperatures of 210, 230 and 250 degrees C at a pressure of 40 bar for H 2 /CO 2 of 3 and GHSV of 720 h -1 as well as at optimal temperature of 250 degrees C and 50 bar with varying H 2 /CO 2 of 3, 6, 9 for 3 g and 6 g catalyst. The maximum methanol yield of 2.53\% and space time yield of 13.59 mg/g cat .h is obtained at H 2 /CO 2 ratio of 9.

}, keywords = {CO2 conversion, CuZA catalyst, H2 toCO2 molar ratio, Kinetic modelling, Methanol}, issn = {0263-8762}, doi = {10.1016/j.cherd.2024.03.032}, author = {Bagwan, Farahanaz M. and Dongapure, Pavan and Kulkarni, Amol A. and Vasireddy, Satyam Naidu} } @article {49282, title = {Exploring the CeO2 support morphology for the carbon dioxide hydrogenation reaction using nickel catalysts}, journal = {Journal of Physical Chemistry C}, volume = {128}, year = {2024}, month = {OCT}, pages = {18782-18792}, type = {Article}, abstract = {

The catalytic activity and stability are examined for the hydrogenation of carbon dioxide under atmospheric pressure over 2 wt \% Ni/CeO2 nanorods (2Ni-CeNRs), nanocubes (2Ni-CeNCs), and nanopolyhedra (2Ni-CeNPs). The 2Ni-CeNR catalysts display excellent catalytic activity and higher stability compared with 2Ni-CeNC and 2Ni-CeNP catalysts. A comprehensive understanding of the surface atomic and electronic structure versus activity has been derived using high-resolution electron microscopy and spectroscopy techniques. High metal dispersion, strong metal-support interaction (SMSI) effect and abundant oxygen vacancies are deduced to play a crucial role in determining the catalytic activity and selectivity of the CO2 hydrogenation reaction.

}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.4c05258}, author = {Gupta, Sharad and Jagtap, Anuradha and Vinod, C. P.} } @article {49372, title = {Exploring thermocatalytic pyrolysis to derive sustainable chemical intermediates from plastic waste; role of temperature, catalyst, and reactor conditions}, journal = {Journal of the Indian Institute of Science}, volume = {104}, year = {2024}, month = {APR}, pages = {383-394}, type = {Review}, abstract = {

Plastic waste is a growing concern globally on account of the increasing use of plastic worldwide, compounded by single-use applications, poor waste collection and management practices, and its consequent leakage into the environment. In addition, plastics are derived from non-renewable fossil resources, and their growing demand is also partly responsible for greenhouse gas emissions and climate change. The aim of this paper is to explore the potential of plastic waste as a material resource, and thermocatalytic pyrolysis as a recycling process, to produce aliphatic and aromatic hydrocarbons, which are important chemical intermediates for various industries. We show that plastic pyrolysis can achieve a high yield of liquid hydrocarbons (similar to 80\%) with a suitable distribution of aliphatic and aromatic compounds, by using different pyrolysis conditions and a catalyst. Specifically, this paper demonstrates the possibility of deriving two key classes of hydrocarbons, i.e., aliphatic (C10-C20 hydrocarbons) and aromatic hydrocarbons (xylene, toluene and benzene derivatives) with a yield of similar to 80\% liquid hydrocarbons via catalytic pyrolysis. We also briefly discuss the challenges and opportunities, and the environmental and economic implications.

}, issn = {0970-4140}, doi = {10.1007/s41745-024-00447-3}, author = {Venkataraghavan, R. and Bhure, Arvind and Khan, Tufeil Sartaj and Shikare, Dipak and Devi, R. Nandini and Dhepe, Paresh Laxmikant} } @article {49021, title = {Exploring unconventional σ-hole interactions: computational insights into the interaction of XeO3 with non-aromatic coordinating solvents}, journal = {Chemphyschem}, volume = {25}, year = {2024}, month = {MAR}, type = {Article}, abstract = {

In order to control the explosiveness and shock sensitivity of XeO3, we have investigated its plausible interaction with various non-aromatic coordinating solvents, serving as potential Lewis base donors, through density functional theory (DFT) calculations. Out of twenty six such solvents, the top ten were thus identified and then thoroughly examined by employing various computational tools such as the mapping of the electrostatic potential surface (MESP), Wiberg bond indices (WBIs), non-covalent interaction (NCI) plots, Bader{\textquoteright}s theory of atoms-in-molecules (AIM), natural bond orbital (NBO) analysis, and the energy decomposition analysis (EDA). The amphoteric nature of XeO3 was also explored by investigating the extent of back donation from the lone pair of Xe to the antibonding orbital of the donating atom/group of the solvent molecules. The C-H \& mldr;O interactions were also found to be a contributing factor in the stabilization of these adducts. Although these aerogen-bonding interactions were found to be predominantly electrostatic, significant contributions from the orbital contributions, as well as dispersion interactions, were observed. The top three non-aromatic solvents (among the twenty six studied) which form the strongest adducts with XeO3 are proposed to be hexamethylphosphoramide (HMPA), N,N {\textquoteleft}-dimethylpropyleneurea (DMPU) and tetramethylethylenediamine (TMEDA).

}, keywords = {Aerogen bonding, Non-Aromatic Solvents, non-covalent interactions, Sigma-hole, XeO3}, issn = {1439-4235}, doi = {10.1002/cphc.202300908}, author = {Dash, Soumya Ranjan and Vanka, Kumar} } @article {49113, title = {Facile synthesis of nanostructured Ni/NiO/N-doped graphene electrocatalysts for enhanced oxygen evolution reaction}, journal = {Nanoscale Advances}, volume = {6}, year = {2024}, month = {MAY}, pages = {2813-2822}, type = {Article}, abstract = {

Electrocatalysts containing a Ni/NiO/N-doped graphene interface have been synthesised using the ligand-assisted chemical vapor deposition technique. NiO nanoparticles were used as the substrate to grow N-doped graphene by decomposing vapours of benzene and N-containing ligands. The method was demonstrated with two nitrogen-containing ligands, namely dipyrazino[2,3-f:2 {\textquoteleft},3 {\textquoteleft}-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (L) and melamine (M). The structure and composition of the as-synthesized composites were characterized by XRD, Raman spectroscopy, SEM, TEM and XPS. The composite prepared using the ligand L had NiO sandwiched between Ni and N-doped graphene and showed an overpotential of 292 mV at 10 mA cm-2 and a Tafel slope of 45.41 mV dec-1 for the OER, which is comparable to the existing noble metal catalysts. The composite prepared using the ligand M had Ni encapsulated by N-doped graphene without NiO. It showed an overpotential of 390 mV at 10 mA cm-2 and a Tafel slope of 78.9 mV dec-1. The ligand-assisted CVD route demonstrates a facile route to control the microstructure of the electrocatalysts. Electrocatalysts containing a Ni/NiO/N-doped graphene interface have been synthesised using the ligand-assisted chemical vapor deposition technique.

}, issn = {2516-0230}, doi = {10.1039/d4na00141a}, author = {Madampadi, Roshni and Patel, Avit Bhogilal and Vinod, C. P. and Gupta, Ritu and Jagadeesan, Dinesh} } @article {49326, title = {Far-red active unsymmetrical squaraine dyes containing N-arylated indoline donors for dye sensitized solar cells}, journal = {Photochemistry and Photobiology}, volume = {100}, year = {2024}, month = {JUL}, pages = {1116-1126}, type = {Article}, abstract = {

Squaraine dyes possess sharp far-red active transition with high extinction coefficient and form aggregates on TiO2 surface. Aggregation of dyes on TiO2 has been considered as a detrimental factor for DSSC device performance, which can be controlled by appending alkyl groups to the dye structures. Hence by integrating alkylated (alkyl groups with both in-plane and out-of-plane) aryl group with indoline moiety to make it compatible with other electrolytes and for controlling the dye-aggregation, a series of squaraine acceptor-based dyes SQA4-6 have been designed and synthesized. SQA4-6 dyes showed absorption between 642 and 653 nm (lambda max), photophysical and electrochemical studies indicated that the HOMO energy levels of this sets of dyes are well aligned with the potentials of I-/I3-\$\$ {\textbackslashmathrm{I}}_3\<\^\>{-} \$\$ and [Co(bpy)3]2+/3+ redox shuttles for better dye regeneration process. DSSC device efficiency of 3\% has been achieved for SQA5 dye with iodolyte (I-/I3-\$\$ {\textbackslashmathrm{I}}_3\<\^\>{-} \$\$) electrolyte in the presence of 0.3 mM of chenodeoxycholic acid (CDCA). The IPCE profile of DSSC device fabricated with SQA4-6 dyes indicated the contribution of aggregated structures for the photocurrent generation. Dye-sensitized solar cell (DSSC) device efficiency of 3\% (Jsc 5.72 mA cm-2, Voc 662 mV and ff 79\%) has been achieved for an unsymmetrical squaraine dye, SQA5 with iodolyte electrolyte and the incident photon to current efficiency (IPCE) profile indicates the contribution of aggregated structures for the photocurrent generation.*image

}, keywords = {aggregation of dye, arylation on N-atom of indoline donor, dye-sensitized solar cell, squaraine dye}, issn = {0031-8655}, doi = {10.1111/php.13907}, author = {Jadhav, Avinash P. and Singh, Ambarish Kumar and Pandya, Rinu and Vanka, Kumar and Krishnamoorthy, Kothandam and Jayaraj, Nithyanandhan} } @article {49308, title = {F-doped nickel cobalt oxide-carbon composite electrocatalysts paired with mechanically robust anion-conducting chitosan membranes for flexible and rechargeable zinc-air batteries}, journal = {ACS Applied Energy Materials}, volume = {7}, year = {2024}, month = {AUG}, pages = {7037-7054}, type = {Article}, abstract = {

High-performing, cost-effective electrocatalysts and anion-conducting polymer electrolyte membranes are essential for realizing commercially affordable zinc-air batteries (ZABs). In this context, the present work deals with the development of a bifunctional electrocatalyst and an anion-exchange quasi-solid-state electrolyte membrane (based on quaternary ammonium group-grafted chitosan) for demonstrating flexible and rechargeable ZABs. The electrocatalyst composed of NiCoO2 nanoparticles supported on a carbon framework showcased substantial advancements in its ability to catalyze both oxygen reduction and evolution reactions (ORR and OER) due to the heteroatom doping by fluorine. For instance, the optimized electrocatalyst (F-NCO-ADC-600) exhibited an onset potential of 0.96 V vs RHE with a half-wave potential of 0.83 V vs RHE for ORR, a comparable performance with the state-of-the-art Pt/C (1.0 and 0.86 V vs RHE, respectively). On a similar note, the same catalyst also displayed an overpotential of 340 mV vs RHE for OER at a current density of 20 mA cm(-2), close to that of a standard RuO2 catalyst (337 mV vs RHE). In the context of polymer electrolytes, the quaternary ammonium-group-grafted chitosan membrane depicted superior ionic conductivity, liquid electrolyte uptake, and mechanical properties, thereby proving to be an efficient anion-conducting polymer electrolyte membrane. The realistic application of the developed electrocatalyst and the polymer electrolyte membrane is demonstrated in the ZAB prototypes. The assembled rechargeable ZAB (RZAB) delivered a power density of 207 mW cm(-2) and maintained high-rate capability and cycling stability, notably in a flexible configuration (f-RZABs). Thus, this work provides a strategy for the rational design of anion-exchange membranes and bifunctional electrocatalysts for f-RZABs.

}, keywords = {anion-conducting polymer electrolytemembrane, F-doping, flexible and rechargeable zinc-air batteries(f-RZABs), oxygen evolution reaction(OER), oxygen reduction reaction (ORR)}, issn = {2574-0962}, doi = {10.1021/acsaem.4c01261}, author = {Kurian, Maria and Ranganath, Suresha P. and Vijayakumar, Vidyanand and Sivadasan, Sneha and Kurian, Rachna Maria and Badiger, Manohar V. and Kurungot, Sreekumar} } @article {49116, title = {Fuel from waste: electrosynthesizing ammonia directly from agricultural digestate through ligand isomerization}, journal = {Green Chemistry}, volume = {26}, year = {2024}, month = {JUN}, pages = {6490-6500}, type = {Article}, abstract = {

We demonstrate that the catalytic metal centre for ammonia production can be selectively activated with only a slight alteration in ligand isomerization (alpha and beta isomers), making it practical and effective even for agricultural effluents. With almost 90\% faradaic efficiency, the beta isomer generates approximately 0.64 mg h-1 cm-2 of ammonia. Energy-efficient ammonia recovery is made possible by the interfacial proton charge assembly that beta-isomerization creates, which attracts the reacting nitrate and repels the competing hydronium ions. With minimal energy consumption, this isomerization approach can interconvert agricultural effluents into ammonia fuel, reaching up to 84\% of its theoretical yield and maintaining stability over 100 hours of continuous electrolysis. Ligand isomerization driven ammonia electrosynthesis from agricultural waste water.

}, issn = {1463-9262}, doi = {10.1039/d4gc00740a}, author = {Mendhe, Rahul Mahadeo and Mondal, Ritwik and Kottaichamy, Alagar Raja and Haridas, Akshay and Kotresh, Harish Makri Nimbegondi and Vinod, Chathakudath Prabhakaran and Thimmappa, Ravikumar and Thotiyl, Musthafa Ottakam} } @article {49325, title = {Genome sequencing and analysis of penicillin V producing Penicillium rubens strain BIONCL P45 isolated from India}, journal = {International Microbiology}, volume = {27}, year = {2024}, month = {OCT}, pages = {1473-1484}, type = {Article}, abstract = {

Background A filamentous fungus Penicillium rubens is widely recognized for producing industrially important antibiotic, penicillin at industrial scale. Objective To better comprehend, the genetic blueprint of the wild-type P. rubens was isolated from India to identify the genetic/biosynthetic pathways for phenoxymethylpenicillin (penicillin V, PenV) and other secondary metabolites. Method Genomic DNA (gDNA) was isolated, and library was prepared as per Illumina platform. Whole genome sequencing (WGS) was performed according to Illumina NovoSeq platform. Further, SOAPdenovo was used to assemble the short reads validated by Bowtie-2 and SAMtools packages. Glimmer and GeneMark were used to dig out total genes in genome. Functional annotation of predicted proteins was performed by NCBI non-redundant (NR), UniProt, Kyoto Encyclopedia of Genes and Genomes (KEGG), and Gene Ontology (GO) databases. Moreover, secretome analysis was performed by SignalP 4.1 and TargetP v1.1 and carbohydrate-active enzymes (CAZymes) and protease families by CAZy database. Comparative genome analysis was performed by Mauve 2.4.0. software to find genomic correlation between P. rubens BIONCL P45 and Penicillium chrysogenum Wisconsin 54-1255; also phylogeny was prepared with known penicillin producing strains by ParSNP tool. Results Penicillium rubens BIONCL P45 strain was isolated from India and is producing excess PenV. The 31.09 Mb genome was assembled with 95.6\% coverage of the reference genome P. chrysogenum Wis 54-1255 with 10687 protein coding genes, 3502 genes had homologs in NR, UniProt, KEGG, and GO databases. Additionally, 358 CAZymes and 911 transporter coding genes were found in genome. Genome contains complete pathways for penicillin, homogentisate pathway of phenyl acetic acid (PAA) catabolism, Andrastin A, Sorbicillin, Roquefortine C, and Meleagrin. Comparative genome analysis of BIONCL P45 and Wis 54-1255 revealed 99.89\% coverage with 2952 common KEGG orthologous protein-coding genes. Phylogenetic analysis revealed that BIONCL P45 was clustered with Fleming{\textquoteright}s original isolate P. rubens IMI 15378. Conclusion This genome can be a helpful resource for further research in developing fermentation processes and strain engineering approaches for high titer penicillin production.

}, keywords = {comparative genomics, Illumina NovoSeq, Penicillin biosynthesis, Penicillium rubens, Secondary metabolites, whole genome sequencing}, issn = {1139-6709}, doi = {10.1007/s10123-024-00491-0}, author = {Sawant, Amol M. and Navale, Vishwambar D. and Vamkudoth, Koteswara Rao} } @article {49084, title = {Hydrogenation of furfural to tetrahydrofurfuryl alcohol over nickel-supported on organoclay catalyst}, journal = {Applied Catalysis A-General}, volume = {674}, year = {2024}, month = {MAR }, pages = {119621}, type = {Article}, abstract = {

Nickel supported on organoclay prepared by the impregnation method provides excellent catalytic activity for the hydrogenation of furfural to tetrahydrofurfuryl alcohol. The relative amount of metal and acidic sites influences the hydrogenation reaction. Additionally, by varying the temperature and the H-2 pressure, we can regulate the interaction of furfural with the active sites. And this may decide the fate of the reaction whether it will undergo a two-step hydrogenation to form tetrahydrofurfuryl alcohol or a rearrangement reaction to form cyclopentanone/cyclopentanol. Water was found to be the best solvent for the selective formation of tetrahydrofurfuryl alcohol. Even though alcohols inhibited rearrangement reaction, the hydrogenation of furfural was more selective towards furfuryl alcohol. Ni/O-clay30A under the optimum conditions of 120 degrees C, 4.0 MPa, and in 1 h offered complete conversion of furfural to tetrahydrofurfuryl alcohol.

}, keywords = {furfural, Hydrogenation, Nickel, organoclay, Tetrahydrofurfuryl alcohol}, issn = {0926-860X}, doi = {10.1016/j.apcata.2024.119621}, author = {Kamble, Paresh A. and Vinod, C. P. and Rathod, Virendra K. and Kantam, Mannepalli Lakshmi} } @article {49057, title = {Hydrogenation of glucose to sorbitol by using nickel hydroxyapatite catalyst}, journal = {Chemcatchem}, volume = {16}, year = {2024}, month = {MAY}, type = {Article}, abstract = {

A series of nickel hydroxyapatite catalysts were synthesized by the co-precipitation method followed by calcination and reduction. These catalysts were employed for the aqueous phase hydrogenation of glucose to sorbitol. The Ni-HAP catalyst with comparatively high surface area and acid-base strength gave high sorbitol selectivity in 1 h. Ni-HAP-4 catalyst with moderate Ni (3.5 wt. \%) content having smaller and highly dispersed nickel particles gives an excellent yield of sorbitol, 97 \% in 1 h. The Ni-HAP-4 catalyst works well with other polar protic solvents. Different characterization techniques like XRD, TEM, SEM-EDS, BET, NH3-TPD, and CO2-TPD were employed to analyze the Ni-HAP-4 catalyst. A facile hydrogenation of glucose to sorbitol has been reported with Ni-HAP catalyst using water as a solvent. The excellent yield of sorbitol, 97 \% in 1 h is possible due to the high surface area and high acid-base strength of the Ni-HAP-4 catalyst. image

}, keywords = {glucose, Hydrogenation, Hydroxyapatite (HAP), Nickel, Sorbitol}, issn = {1867-3880}, doi = {10.1002/cctc.202301590}, author = {Kamble, Paresh A. and Vinod, Chathakudath P. and Rathod, Virendra K. and Lakshmi Kantam, Mannepalli} } @article {49316, title = {HyStor: an experimental database of hydrogen storage properties for various metal alloy classes}, journal = {International Journal of Hydrogen Energy}, volume = {90}, year = {2024}, month = {NOV }, pages = {460-469}, type = {Article}, abstract = {

In this work, we introduce the HyStor database, consisting of 1282 metal alloys along with their maximum hydrogen storage capacity (H2wt\%) at a given absorption temperature. The curated HydPark database consist of 831 entries. We sourced compositions from research articles and various patent documents, resulting in addition of 451 compositions to the HydPark database. The addition is reflected in the data across all existing classes of alloys. Further, low entropy alloys (LEA), medium entropy alloys (MEA) and high entropy alloys (HEA) have been newly included classes. This has broadened the scope of the database to encompass the latest materials of interest for hydrogen storage. HyStor contains representation of 54 elements, with a temperature range of 200-800 K, and H2wt\% ranging from 0.1 to 7.19. We conducted thorough checks for duplicate entries, erroneous data, and conflicting compositions within the database to ensure data quality. Furthermore, we conducted multiple tests to identify potential outlier compositions. The data curation and updation reflects into slight improved error metrics of the HYST model, reducing the Mean Absolute Error (MAE) from 0.31 to 0.29 and increasing the R2 score from 0.77 to 0.79.

}, keywords = {Databases, machine learning, Metal hydrides, Solid-state hydrogen storage}, issn = {0360-3199}, doi = {10.1016/j.ijhydene.2024.09.390}, author = {Wilson, Nikhil and Verma, Ashwini and Maharana, Piyush Ranjan and Sahoo, Ameeya Bhusan and Joshi, Kavita} } @article {49464, title = {Immunogenicity of SARS-CoV-2 vaccines BBV152 (COVAXIN{\textregistered}) and ChAdOx1 nCoV-19 (COVISHIELD{\texttrademark}) in seronegative and seropositive individuals in India: a multicentre, nonrandomised observational study}, journal = {Lancet Regional Health - Southeast Asia}, volume = {22}, year = {2024}, month = {MAR}, type = {Article}, abstract = {

Background:\ There are limited global data on head-to-head comparisons of vaccine platforms assessing both humoral and cellular immune responses, stratified by pre-vaccination serostatus. The COVID-19 vaccination drive for the Indian population in the age group 18-45 years began in April 2021 when seropositivity rates in the general population were rising due to the delta wave of COVID-19 pandemic during April-May 2021.

Methods:\ Between June 30, 2021, and Jan 28, 2022, we enrolled 691 participants in the age group 18-45 years across four clinical sites in India. In this non-randomised and laboratory blinded study, participants received either two doses of Covaxin{\textregistered} (4 weeks apart) or two doses of Covishield{\texttrademark} (12 weeks apart) as per the national vaccination policy. The primary outcome was the seroconversion rate and the geometric mean titre (GMT) of antibodies against the SARS-CoV-2 spike and nucleocapsid proteins post two doses. The secondary outcome was the frequency of cellular immune responses pre- and post-vaccination.

Findings:\ When compared to pre-vaccination baseline, both vaccines elicited statistically significant seroconversion and binding antibody levels in both seronegative and seropositive individuals. In the per-protocol cohort, Covishield{\texttrademark} elicited higher antibody responses than Covaxin{\textregistered} as measured by seroconversion rate (98.3\% vs 74.4\%, p \< 0.0001 in seronegative individuals; 91.7\% vs 66.9\%, p \< 0.0001 in seropositive individuals) as well as by anti-spike antibody levels against the ancestral strain (GMT 1272.1 vs 75.4 binding antibody units/ml [BAU/ml], p \< 0.0001 in seronegative individuals; 2089.07 vs 585.7 BAU/ml, p \< 0.0001 in seropositive individuals). As participants at all clinical sites were not recruited at the same time, site-specific immunogenicity was impacted by the timing of vaccination relative to the delta and omicron waves. Surrogate neutralising antibody responses against variants-of-concern including delta and omicron was higher in Covishield{\texttrademark} recipients than in Covaxin{\textregistered} recipients; and in seropositive than in seronegative individuals after both vaccination and asymptomatic infection (omicron variant). T cell responses are reported from only one of the four site cohorts where the vaccination schedule preceded the omicron wave. In seronegative individuals, Covishield{\texttrademark} elicited both CD4+ and CD8+ spike-specific cytokine-producing T cells whereas Covaxin{\textregistered} elicited mainly CD4+ spike-specific T cells. Neither vaccine showed significant post-vaccination expansion of spike-specific T cells in seropositive individuals.

}, doi = {10.1016/j.lansea.2024.100361.}, author = {Asokan, Mangaiarkarasi S. and Joan, Roshni Florina and Babji, Sudhir and Dayma, Girish and Nadukkandy, Prajitha and Subrahmanyam, Vinutha and Pandey, Archana and Malagi, Girish and Arya, Pooja and Mahajan, Vibhuti and Bhavikatti, Jayateerth and Pawar, Ketakee and Thorat, Aishwarya and Shah, Priyanki and Goud, Ramakrishna B. and Roy, Bishnudeo and Rajukutty, Shon and Immanuel, Sushil and Agarwal,Dhiraj and Saha, Sankhanil and Shivaraj, Akshatha and Panikulam, Patricia and Shome, Rajeshwari and Gulzar, Shah-E-Jahan and Sharma, Anusmrithi U. and Naik, Ajinkya and Talashi, Shruti and Belekar, Madhuri and Yadav, Ritu and Khude, Poornima and V, Mamatha and Shivalingaiah, Sudarshan and Deshmukh, Urmila and Bhise, Chinmayee and Joshi, Manjiri and Inbaraj, Leeberk Raja and Chandrasingh, Sindhulina and Ghose, Aurnab and Jamora, Colin and Karumbati, Anandi S. and Sundaramurthy, Varadharajan and Johnson, Avita and Ramesh, Naveen and Chetan, Nirutha and Parthiban, Chaitra and Ahmed, Asma and Rakshit, Srabanti and Adiga, Vasista and D{\textquoteright}souza, George and Rale, Vinay and George, Carolin Elizabeth and John, Jacob and Kawade, Anand and Chaturvedi, Akanksha and Raghunathan, Anu and Dias, Mary and Bhosale, Anand and Raghu, Padinjat and Shashidhara, L. S. and yakarnam, Annapurna V. and Bal, Vineeta and Kang, Gagandeep and Mayor, Satyajit} } @article {49280, title = {In silico discovery of a neutral 2π aromatic silicon aluminum compound}, journal = {Organometallics}, volume = {43}, year = {2024}, month = {JUL}, pages = {1583-1592}, type = {Article}, abstract = {

The recently developed ab initio nanoreactor (AINR) approach to identifying reaction intermediates and pathways without the necessity of experimental input has been employed in the current work to locate new cyclic silicon-based structures that have the potential to display aromaticity. Using this approach, we have identified many cyclic silicon-based molecules that have been experimentally reported over the past three decades. More importantly, the current work showcases an interesting new molecule that has been discovered through this approach: a four-membered cyclic compound of silicon and aluminum that displays significant 2 pi aromaticity and is capable of the activation of important small molecules such as ammonia.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.4c00151}, author = {Sharma, Himanshu and Vanka, Kumar} } @article {49461, title = {Integrated genomic and functional analysis of Streptomyces sp. UP1A-1 for bacterial wilt control and solanaceae yield increase}, journal = {Gene Reports}, volume = {37}, year = {2024}, month = {DEC}, type = {Article}, abstract = {

Ralstonia solanacearum\ is one of the most destructive soil-borne pathogen, causing bacterial wilt to the solanaceae vegetables.\ Streptomyces\ sp. UP1A-1 isolated from healthy solanaceae rhizosphere soil, exhibited the lowest disease incidence and increased fruit yield of solanaceae vegetables. However, the genomic and functional properties of UP1A-1 are unclear. Therefore, we conducted the present study to elucidate the genomic characteristics of UP1A-1 by whole genome sequencing. The results indicate that the genome of\ Streptomyces\ sp. UP1A-1 consists of 8,252,902\ bp and contains 72.42\ \%\ G\ +\ C. We identified the genes that confer plant growth promoting (PGP) function, which include those involved in siderophore production, indole-3-acetic acid biosynthesis, phosphate solubilization, nitrogen metabolism, and potassium metabolism. We also identified several other genes, such as chitinase, peroxidase, superoxide dismutase, catalase, proline biosynthesis, and glucose dehydrogenase, which are believed to be involved in the control of wilt disease. These genes revealed that the strain UP1A-1 has physiologically adapted to varied environmental conditions and could potentially control both abiotic and biotic stresses.

}, doi = {https://doi.org/10.1016/j.genrep.2024.102012}, author = {Kaari, Manigundan and Manikkam, Radhakrishnan and Joseph, Jerrine and Krishnan, Sakthivel and Annamalai, Kishore Kumar and Khan, Abujunaid and Rajput, Vinay and Dastager, Syed Gulam and Dharne, Mahesh S. and Umar, Md and Venugopal, Gopikrishnan and Alexander, Balamurugan} } @article {49017, title = {Iron-catalyzed (E)-selective hydrosilylation of alkynes: scope and mechanistic insights}, journal = {Catalysis Science and Technology}, volume = {14}, year = {2024}, month = {MAY}, type = {Article}, abstract = {

Iron-catalyzed hydrosilylation of internal alkynes has been rarely reported. Even in these rare cases, additives have been used for the success of the reaction, which often creates a problem for the functional group tolerance of the reaction. Herein, we report an additive-free iron-catalyzed (E)-selective hydrosilylation of internal alkynes in the presence of a phosphine ligand. A low-valent Fe(0) complex [Fe(CO)(3)(BDA)] {[Fe-1]} catalyzed the hydrosilylation of alkynes at 60 to 120 degrees C, exhibited a broad substrate (24 substrates) scope and tolerated different functional groups. The synthetic utility of the reaction was demonstrated by a gram scale experiment, preparing alkenes, and by chemo-selective hydrosilylation. The modus operandi of the reaction has been investigated by i) homogeneity test, ii) radical trapping experiments, iii) X-ray photoelectron spectroscopy, and iv) by preparing a Fe(II) complex as catalyst control. These mechanistic investigations revealed a two-electron pathway for the hydrosilylation of alkynes. In addition, kinetic investigations were undertaken to shed light on the rates of the reaction. Kinetic studies suggest the absence of an induction period, and the reaction is first order with respect to the concentration of iron catalyst [Fe-1] and zeroth order with respect to the substrate (alkyne). The Hammett plot suggests that strongly electron-withdrawing groups on the alkyne favour the hydrosilylation reaction. Meanwhile Eyring analysis suggests that the rate-determining step likely involves an associative pathway. Based on the findings of the mechanistic and kinetic investigation, a plausible Chalk-Harrod-type mechanism is likely to be operative. The proposed mechanism is substantiated by computational investigations, which suggested that the Chalk-Harrod mechanism is kinetically more favored by 15.8 kcal mol(-1) over the modified Chalk-Harrod mechanism.

}, issn = {2044-4753}, doi = {10.1039/d3cy01775c}, author = {Sen, Anirban and Tewari, Tanuja and Kumar, Rohit and Vinod, C. P. and Sharma, Himanshu and Vanka, Kumar and Chikkali, Samir H.} } @article {49050, title = {Kinetic model of hydrogenation of glucose to sorbitol on a Ni/Bentonite catalyst}, journal = {Industrial and Engineering Chemistry Research}, volume = {63}, year = {2024}, month = {MAR }, pages = {4771-4781}, type = {Article}, abstract = {

In the present work, we studied the hydrogenation of glucose to sorbitol using a nickel/bentonite catalyst. The Ni/bentonite catalyst was prepared by the wet impregnation method and characterized by different methods to understand the catalyst surface morphology, surface area, metal content, pore size, etc. Different reaction parameters such as temperature, hydrogen pressure, metal loading, catalyst loading, and agitation speed were studied to achieve a glucose conversion of 96.8\% and a sorbitol selectivity of 95.3\%. The reusability test was performed to examine the stability of the catalyst. The kinetic models such as the Eley-Rideal and Langmuir-Hinshelwood-Hougen-Watson models were used to study the hydrogenation of glucose and activation energy required for the reaction.

}, issn = {0888-5885}, doi = {10.1021/acs.iecr.3c03808}, author = {Pandya, Harmitkumar and Vinod, Chathakudath Prabhakaran and Rathod, Virendra and Kantam, Mannepalli Lakshmi} } @article {48938, title = {Lanthanide mimicking by magnesium for oxazolidinone synthesis}, journal = {Chemistry- a european journal}, volume = {30}, year = {2024}, month = {JAN }, type = {Article}, abstract = {

In the last decade, magnesium complexes have emerged as a viable alternative to transition-metal catalysts for the hydrofunctionalization of unsaturated bonds. However, their potential for advanced catalytic reactions has not been thoroughly investigated. To address this gap, we have developed a novel magnesium amide compound (3) using a PNP framework that is both bulky and flexible. Our research demonstrates that compound 3 can effectively catalyze the synthesis of biologically significant oxazolidinone derivatives. This synthesis involves a tandem reaction of hydroalkoxylation and cyclohydroamination of isocyanate using propargyl alcohol. Furthermore, we conducted comprehensive theoretical calculations to gain insights into the reaction mechanism. It is important to note that these types of transformations have not been reported for magnesium and would significantly enhance the catalytic portfolio of the 7th most abundant element. A monomeric magnesium compound was employed as a catalyst for the cascade cyclization of propargylic alcohol and isocyanate, resulting in the formation of pharmaceutically significant oxazolidinone derivatives. This transformation, previously attributed solely to transition metals or lanthanides, signifies a noteworthy advancement.image

}, keywords = {catalysis, Magnesium, oxazolidinone, pincer ligand, Sustainability}, issn = {0947-6539}, doi = {10.1002/chem.202303478}, author = {Kumar, Rohit and Mahata, Biplab and Gayathridevi, S. and Raj, K. Vipin and Vanka, Kumar and Sen, Sakya S.} } @article {49261, title = {Ligand isomerization driven electrocatalytic switching}, journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION}, volume = {63}, year = {2024}, month = {JUL}, type = {Journal Article}, keywords = {Catalysts, CO2 reduction, O-2 REDUCTION, oxygen reduction}, issn = {1433-7851}, doi = {10.1002/anie.202405664}, author = {Kottaichamy, Alagar Raja and Nazrulla, Mohammed Azeezulla and Parmar, Muskan and Thimmappa, Ravikumar and Devendrachari, Mruthyunjayachari Chattanahalli and Vinod, Chathakudath Prabhakaran and Volokh, Michael and Kotresh, Harish Makri Nimbegondi and Shalom, Menny and Thotiyl, Musthafa Ottakam} } @article {49313, title = {New insights into the composition and catalytic performance of VOx-Ga/γ-Al2O3 for the oxidative dehydrogenation of propane to propene}, journal = {New Journal of Chemistry}, volume = {48}, year = {2024}, month = {AUG }, pages = {15077-15087}, type = {Article}, abstract = {

Oxidative dehydrogenation (ODH) of propane is a promising alternative route for propene production. In this work, we developed a series of vanadium and gallium oxides supported on gamma-Al2O3 catalysts by an incipient wetness impregnation method. Among the employed catalysts, the VGA-2 showed superior catalytic activity, and the catalyst was demonstrated for longevity in ODH of propane with a stable activity using a continuous flow fixed bed reactor at 400 degrees C. H-2-TPR and UV-visible spectra showed the presence of highly dispersed monomeric VOx species with tetrahedral coordination geometry, which influences product selectivity. The characterization results also conferred that the redox nature of vanadium (V5+ and V4+) oxide and higher V5+ content on the surface of the VGA-2 catalysts are more favourable for C-H activation. In addition, the pyridine-FTIR and Ga-71 solid-state NMR studies further substantiated the presence of Lewis acid sites and tetrahedrally coordinated Ga3+Ox species that are highly responsible for the ODHP activity, respectively. Furthermore, in situ-DRIFTS studies conferred that the propane adsorption at ambient temperature showed the formation of intermediate propoxide species with the evolution of sigma-bonds and with further increase in the temperature to 325 degrees C; the stretching vibrations of the =C-H and -C-H bonds in the propylene molecule were observed. The spent catalysts were also analyzed by thermogravimetric analysis, where the optimized catalyst (VGA-2) showed the least coke deposition.

}, issn = {1144-0546}, doi = {10.1039/d3nj05109a}, author = {Kandasamy, Prabu and Gawali, Sheetal and Venugopalan, Aswathy Thareparambil and Manikandan, Marimuthu and Mekala, Siva Prasad and Shelke, Ankita and Ajithkumar, Thalasseril G. and Bhatte, Kushal and Raja, Thirumalaiswamy} } @article {49009, title = {Nickel-catalyzed tandem conversion of paraformaldehyde : methanol to hydrogen and formate/chemo- and stereoselective hydrogenation of alkynes under neutral conditions}, journal = {Catalysis Science and Technology }, volume = {14}, year = {2024}, month = {MAY}, pages = {2779-2793}, type = {Article}, abstract = {

The development of new catalytic protocols for clean and COx-free hydrogen generation from fundamental feedstocks is always interesting and challenging. Herein, we disclose nickel-catalyzed dihydrogen generation from a mixture of paraformaldehyde-methanol under base-free and activator-free conditions. The dihydrogen generation from this redox combination under neutral, oxidative coupling conditions has been integrated with the hydrogen transfer reactions such as chemo- and stereoselective hydrogenation of alkynes in a tandem manner. This unprecedented strategy provides diverse highly stereoselective olefins with excellent tolerance of reducible functional groups such as ether, silyl ether, aldehyde, keto, ester, nitrile, halides including bromo and iodo groups, and heteroarenes. Additionally, we demonstrated catalytic stereo-interconversion of alkenes under benign conditions. The affordable gram-scale synthesis of some important pharmaceutical bioactive molecules has further enhanced their synthetic value. A tandem dihydrogen generation from a mixture of paraformaldehyde-methanol under base-free conditions followed by semihydrogenation of alkynes is reported.

}, issn = {2044-4753}, doi = {10.1039/d3cy01699d}, author = {Subaramanian, Murugan and Padhy, Subarna Sukanya and Gouda, Chandrakanth and Das, Tamal and Vanka, Kumar and Balaraman, Ekambaram} } @article {49066, title = {Photocatalytic CO2 reduction to syngas using nickel phosphide-loaded CdS under visible light irradiation}, journal = {Journal of Physics-Energy}, volume = {6}, year = {2024}, month = {APR }, pages = {025019}, type = {Article}, abstract = {

Photocatalytic CO2 reduction is a sustainable pathway to produce syngas (H-2 + CO), which is a key feedstock for the production of several important liquid fuels on the industrial scale. However, achieving an appropriate tunable ratio of H-2:CO in syngas for commercial purposes is a challenging task. In this work, we present a low-cost and non-noble metal, phosphide-based co-catalyst-Ni2P-loaded cadmium sulfide (CdS) photocatalyst system, for photocatalytic CO2 reduction. As a co-catalyst, Ni2P fosters an efficient charge separation of photoexcited charges generated in the CdS production of syngas. In total, 3 wt.\% Ni2P/CdS exhibited exceptional performance of 50.6 mu mol g(-1) h(-1) in the CO evolution rate and 115 mu mol g(-1) h(-1) in the H-2 evolution rate, with a syngas composition varying from 2 to 4 in the H-2:CO ratio. Furthermore, first-principles density functional theory calculations were performed to study the surface energetics of the catalyst system and the results are found to be consistent with our experimental findings. Indeed, they establish that the composite favors CO2 photoreduction into syngas more efficiently than pure surfaces.

}, keywords = {CdS, CO2 reduction, Photocatalysis, Syngas, transition metal phosphides}, issn = {2515-7655}, doi = {10.1088/2515-7655/ad3676}, author = {Yadav, Poonam and Kumar, Santosh and Velankanni, Nandhakumar and Kuehne, Thomas D. and Gosavi, Suresh and Raghupathy, Ramya Kormath Madam and Bhosale, Reshma and Held, Georg and Shelke, Manjusha and Ogale, Satishchandra} } @article {49219, title = {Photocatalytic regeneration of reactive cofactors with inP quantum dots for the continuous chemical synthesis}, journal = {ACS Catalysis}, volume = {14}, year = {2024}, month = {APR}, pages = {6740-6748}, type = {Article}, abstract = {

The shuttling of redox-active nicotinamide cofactors between the light and dark cycles is the key to the continuous production of biomass in photosynthesis. The replication of such processes in artificial photosynthetic systems demands fast photoregeneration as well as simultaneous integration of these nicotinamide cofactors into the dark cycle. Here, we report the design of an artificial photosynthetic system for the continuous production of butanol via the constant photoregeneration and consumption of nicotinamide cofactors, powered by an indium phosphide quantum dot (InP QD) photocatalyst and alcohol dehydrogenase (ADH) enzyme, respectively. A strong electrostatic attraction between the oppositely charged InP QDs and electron mediators significantly enhanced the charge extraction and utilization processes, enabling a fast (similar to 30 min, with a turn over frequency of similar to 1333 h(-1)), quantitative (\>99\%), and selective photoregeneration of enzymatically active nicotinamide cofactors in the light cycle. These photoregenerated nicotinamide cofactors were further coupled in the dark cycle to trigger the ADH oxidoreductase enzyme for the production of butanol, via sequential as well as simultaneous light-dark cycles. The amount of butanol produced under simultaneous light-dark cycles was higher than the stoichiometric limit, proving the constant regeneration and consumption of nicotinamide cofactors in light and dark cycles, respectively. Thus, a proper design and integration of the InP QD-based photocatalytic cycle with the enzymatic cycle led to the effective electron shuttling between light and dark cycles, as seen in photosynthesis.

}, keywords = {artificial photosynthesis, biologicalcofactors, charge transfer, indiumphosphide, Photocatalysis, quantum dots}, issn = {2155-5435}, doi = {10.1021/acscatal.4c00817}, author = {Chakraborty, Indra Narayan and Jain, Vanshika and Roy, Pradyut and Kumar, Pawan and Vinod, Chathakudath P. and Pillai, Pramod P.} } @article {49101, title = {Polymer nanocomposites with UiO-derived zirconia fillers for energy generation and pressure-sensing devices: the role of crystal structure and surface characteristics}, journal = {ACS Applied Nano Materials}, volume = {7}, year = {2024}, month = {MAR }, pages = {5809-5818}, type = {Article}, abstract = {

Piezoelectric energy harvesting and pressure sensing using polymer nanocomposites have opened up promising avenues in the field of flexible electronics. Herein, the influence of varying crystal structures of zirconia nanoparticles on a piezoelectric energy-generating zirconia-poly(vinylidene difluoride) (PVDF) composite is investigated, and the fabrication of a security alert pavement unit using the material with an optimized composition is demonstrated. More specifically, two metal-organic frameworks, UiO-66 and UiO-67, were employed to synthesize four different types of zirconia nanoparticles with precise control of the monoclinic and tetragonal phases. Polymer nanocomposite with monoclinic zirconia nanoparticles derived from UiO-66 (ZrO2-66m) performed better than other derivatives with 61\% enhancement in the beta phase with respect to pure PVDF. It was hypothesized that the stable crystalline structure of the monoclinic phase might act as a better nucleating agent, and among monoclinic derivatives, ZrO2-66m was found to be more hydrophobic, probably enabling a better interaction with PVDF. Subsequently, a prototype device with a PVDF-ZrO2-66m (P/66m) film was made and tested for its energy generation. The maximum output voltage generated by the device under an irregular biomechanical hand tapping force of 8-9 N was 80 V, while the maximum open circuit current was found to be 65 mu A. The prototype displayed a power of 2162.24 mu W at a load resistance of 1 M Omega. A laboratory scale demonstration was executed with the prototype as an energy-generating and security alert pavement unit. A wireless, Bluetooth-based security alert system supported by an Android application was developed and demonstrated as a promising application with the fabricated prototype. The results and demonstrations validate that the PVDF-monoclinic ZrO2 nanoparticle nanocomposites will be an excellent value addition for flexible, durable energy generation and pressure-sensing applications.

}, keywords = {energy generation and pressure sensing, piezoelectric materials, PVDF/ZrO2 polymernanocomposite, self-powered devices, wearable electronics}, doi = {10.1021/acsanm.3c04730}, author = {Mukherjee, Gargi and Verma, Ankur and Madhu, Arjun Hari and Prasad, Bhagavatula L. V. and Karumuthil, Subash Cherumannil} } @article {49434, title = {Power generation with negative CO2 emissions through bio-electricity with CCS using dry co-gasification of coal-biomass blends}, journal = {Clean Technologies and Environmental Policy}, year = {2024}, month = {SEP}, type = {Article; Early Access}, abstract = {

Among the measures proposed for decarbonization of electricity generation, large reductions in CO2 emissions are possible by the adoption of bio-electricity with carbon dioxide capture and sequestration. In the present study, thermodynamic analysis of a thermal power plant that produces electricity through co-gasification of high-ash coal and Casuarina equisetifola (CE), a crop which grows along the Indian coastline, and which is not in competition with other agricultural crops for land and water use, is considered for integrated gasification combined cycle (IGCC) with CO2 capture via oxyfuel combustion and gasification technology. The integrated power plant layout includes the energy required for CO2 gasification of coal, biomass blended fuel, air separation to produce oxygen for oxyfuel combustion as well as for purification and compression of the flue gas up to 30 bar. Simulation results show that a net efficiency of 37\% can be achieved using high-ash Indian coal and CE blends up to 30\% of the latter. Synergetic effect of co-gasification components is observed in mass, molar and thermal energy flowrates for biomass blended fuel. With the help of CCS, CO2 emissions are reduced to 69.91 gCO(2)/kWh for 100\% coal-based IGCC-CC plant and further to -21.69 gCO(2)/kWh (negative CO2 emissions) for 30\% biomass blending, thus paving way for CO2-negative power generation.

}, keywords = {BECCS, Combustion, Dry co-gasification, IGCC-CC plant, Negative CO2 emissions, Oxyfuel, Thermodynamic analysis}, issn = {1618-954X}, doi = {10.1007/s10098-024-03001-y}, author = {Vasireddy, Satyam Naidu and Jayanti, Sreenivas} } @article {49429, title = {Rational monomer design for the synthesis of conjugated polymers by direct heteroarylation polymerization}, journal = {ACS Polymers Au}, volume = {4}, year = {2024}, month = {JUL}, pages = {449{\textendash}459}, type = {Article}, abstract = {

This study focuses on the design concepts that contribute to the C{\textendash}H activation in bithiophene-flanked monomers incorporating naphthalene diimide (NDI), perylene diimide (PDI), and fluorene (FLU) and their polymerization by direct heteroarylation. Density functional theory (DFT) calculations reveal distinct energy requirements for C{\textendash}H bond abstraction, which is dictated by the electron-withdrawing strength of the central aromatic core flanked by bithiophene. These provide insights into the reactivity of each monomer for C{\textendash}H bond activation. Proton NMR spectroscopic experimental results confirm the favorable energetic profiles predicted by DFT, with NDI- and PDI-flanked monomers exhibiting lower energy requirements than fluorene-flanked monomers. Successful polymer synthesis is demonstrated for NDI and PDI, while the fluorene-flanked monomer shows challenges due to its higher energy demands.

}, doi = {https://doi.org/10.1021/acspolymersau.4c00050}, author = {Kakde, Navnath R. and Sharma, Himanshu and Dalvi, Nitin V. and Vanka, Kumar and Asha, S. K} } @article {49270, title = {Reaction kinetics for catalytic hydrogenation of quinoline to decahydroquinoline as liquid organic hydrogen carrier}, journal = {International Journal of Hydrogen Energy}, volume = {92}, year = {2024}, month = {NOV}, pages = {102-112}, type = {Article}, abstract = {

The catalytic hydrogenation of quinoline to decahydroquinoline (DHQ) formation is studied for various parameters such as temperature, hydrogen pressure, reaction time, solvents, reactant-to-solvent ratio, and catalyst loading over 5\%Pd loaded on alumina (Pd/Al2O3) to obtain optimal reaction conditions. The hydrogen uptake of quinoline in the liquid phase reaction using isopropylalcohol (IPA) is studied in an autoclave reactor. The optimum reaction parameters of 50 bar H2 pressure and 175oC with reactant to solvent ratio of 1:9 for reaction time of 5 h are observed. The effect of IPA solvent showed that hydrogen uptake of 6.91 wt\% with complete hydrogenation of quinoline and DHQ yield of more than 99\% is observed. The reaction kinetic model is developed for a simplified reaction mechanism and is simulated using the Markov Chain Monte Carlo (MCMC) simulation tool to predict the rate constants and the experimental observations are validated with the model predictions. The activation energy for quinoline hydrogenation to py-THQ formation is estimated to be 136.57 kJ/mol. It is envisaged that quinoline hydrogenation to pz-THQ is the rate-limiting step in the DHQ formation.

}, keywords = {Decahydroquinoline (DHQ), Hydrogen uptake, Liquid organic hydrogen carrier (LOHC), Markov chain Monte Carlo (MCMC) simulation, Thermal screening unit (TSU), tool}, issn = {0360-3199}, doi = {10.1016/j.ijhydene.2024.10.247}, author = {Bagwan, Farahanaz M. and Kinage, Anil K. and Vasireddy, Satyam Naidu} } @article {49227, title = {Ready access to [5,6,5]-Trioxa-spiro and fused ketals via ag-catalyzed cascade annulation of 4-pentyn-1-ols and aldehydes}, journal = {Organic Letters}, volume = {26}, year = {2024}, month = {AUG}, pages = {7116-7121}, type = {Article}, abstract = {

In this study, we unveil the versatility of 4-pentyn-1-ols as carbonyl surrogates for the unprecedented synthesis of diverse oxygen heterocycles, including [5,6,5]-bis-spiroketals (trioxadispiroketals) and [5,6,5]-furano-spiroketals related to bioactive natural products. These reactions commence with the pi-activation-induced intramolecular hydroalkoxylation of 4-pentyn-1-ols, yielding cyclic enol ethers, which undergo subsequent three-component annulation with aldehydes in a [2+2+1+1] fashion, resulting in the formation of [5,6,5]-bis-spiroketals. Notably, the distinctive steric features of alkynyl alcohols, particularly those with a secondary or tertiary alcohol functionality, dictate divergent reaction pathways, leading to the formation of [5,6,5]-furano-spiroketals.

}, issn = {1523-7060}, doi = {10.1021/acs.orglett.4c02357}, author = {Vinodkumar, Ramavath and Nakate, Ashwini K. and Gamidi, Rama Krishna and Kontham, Ravindar} } @article {49364, title = {Relaxation of the 2a1 ionized water dimer: an interplay of intermolecular Coulombic decay (ICD) and proton transfer processes}, journal = {Journal of Chemical Physics}, volume = {160}, year = {2024}, month = {JUN }, pages = {214302}, type = {Article}, abstract = {

This article investigates the relaxation dynamics of the ionized 2a(1) state of a water molecule within a water dimer. The study was motivated by findings from two previous pieces of research that focused on the relaxation behaviors of the inner-valence ionized water dimer. The present study discloses an observation indicating that water dimers display specific fragmentation patterns following inner-valence ionization, depending on the position of the vacancy. Vacancies were created in the 2a(1) state of the proton-donating water molecule (PDWM) and proton-accepting water molecule (PAWM). Utilizing Born-Oppenheimer molecular dynamics simulations, the propagation of the 2a(1) ionized state was carried out for both scenarios. The results revealed proton transfer occurred when the vacancy resided in the PDWM, accompanied by the closing of decay channels for O-H bond distance (RO-H) \> 1.187 \& Aring; (matching Richter et al.{\textquoteright}s findings). Conversely, when vacancy was on PAWM, we observed no closing of decay channels (aligning with Jahnke et al.{\textquoteright}s findings). This difference translates to distinct fragmentation pathways. In PDWM cases, 2a(1) state ionization leads to H3O+ -OH center dot formation. In contrast, PAWM vacancies result in decay pathways leading to H2O+-H(2)O(+ )products.

}, issn = {0021-9606}, doi = {10.1063/5.0199888}, author = {Kumar, Ravi and Ghosh, Aryya and Vaval, Nayana} } @article {49192, title = {Resorcinol-Azodianiline Covalent Organic Framework Supported FeOOH Quantum Dot-Catalyzed Electrochemical Ammonia Synthesis under Ambient Conditions}, journal = {CHEMISTRY OF MATERIALS}, volume = {36}, year = {2024}, month = {AUG}, pages = {8229-8238}, type = {Journal Article}, keywords = {conversion, nitrogen, Recent Progress, reduction}, issn = {0897-4756}, doi = {10.1021/acs.chemmater.4c00859}, author = {Shekhar, Pragalbh and Kosugi, Kento and Singh, Himan Dev and Kushwaha, Rinku and Rase, Deepak and Matsuzaki, Takumi and Jain, Chitvan and Singh, Piyush and Singh, Yashraj and Vinod, Chathakudath Prabhakaran and Kondo, Mio and Masaoka, Shigeyuki and Vaidhyanathan, Ramanathan} } @article {49044, title = {Role of aromatic alcohol additives on asymmetric organocatalysis reactions: insights from theory}, journal = {Chemistry-an asian jounrnal}, volume = {19}, year = {2024}, month = {FEB }, type = {Article}, abstract = {

The presence of an aromatic additive has been seen to enhance, often significantly, the enantioselectivity and yield in asymmetric organocatalysis. Considering their success across a dizzying range of organocatalysts and organic transformations, it would seem unlikely that a common principle exists for their functioning. However, the current investigations with DFT suggest a general principle: the phenolic additive sandwiches itself, through hydrogen bonding and pi \& sdot;\& sdot;\& sdot;pi stacking, between the organocatalyst coordinated electrophile and nucleophile. This is seen for a wide range of experimentally reported systems. That such complex formation leads to enhanced stereoselectivity is then demonstrated for two cases: the cinchona alkaloid complex (BzCPD), catalysing thiocyanation (2-naphthol additive employed), as well as for L-pipecolicacid catalysing the asymmetric nitroaldol reaction with a range of nitro-substituted phenol additives. These findings, indicating that dual catalysis takes place when phenolic additives are employed, are likely to have a significant impact on the field of asymmetric organocatalysis. The current DFT based study, on a wide range of organocatalysis systems, reveals a general principle by which phenolic additives influence asymmetric organocatalysis reactions. It is shown that the phenolic additive forms a sandwich complex, through hydrogen bonding and pi \& sdot;\& sdot;\& sdot;pi stacking interactions, with the organocatalyst coordinated electrophile and nucleophile, and enhances the enantioselectivity of the system as a result. image

}, keywords = {Additive, Asymmetric Organocatalysis, Cinchona Alkaloid, Density functional theory, Enantioselective Thiocyanation}, issn = {1861-4728}, doi = {10.1002/asia.202300997}, author = {Banerjee, Subhrashis and Vanka, Kumar} } @article {49089, title = {Size matters: computational insights into the crowning of noble gas trioxides}, journal = {Inorganic Chemistry}, volume = {63}, year = {2024}, month = {FEB}, pages = {4099-4107}, type = {Article}, abstract = {

In pursuit of enhancing the stability of the highly explosive and shock-sensitive compound XeO3, we performed quantum chemical calculations to investigate its possible complexation with electron-rich crown ethers, including 9-crown-3, 12-crown-4, 15-crown-5, 18-crown-6, and 21-crown-7, as well as their thio analogues. Furthermore, we expanded our study to other noble gas trioxides (NgO(3)), namely, KrO3 and ArO3. The basis set superposition error (BSSE) corrected interaction energies for these adducts range from -13.0 kcal/mol to -48.2 kcal/mol, which is notably high for sigma-hole-mediated noncovalent interactions. The formation of these adducts was observed to be more favorable with the increase in the ring size of the crowns and less favorable while going from XeO3 to ArO3. A comprehensive analysis by various computational tools such as the mapping of the electrostatic potential (ESP), Wiberg bond indices (WBIs), Bader{\textquoteright}s theory of atoms-in-molecules (AIM), natural bond orbital (NBO) analysis, noncovalent interaction (NCI) plots, and energy decomposition analysis (EDA) revealed that the C-H center dot center dot center dot O interactions, as well as dispersion interactions, play a pivotal role in stabilizing adducts involving larger crowns. A noteworthy outcome of our study is the revelation of a coordination number of 9 for xenon in the complex formed between XeO3 and the thio analogue of 18-crown-6, which is higher than the largest number reported to date.

}, issn = {0020-1669}, doi = {10.1021/acs.inorgchem.3c03782}, author = {Dash, Soumya Ranjan and Sharma, Himanshu and Tiwari, Mrityunjay K. and Greb, Lutz and Vanka, Kumar} } @article {48944, title = {Solid state hydrogen storage: Decoding the path through machine learning}, journal = {International Journal of Hydrogen Energy }, volume = {50}, year = {2024}, month = {JAN}, pages = {1518-1528}, type = {Article}, abstract = {

We present a machine learning (ML) framework HEART (HydrogEn storAge propeRty predicTor) for identifying suitable families of metal alloys for hydrogen storage under ambient conditions. Our framework includes two ML models that predict the hydrogen storage capacity (HYST) and the enthalpy of hydride formation (THOR) of multi-component metal alloys. We demonstrate that a chemically diverse set of features effectively describes the hydrogen storage properties of the alloys. In HYST, we use absorption temperature as a feature which improved H2wt\% prediction significantly. For out-of-the-bag samples, HYST predicted H2wt\% with R2 score of 0.81 and mean absolute error (MAE) of 0.45 wt\% whereas R2 score is 0.89 and MAE is 4.53 kJ/molH2 for THOR. These models are further employed to predict H2wt\% and Delta H for similar to 6.4 million multi-component metal alloys. We have identified 6480 compositions with superior storage properties (H2wt\% \> 2.5 at room temperature and Delta H \< 60 kJ/molH2). We have also discussed in detail the interesting trends picked up by these models like temperature dependent variation in the rate of hydrogenation and alloying effect on H2wt\% and Delta H in different families of alloys. Importantly certain elements like Al, Si, Sc, Cr, and Mn when mixed in small fractions with hydriding elements like Mg, Ti, V etc. systematically reduce Delta H without significantly compromising the storage capacity. Further upon increasing the number of elements in the alloy i.e from binary to ternary to quaternary, the number of compositions with lower enthalpies also increases. From the 6.4 million compositions, we have reported new alloy families having potential for hydrogen storage at room temperature. Finally, we demonstrate that HEART has the potential to scan vast chemical spaces by narrowing down potential materials for hydrogen storage.

}, keywords = {Enthalpy of hydride formation, Hydrogen storage capacity, Metal hydrides, Predictive machine learning models, Solid-state hydrogen storage}, issn = {0360-3199}, doi = {10.1016/j.ijhydene.2023.10.056}, author = {Verma, Ashwini and Wilson, Nikhil and Joshi, Kavita} } @article {49246, title = {Switchable molecular electrocatalysis}, journal = {CHEMICAL SCIENCE}, volume = {15}, year = {2024}, month = {AUG }, pages = {13262-13270}, type = {Journal Article}, keywords = {CO2 reduction, COBALT PHTHALOCYANINE, NANOPOROUS GOLD, oxygen reduction}, issn = {2041-6520}, doi = {10.1039/d4sc01284d}, author = {Dutt, Shifali and Kottaichamy, Alagar Raja and Dargily, Neethu Christudas and Mukhopadhyay, Sanchayita and Nayak, Bhojkumar and Devendrachari, Mruthyunjayachari Chattanhali and Vinod, Chatakudhath Prabakaran and Kotresh, Harish Makri Nimbegondi and Thotiyl, Musthafa Ottakam} } @article {49334, title = {Synergistic effects of the substrate-ligand interaction in metal-organic complexes on the de-electronation kinetics of a vitamin C fuel cell}, journal = {Dalton Transactions}, volume = {53}, year = {2024}, month = {AUG }, pages = {13384-13393}, type = {Article}, abstract = {

The rising demand for portable energy conversion devices has spurred the advancement of direct liquid fuel cells (DLFCs) employing fuels such as alcohol, ammonia, hydrazine, and vitamin C. In these devices, various precious metal platforms have been explored to increase the de-electronation kinetics and reduce catalyst poisoning, but with substantial cost implications. We demonstrate the crucial role of ligands in non-precious organometallic complexes in influencing the de-electronation kinetics of fuel molecules through a unique substrate-ligand synergistic interaction. This unique chemistry imparts electron deficiency at the catalytic metal center while simultaneously populating the ligand with an extensive proton charge assembly. This distinct substrate-ligand interaction enhances the DLFC performance by coulombically dragging the substrate with a distinct amplification in its de-electronation kinetics. By integrating this approach with a ferricyanide/ferrocyanide half-cell reaction, a precious metal-free vitamin C fuel cell is developed, which is capable of generating an open circuit voltage of similar to 950 mV, a peak power density of similar to 97 mW cm-2 at a peak current density of similar to 215 mA cm-2 with the performance metrics nearly 1.7 times higher than a precious metal based DLFC. This highlights the potential of the substrate-ligand synergy in the design of efficient molecular catalysts for energy conversion applications. A precious metal-free biomass fuel cell through substrate-ligand interactions.

}, issn = {1477-9226}, doi = {10.1039/d4dt01370k}, author = {Parmar, Muskan and Mukhopadhyay, Sanchayita and Mondal, Ritwik and Nayak, Bhojkumar and Dargily, Neethu Christudas and Kotresh, Harish Makri Nimbegondi and Vinod, Chathakudath Prabhakaran and Ottakam Thotiyl, Musthafa} } @article {49207, title = {Synergistic humidity-responsive mechanical motion and proton conductivity in a cationic covalent organic framework}, journal = {CHEM}, volume = {10}, year = {2024}, month = {AUG }, type = {Journal Article}, keywords = {ACTUATORS, Crystalline, DRIVEN, SOFT}, issn = {2451-9294}, doi = {10.1016/j.chempr.2024.04.018}, author = {Das, Gobinda and Shinde, Dhanraj B. and Melapurakkal, Amrutha and Shelke, V, Manjusha and Garai, Bikash and Bazin, Philippe and Blal, Abdelhafid Ait and Benyettou, Farah and Prakasam, Thirumurugan and Halim, Rasha Abdul and Ibrahim, Fayrouzabou and Sharma, Sudhir Kumar and Varghese, Sabu and Weston, James and Jagannathan, Ramesh and Addicoat, Matthew A. and Gandara, Felipe and Olson, Mark A. and El-Roz, Mohamad and Trabolsi, Ali} } @article {49378, title = {Synthesized novel chromogenic reagent and sensor: detection and identification of dichlorvos}, journal = {Heliyon}, volume = {10}, year = {2024}, month = {MAY}, pages = {e31217}, type = {Article}, abstract = {

We developed a novel chromogenic reagent and sensor by selective approach, for the detection and identification of dichlorvos, which we tested with the thin layer chromatography method. For the first time, we reported in situ-generated glyoxal as a hydrolysis product, which then interacts with isoniazid to produce a yellow-colored cyclic compound. We used well-known spectroscopic techniques to confirm the chemical identity of the final product. We initially investigated the reaction using a variety of approaches, followed by attempts to establish the reaction mechanism using Density Functional Theory by Gaussian software.

}, keywords = {DFT analysis, Dichlorvos, Gloyxal, Hydrazone, Isoniazid}, doi = {10.1016/j.heliyon.2024.e31217}, author = {Gedam, Ashwin D. and Katiya, Manish M. and Dhonde, Madhukar G. and Ganorkar, Kapil S. and Thakare, Vijay J. and Mandlik, Prashant R. and Jadhao, Nitin L. and Gajbhiye, Jayant M. and Kumar, Ravi and Vaval, Nayana} } @article {49318, title = {Tailoring helical ends of π-extended [6]heterohelicenes to control optical, and electrochemical features}, journal = {Chemical Communications}, volume = {60}, year = {2024}, month = {OCT }, pages = {11944-11947}, type = {Article}, abstract = {

The inherent helical chirality and improved pi-stacking capabilities endow helicenes with fascinating photophysical characteristics when decorated with lateral pi-extensions. Here, we report the synthesis and physicochemical characterization of expanded hetero[6]helicenes fused with thiadiazole and selenadiazole rings at the helical ends. Comparing these heterohelicenes revealed the impact of the heteroatom-embedded aromatic rings on the excited state and redox features. A small structural variation of the terminal rings from thiadiazole to selenadiazole caused a striking change in the heterohelical nanographenes. The inherent helical chirality and improved pi-stacking capabilities endow helicenes with fascinating photophysical characteristics when decorated with heteroatoms.

}, issn = {1359-7345}, doi = {10.1039/d4cc03707c}, author = {Kumar, Viksit and Dongre, Sangram D. and Venugopal, Geethu and Narayanan, Aswini and Babu, Sukumaran Santhosh} } @article {49186, title = {Taming XeO3 with aza-crowns: computational studies into σ-hole mediated host-guest interactions}, journal = {ChemPhysChem}, volume = {25}, year = {2024}, month = {SEP}, pages = {e202400302}, type = {Article}, abstract = {

Various aza-crowns with different sizes and substituents have been explored computationally as potential hosts for stabilizing the explosive guest xenon trioxide (XeO3) through sigma-hole-mediated aerogen bonding interactions. Interestingly, aza-crowns demonstrate superior binding towards XeO3 compared to their oxygen and thio counterparts. However, unlike the latter cases, where the binding was found to be increasingly favorable with the increase in the size of the crowns, aza-crowns exhibit a variable size preference for XeO3, peaking with aza-15-crown-5, and reducing thereafter with increase in crown size.

}, keywords = {aza-crowns, host-guest systems, noncovalent interactions, sigma (sigma) hole, Xenon}, issn = {1439-4235}, doi = {10.1002/cphc.202400302}, author = {Dash, Soumya Ranjan and Vanka, Kumar} } @article {49388, title = {Temperature-controlled hydrothermal synthesis of α-MnO2 nanorods for catalytic oxidation of cyclohexanone}, journal = {CHEMPLUSCHEM}, volume = {89}, year = {2024}, month = {JUL}, type = {Journal Article}, keywords = {Adipic Acid, conversion, MANGANESE OXIDES}, issn = {2192-6506}, doi = {10.1002/cplu.202300589}, author = {Jha, Ratnesh Kumar and Manikandan, Marimuthu and Prabu, Marimuthu and Vineeth, Nidhi R. and Dharmalingam, Praveen and Archana, Ramakrishnan and Harsha, Murudappa and Shankar, Sonu Ram and Bhatte, Kushal and Raja, Thirumalaiswamy} } @article {49356, title = {Temperature-programmed reduction method for stabilization of the inorganic framework of SAPO-37 materials: promising catalysts for MTBE production}, journal = {Chemical Communications}, volume = {60}, year = {2024}, month = {AUG}, type = {Article}, abstract = {

A temperature-programmed reduction method was developed to stabilize SAPO-37 and molybdenum-(oxy)-carbide-loaded SAPO-37 (SAP-37MoCR). The inorganic framework (Faujasite type SAPO-37) was retained for the first time even after treatment at 550 degrees C and was confirmed through powder XRD and SEM analysis. SAP-37MoCR exhibits strong acidic sites and is a promising catalyst for MTBE synthesis. Furthermore, the catalyst is stable and recyclable. Temperature-programmed reduction (TPR) is a new method of stabilising inorganic framework materials, viz., SAPO-37-type zeolite. The template could be converted into intermediate carbide species with metal ions.

}, issn = {1359-7345}, doi = {10.1039/d4cc01839g}, author = {Shabana, K. Khadheejath and Narendranath, Soumya B. and Nimisha, N. P. and Venkatesha, N. J. and Sheetal, G. and Sakthivel, A.} } @article {49390, title = {Template-asisted visible light-induced [2+2] photodimerization in a pseudopolymorphic binary solid: topotactic transformation vs photoinduced crystal melting}, journal = {CRYSTAL GROWTH \& DESIGN}, volume = {24}, year = {2024}, month = {MAY }, pages = {5193-5199}, type = {Journal Article}, keywords = {CATION-PI INTERACTIONS, SINGLE-CRYSTAL, STATE PHOTODIMERIZATION, Supramolecular}, issn = {1528-7483}, doi = {10.1021/acs.cgd.4c00426}, author = {Ahsan, Mollah Rohan and Varma, Harshit and Mishra, Manish Kumar and Mukherjee, Arijit} } @article {49213, title = {Trapping an elusive Fe(IV)-superoxo intermediate inside a self-assembled nanocage in water at room temperature}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, volume = {146}, year = {2024}, month = {JUL }, pages = {21729-21741}, type = {Journal Article}, keywords = {CATALYTIC EPOXIDATION, DIOXYGEN ACTIVATION, NONHEME IRON, X-RAY-ABSORPTION}, issn = {0002-7863}, doi = {10.1021/jacs.4c05849}, author = {Gera, Rahul and De, Puja and Singh, Kundan K. and Jannuzzi, Sergio A. V. and Mohanty, Aisworika and Velasco, Lucia and Kumar, Pankaj and Marco, J. F. and Nagarajan, Kalaivanan and Pecharroman, Carlos and Rodriguez-Pascual, P. M. and DeBBeer, Serena and Moonshiram, Dooshaye and Gupta, Sayam Sen and Dasgupta, Jyotishman} } @article {49283, title = {Triazatruxene amine donor-based visible-light-responsive unsymmetrical squaraine dyes for dye-sensitized solar cells}, journal = {ACS Applied Energy Materials}, volume = {7}, year = {2024}, month = {SEP}, pages = {7982-7991}, type = {Article}, abstract = {

Optimized charge-transfer dynamics at the dye-TiO2/electrolyte interface are required for an enhanced dye-sensitized solar cell (DSSC) device performance. Such an optimized interface enhances the charge-injection, dye-regeneration, and diminished charge-recombination processes, synergistically enhancing the device efficiency. In this study, octupolar-structured sensitizers are designed to improve the interaction between the dye and the redox electrolyte for increasing the dye-regeneration process upon photoexcitation. Accordingly, a set of unsymmetrical squaraine dyes with indoline and triazatruxene amine donor-based D-A-D dyes are designed (KV1-KV3), synthesized, and sensitized with a semiconducting metal oxide (TiO2) film. The sensitizer forms a monolayer on the TiO2 surface, leading to a dye-dye interaction, which broadens the absorption spectrum. The N atom of the triazatruxene amine donor was left unsubstituted in KV1, whereas a hexyl chain was installed in KV2 and KV3 and a branched alkyl chain was installed on the core N atoms in KV3 to control the self-assembly of dyes on the TiO2 surface. Self-assembly of alkyl groups wrapped in KV1-KV3 dyes on the TiO2 surface aids surface passivation and broadens the absorption profile, improving the light-harvesting capabilities. The DSSC devices based on KV2 exhibited a high power conversion efficiency of 7.85\% (V-oc = 794 mV, J(sc) = 14.76 mA/cm(2), and FF = 67\%), with an onset incident photon-to-current conversion efficiency response from 680 nm.

}, keywords = {aggregationof dyes, Dye-sensitized solar cells, metal-free organic dyes, self-assembly of dye, squaraine dyes, triazatruxene}, issn = {2574-0962}, doi = {10.1021/acsaem.4c01591}, author = {Ingole, Kiran Balaso and Deshmukh, Shivdeep Suresh and Verma, Tushar Singh and Krishnamurty, Sailaja and Krishnamoorthy, Kothandam and Nithyanandhan, Jayaraj} } @article {49027, title = {Tridentate NacNac tames T-shaped nickel(I) radical}, journal = {Chemistry- a european journal}, volume = {30}, year = {2024}, month = {FEB}, type = {Article}, abstract = {

The reaction of a nickel(II) chloride complex containing a tridentate beta-diketiminato ligand with a picolyl group [2,6-iPr2-C6H3NC(Me)CHC(Me)NH(CH2py)]Ni(II)Cl (1)] with KSi(SiMe3)3 conveniently afforded a nickel(I) radical with a T-shaped geometry (2). The compound{\textquoteright}s metalloradical nature was confirmed through electron paramagnetic resonance (EPR) studies and its reaction with TEMPO, resulting in the formation of a highly unusual three-membered nickeloxaziridine complex (3). When reacted with disulfide and diselenide, the S-S and Se-Se bonds were cleaved, and a coupled product was formed through carbon atom of the pyridine-imine group. The nickel(I) radical activates dihydrogen at room temperature and atmospheric pressure to give the monomeric nickel hydride. A thermally stable, T-shaped, nickel(I) radical was straightforward obtained by reduction of a tridentate nacnac nickel(II) chloride with KSi(TMS)3. The metalloradical character of the compound was demonstrated by the formation of a highly unusual nickeloxaziridine complex upon addition of TEMPO. The Ni(I) species displays a rich chemistry towards activation S-S, and Se-Se bond leading to unusual C-C coupled product as well as dihydrogen activation at room temperature and atmospheric pressure to generate monomeric nickel hydride.+image

}, keywords = {C-C Bond formation, Hydrogen Activation, Metalloradical, Nickel, Tridentate nacnac}, issn = {0947-6539}, doi = {10.1002/chem.202303957}, author = {Pahar, Sanjukta and Sharma, Vishal and Raj, K. Vipin and Sangole, Mayur P. and George, Christy P. and Singh, Kirandeep and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {49392, title = {{\textquoteleft}Turning on{\textquoteright} to glutathione: a rhodamine-based fluorescent chemodosimeter with nanomolar sensitivity}, journal = {ChemistrySelect}, volume = {9}, year = {2024}, month = {OCT}, pages = {e202402943}, type = {Article}, abstract = {

A new colorimetric and fluorescence turn-on chemodosimeter for selective detection of GSH over Cys and Hcy with 34-fold enhancement in emission intensity is reported. Probe 1 exhibited ultra-sensitivity toward GSH with 0.125 nM detection limit and successfully displayed GSH detection in MCF-7 live cells. The mechanism of sensing is established by density functional theoretical calculations.

}, keywords = {Chemodosimeter, Fluorescence turn-on, GSH, MCF-7 cells, Rhodamine}, issn = {2365-6549}, doi = {10.1002/slct.202402943}, author = {Badekar, Pooja S. and Deo, Harshada S. and Varma, Mokshada E. and Kulkarni, Prasad P. and Maibam, Ashakiran and Krishnamurty, Sailaja and Kumbhar, Anupa A.} } @article {49279, title = {Uncovering diverse reactivity of NHCs withdiazoalkane: C-H activation, C=C bond formation,and access to N-heterocyclic methylenehydrazine}, journal = {Chemical Science}, volume = {15}, year = {2024}, month = {NOV}, pages = {18387-18394}, type = {Article}, abstract = {

N-heterocyclic carbenes (NHCs) have attracted significant attention due to their strong sigma-donating capabilities, as well as their transition-metal-like reactivity towards small molecules. However, their interaction with diazoalkanes remains understudied. In this manuscript, we explore the reactivity of a series of stable carbenes, encompassing a wide range of electronic properties, with Me3SiCHN2. 5-SIPr activates the C-H bond of Me3SiCHN2, resulting in the formation of a novel diazo derivative (1), while carbenes such as 5-IPr, 6-SIPr, and diamido carbene yield N-heterocyclic methylenehydrazine derivatives (3, 4, and 8). The reaction of Me3SiCHN2 with 5-ItBu unexpectedly leads to the formation of a triazole ring linked with the imidazole moiety via a CC double bond (6) alongside the azine product (7). Substituting the diazoalkane with diazoester consistently yields azine derivatives (9-12 and 14). Only in the case of 5-ItBu, an imidazolium salt with tetrazenide anion (13) was obtained as a side product. The reaction of 4 with HCl resulted in the desilylprotonation to form a salt, 5a, which undergoes deprotonation upon using bases such as Et3N and KHMDS to form N-heterocyclic methylene hydrazine, 5. Theoretical calculations have been conducted to elucidate the diverse mechanisms underlying product formation.

}, issn = {2041-6520}, doi = {10.1039/d4sc05740f}, author = {Balayan, Kajal and Sharma, Himanshu and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {49265, title = {Unprecedented C-F bond cleavage in perfluoronaphthalene during cobaltocene reduction}, journal = {DALTON TRANSACTIONS}, volume = {53}, year = {2024}, month = {NOV }, pages = {17789-17793}, type = {Journal Article}, issn = {1477-9226}, doi = {10.1039/d4dt02791d}, author = {Kundu, Gargi and Pramanik, Debjit and Dash, Soumya Ranjan and Kumar, Ravi and Sangole, Mayur and Tothadi, Srinu and Ghosh, Aryya and Vanka, Kumar and Singh, Kirandeep and Sen, Sakya S.} } @article {49059, title = {Unraveling the cooperative mechanisms in ultralow copper-loaded WC@NGC for enhanced CO2 electroreduction to acetic acid}, journal = {Chemistry of Materials }, volume = {36}, year = {2024}, month = {MAR }, pages = {3464-3476}, type = {Article}, abstract = {

Electrochemical CO2 reduction reaction (eCO(2)RR) has been explored on tungsten carbide (WC) nanoparticles embedded on N-doped graphitic carbon (NGC), demonstrating excellent activity toward the formation of acetic acid at an extremely lower potential. The activity has been further enhanced by loading ultralow copper sites into the catalyst system, exhibiting 80.02\% Faradaic efficiency (FE) toward acetic acid at an applied potential of -0.3 V (vs RHE). Potential-dependent in situ infrared (IR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, ex situ extended X-ray absorption fine structure (EXAFS) studies, and computational analysis confirm that synergy between uniformly dispersed Cu atoms and WC lattice plays a crucial role in the formation of acetic acid with high FE at a lower potential. It has been observed that the W atom of WC strongly chemisorbs CO2 with a significant change in the C-O bond length and the O-C-O bond angle, in contrast to weaker adsorption on Cu-based catalyst surfaces. The presence of a Cu site enhances the adsorption of CO2, thereby increasing the possibility of C-C coupling kinetically. Most importantly, hydrogen evolution predominates on the catalyst{\textquoteright}s surface at higher applied potentials (-0.5 to -1.1 V vs RHE), elucidating the mechanism underlying enhanced charge transfer between copper and WC, a phenomenon ascertained through in situ IR spectroscopy and ex situ XPS analysis

}, issn = {0897-4756}, doi = {10.1021/acs.chemmater.4c00405}, author = {Bagchi, Debabrata and Riyaz, Mohd and Raj, Jithu and Roy, Soumyabrata and Singh, Ashutosh Kumar and Cherevotan, Arjun and Vinod, Chathakudath P. and Peter, Sebastian C.} } @article {49347, title = {Unravelling polymorphism-driven luminescence in GFP chromophore analogues: insights into the phase transition and morphology-dependent optical waveguide properties}, journal = {Journal of Materials Chemistry C}, volume = {12}, year = {2024}, month = {JUN }, pages = {8368-8379}, type = {Article}, abstract = {

The advent of multi-emission organic solid-state materials in response to external stimuli has sparked the scientific community due to their potential application in developing sophisticated optoelectronic sensors and bioanalytical tools. This article presents green fluorescent protein chromophore (GFPc) analogue-based polymorphs exhibiting significantly different emissions due to various noncovalent interactions in the supramolecular environment and conformational alterations in the crystalline state. In both compounds (A and B), the polymorphs undergo monotropic thermal phase transitions that are characterized by DSC, HSM, and VT-PXRD techniques. The distinct fluorescent emission characteristics of these polymorphs demonstrated morphology-related optical waveguiding features. Specifically, the plate-type Form A1 emitted light with a 2D blue hue, while the needle-type Form A2 emitted light with a yellowish-green colour. Additionally, the impressive waveguiding capabilities of Form B1 were explored in both straight and singly/doubly bending configurations to facilitate fluorescence propagation. Consequently, there is significant interest in developing organic materials based on GFP chromophores, which exhibit low emission in solution but display multi-fluorescent emission in the solid state. These materials are promising for applications such as optoelectronic devices, security tags, live cell imaging, and fluorescent inks. Polymorphs of GFPc analogs A and B display differences in their optical waveguiding properties in 1D and 2D depending on the crystal shapes. Furthermore, Form B1 demonstrates efficient optical waveguiding capabilities even when the crystal is bent.

}, issn = {2050-7526}, doi = {10.1039/d3tc04676a}, author = {Dabke, Niteen B. and Raut, Yash and Mali, Bhupendra P. and Pandya, Rinu and Vanka, Kumar and Manoj, Kochunnoonny and Gonnade, Rajesh G.} } @article {49381, title = {Unravelling the prebiotic origins of the simplest α-ketoacids in cometary ices: a computational investigation}, journal = {CHEMICAL COMMUNICATIONS}, volume = {60}, year = {2024}, month = {OCT }, pages = {11283-11286}, type = {Journal Article}, keywords = {GLYOXYLATE, Hydrocarbons, Metabolism, Precursors}, issn = {1359-7345}, doi = {10.1039/d4cc03074e}, author = {Dash, Soumya Ranjan and Pandya, Rinu and Singh, Geetika and Sharma, Himanshu and Das, Tamal and Haldar, Hritwik and Hotha, Srinivas and Vanka, Kumar} } @article {49118, title = {Unveiling the cell wall-targeting mechanisms and multifaceted virulence modulation by a eugenol glycoconjugate against aspergillus fumigatus: insights from in vitro and in ovo studies}, journal = {Journal of Applied Macrobiology }, volume = {135}, year = {2024}, month = {JAN }, type = {Article}, abstract = {

Aim The primary objective of this study was to elucidate the putative cell wall-associated targets of compound 6i, a glycoconjugate of eugenol, in Aspergillus fumigatus, while also evaluating its toxicity and assessing histopathologic alterations in the liver, heart, and kidney of compound 6i-treated embryos using an in ovo model.Method To achieve this aim, compound 6i was synthesized, and a series of biochemical assays were performed to determine its impact on the fungal cell wall. Additionally, quantitative real time-PCR and liquid chromatography-mass spectrometry/mass spectrometry analyses were conducted to investigate changes in gene and protein expression profiles associated with melanin biosynthesis, conidiation, siderophore production, transcriptional regulation of beta-glucan biosynthesis, and calcineurin activity in A. fumigatus.Results The experimental findings revealed that compound 6i exhibited notable antifungal activity against A. fumigatus by perturbing cell wall integrity, hindering ergosterol, glucan, and chitin biosynthesis, and inhibiting catalase production. Moreover, relative gene expression and proteomic analyses demonstrated that compound 6i exerted both downregulatory and upregulatory effects on several crucial genes and proteins involved in the aforementioned fungal processes. Furthermore, increased expression of oxidative stress-related proteins was observed in the presence of compound 6i. Notably, the glycoconjugate of eugenol did not elicit cytotoxicity in the liver, heart, and kidney of chick embryos.Conclusion The current investigation elucidated the multifaceted mechanisms by which compound 6i exerts its antifungal effects against A. fumigatus, primarily through targeting cell wall components and signaling pathways. These findings underscore the potential of the eugenol glycoconjugate as a promising antifungal candidate, warranting further exploration and development for combating A. fumigatus infections.

}, keywords = {Aspergillus fumigatus, cell wall integrity, Eugenol, Glycoconjugate, Transcription regulators, Virulence}, issn = {1364-5072}, doi = {10.1093/jambio/lxae009}, author = {Gupta, Lovely and Verma, Shalini and Goswami, Lakshmi and Kamboj, Himanshu and Sen, Pooja and Bhattacharya, Asish K. and Vijayaraghavan, Pooja} } @article {49288, title = {Unveiling the inverse sandwich complexes of XeO3: a computational exploration}, journal = {Inorganic Chemistry}, volume = {63}, year = {2024}, month = {JUL }, pages = {13585-13593}, type = {Article}, abstract = {

Our study introduces the design of inverse sandwich (iSw) complexes incorporating a noble gas compound: xenon trioxide (XeO3). Through comprehensive computational analyses, we have investigated the critical factors influencing their stability by employing a variety of state-of-the-art computational tools. We demonstrated that the coordination number of xenon in the iSw complex of XeO3 with 18-crown-6 is influenced by the presence of a rare, weakly stabilizing XeXe interaction between the XeO3 molecules. Furthermore, we observed that the stability of iSw complexes of 1,3,5-triphenylbenzene (TPB) and its derivatives is not solely attributed to aerogen bonding, but also involves contributions from C-HO interactions and back-donation from the lone pair of Xe to the antibonding C-C orbitals of TPB. Additionally, the significant contributions from orbital interactions and dispersion interactions in the TPB derivatives highlight the multifaceted amphoteric properties of XeO3 and reveal that the iSw complexes of TPB and derivatives are not predominantly governed by electrostatic interactions, contrary to conventional belief.

}, issn = {0020-1669}, doi = {10.1021/acs.inorgchem.4c01744}, author = {Dash, Soumya Ranjan and Vanka, Kumar} } @article {49031, title = {Visible, far-red, and near-infrared active unsymmetrical squaraine dyes based on extended conjugation within the polymethine framework for dye-sensitized solar cells}, journal = {ACS Applied Energy Materials}, volume = {7}, year = {2024}, month = {FEB }, pages = {1461-1475}, type = {Article}, abstract = {

Alkyl group wrapped visible, far-red, and NIR active unsymmetrical squaraine dyes with pi-extension in the polymethine framework-based AM4-AM7 have been designed, synthesized, and utilized as sensitizers for dye-sensitized solar cells. To extend the pi-conjugation within the polymethine framework, thiophene moieties have been incorporated between the donor and acceptor moieties. Absorption spectroscopic studies revealed that pi-extension with each -C \& boxH;C- unit resulted similar to 100 nm of redshift in the charge transfer transition with the lambda(maximum) of 541, 643, 747, and 833 nm for AM4, AM5, AM6, and AM7 dyes, respectively, with the molar extinction coefficient of \>10(5) M(-1)cm(-1). The pi-extended conjugation-based AM6 and AM7 dyes showed improved light-harvesting efficiency (LHE), where the AM7 dye showed an LHE of 386 nm at 60\%. Electrochemical studies of AM dyes revealed that the HOMO energy level of the sensitizers has been modulated systematically. Further, pi-extension within the polymethine framework showed a dramatic effect on V-OC, J(SC), and device efficiency when move from visible active AM4 to far-red active to NIR active AM7 dyes. The DSSC efficiencies of 7.35, 5.18, 0.08, and 0.053\% have been achieved with the I-/I-3(-) electrolyte (Z-50) for the AM4, AM5, AM6, and AM7 dyes, respectively. Further, AM4 dye has been cosensitized with AM5, AM6, and AM7 dyes, where AM4:AM5 (1:1) composition achieved the maximum efficiency of 8.12\% with I-/I-3(-) electrolyte (Z-50) compared to the other cosensitization compositions.

}, keywords = {aggregation of dyes, DSSC device efficiency, light-harvesting efficiency, pi-extension, polymethine framework, squaraine dyes}, issn = {2574-0962}, doi = {10.1021/acsaem.3c02610}, author = {Singh, Amrita and Singh, Ambarish Kumar and Dixit, Ruchi and Vanka, Kumar and Krishnamoorthy, Kothandam and Nithyanandhan, Jayaraj} } @article {49837, title = {Achmatowicz rearrangement-enabled unified total syntheses of (+)-passifetilactones A-C}, journal = {RSC Advances}, volume = {15}, year = {2025}, month = {OCT}, pages = {39919-39930}, type = {Article}, abstract = {

In this manuscript, we report the enantio- and diastereoselective total synthesis of three cytotoxic 2-pyrone-derived natural products passifetilactones A-C. Our strategy leverages a unified synthetic approach that originates from simple furan-based building blocks. Key transformations include the Corey-Bakshi-Shibata (CBS) reduction to access chiral furan-derived alcohol, NBS-mediated Achmatowicz rearrangement to construct the alpha-hydroxy-delta-pyrone core, followed by a highly stereoselective, iridium-catalyzed dynamic kinetic intramolecular redox isomerization to access the delta-hydroxy-alpha-pyrone framework. This streamlined route enables efficient access to passifetilactones A, B, and C in 13, 5, and 8 steps, with overall yields of 12\%, 54\%, and 37\%, respectively.

}, doi = {10.1039/d5ra06982c}, author = {Verma, Aman Kumar and Jeddi, Dharmaraju and Kontham, Ravindar} } @article {49851, title = {Ag(I)-catalyzed heterocyclization/[3+2] cycloaddition of α-alkynylenones with β-enaminones: tandem access to highly substituted cyclopenta[c]furans}, journal = {Journal of Organic Chemistry}, volume = {90}, year = {2025}, month = {SEP }, pages = {12466-12479}, type = {Article}, abstract = {

A robust Ag(I)-catalyzed tandem heterocyclization/[3 + 2] cycloaddition of alpha-alkynylenones with beta-enaminones was developed, enabling efficient synthesis of cyclopenta[c]furans with good yields, operational simplicity, and broad substrate scope. In addition, it also presents an extended methodology to synthesize unsymmetrical tri(hetero)aryl methane having chromone and furan/pyrrole scaffolds by a slight modification of starting materials. Moreover, the synthesized cyclopenta[c]furans exhibit good fluorescence properties with quantum yields ranging from 0.33 to 0.53, as suggested by the photophysical studies.

}, issn = {0022-3263}, doi = {10.1021/acs.joc.5c01707}, author = {Vara, Vijay and Thete, Kishor R. and Panikar, Sera Deepu and Khan, Akram A. and Muthukrishnan, M.} } @article {49604, title = {AgOTf-catalyzed cascade annulation of 5-hexyn-1-ols and aldehydes: enabling the diastereoselective synthesis of [6,6,6]-trioxa-fused ketals and hexahydro-2H-chromenes}, journal = {Chemical Communications}, volume = {61}, year = {2025}, month = {JAN }, pages = {973-976}, type = {Article}, abstract = {

We report the unprecedented diastereoselective synthesis of novel [6,6,6]-trioxa-fused ketals via AgOTf-catalyzed cascade annulation of 5-hexyn-1-ols (with primary or secondary hydroxyl groups) and aldehydes through a [2+2+1+1] pathway. In contrast, 5-hexyn-1-ols with tertiary hydroxyl groups yield hexahydro-2H-chromenes via a [3+1+1+1] pathway.

}, issn = {1359-7345}, doi = {10.1039/d4cc05546b}, author = {Vinodkumar, Ramavath and Nakate, Ashwini K. and Krishna, Gamidi Rama and Kontham, Ravindar} } @article {49858, title = {Aldol Condensation of Furfural with Acetone by Using Mg-Al-O-t-Bu HT Catalyst and Kinetic Studies}, journal = {Industrial \& Engineering Chemistry Research}, volume = {64}, year = {2025}, month = {DEC}, pages = {24938-24948}, type = {Article}, abstract = {

An environment-friendly method for producing jet fuel precursors involves the aldol condensation of biomass-derived chemicals. In this study, the condensation reaction between furfural and acetone was performed using a Mg-Al-O-t-Bu hydrotalcite (HT) catalyst, achieving a furfural conversion of 99\% and a selectivity of 82\% toward 4-(2-furyl)-3-buten-2-one (FAc). The kinetics of the process were evaluated using a Langmuir-Hinshelwood-Hougen-Watson (LHHW) model across a range of temperatures, and the model showed an excellent fit to the experimental data. The effect of different catalysts, reaction temperatures, catalyst loadings, molar ratios, and reaction times was systematically investigated. The Mg-Al-O-t-Bu HT catalyst was extensively analyzed through techniques such as XRD, XPS, FTIR, nitrogen adsorption-desorption measurements, and CO2-TPD. The catalyst exhibited excellent stability, maintaining its performance consistently across five successive reaction cycles with no notable decline in activity. These findings highlight the industrial relevance of Mg-Al-O-t-Bu HT as a robust and recyclable solid base catalyst for biomass upgrading, with strong potential for process scale-up in renewable fuel production.

}, issn = {0888-5885}, doi = {10.1021/acs.iecr.5c03287}, author = {Patil, Sneha and Kamble, Paresh and Vinod, Chathakudath Prabhakaran and Rathod, Virendra and Kantam, Mannepalli Lakshmi} } @article {50014, title = {Bioinspired synthesis of bridged isochromane fused pyrazoles by a silver catalyzed cascade reaction and its application for antibacterial activity}, journal = {JACS Au}, volume = {5}, year = {2025}, month = {AUG}, pages = {4184{\textendash}4195}, type = {Article}, abstract = {

A stereoselective silver catalyzed one pot vinylogous aldol addition followed by a cascade [4+2] cycloaddition reaction of α-arylidene pyrazolinones to\ in situ\ generated isochromenylium ions has been developed, which provides an unprecedented bridged [2.2.2] [3.3.1] pentacyclic [5-6-6-6-6] skeleton consisting of an isochroman, chroman, and a pyrazole unit in one molecule with good to high yields as a single diastereomer. This method offers mild reaction conditions, wide substrate compatibility, excellent scalability and easy derivatization. A DFT study was carried out to clarify the reaction mechanism. It was exciting to observe that the unprecedented bridged isochromans synthesized here have shown excellent selectivity toward Gram-positive and Gram-negative bacteria. We demonstrate that while some structures are broad spectrum antibacterial there are two distinct structures that can be explored for selective activity.

}, keywords = {Antibacterial, Bridged [2.2.2] [3.3.1], ROS, Stereoselective, Vinylogous aldol addition, [4+2] cycloaddition}, doi = {https://doi.org/10.1021/jacsau.5c00105}, author = {Singh, Bhuvnesh and Tewari, Shreya and Kaur, Manleen and Sharma, Himanshu and Vanka, Kumar and Singh, Neetu and Singh, Ravi P.} } @article {49725, title = {Catalytic hydrogenation of cinnamaldehyde over nanocrystalline nickel-doped lanthanum aluminate: synergistic effect of nickel and oxygen vacancies}, journal = {ChemCatChem}, volume = {17}, year = {2025}, month = {JUN}, type = {Article}, abstract = {

Nickel-doped lanthanum aluminium perovskite, LaAl1-xNixO3-delta with x = 0, 0.1, 0.2, 0.3, 0.4,0.5, 0.6, and 0.75 (LANx), were obtained through a combustion method followed by a calcination process. The obtained LANx materials crystallized in the cubic structure by the Pm-3m (221) space group. The nanocrystalline nature of the LANx materials was confirmed by the average crystalline size determined using Debye-Scherrer formula. X-ray photoelectron spectroscopy (XPS) studies showed that nickel was present in the +2 and +3 oxidation states. The introduction of nickel resulted in distinct peaks in TPR in the temperature range of 200-600 degrees C, with an enhanced reducibility of the materials. The LANx materials were thoroughly assessed for their effectiveness in the hydrogenation of cinnamaldehyde. The maximum catalytic activity (cinnamaldehyde conversion of 98\% with a hydrocinnamylalcohol selectivity 96.5\%) was observed with the presence of the LAN7 catalyst at 150 degrees C for 6 h at a H2 pressure of 10 bar. The catalytic activity is maintained even after four cycles, which broadens the application scope as the material is sustainable, scalable, cost-effective, and a potential alternative to reported noble metal catalysts. The synergistic effect of nickel and oxygen vacancies in the catalyst improves the reducibility and provides a promising catalytic activity in the cinnamaldehyde hydrogenation.

}, keywords = {Cinnamaldehyde, Hydrocinnamylalcohol, Hydrogenation, Nickel, Perovskite oxide}, issn = {1867-3880}, doi = {10.1002/cctc.202500011}, author = {Bhavisha, Meloth and Balamurugan, Sarkarainadar and Venkatesha, Naragalu J. and Gopinath, Chinnakonda S. and Sakthivel, Ayyamperumal} } @article {49499, title = {Ce[N(SiMe3)2]3(THF)3-catal yzed hydroboration of CO2, esters and epoxides with pinacolborane: selective synthesis of methanol in multigram scale}, journal = {Chemistry-A European Journal}, volume = {31}, year = {2025}, month = {MAR}, type = {Article}, abstract = {

In this work, we have reduced CO2 with HBpin to afford borylated methanol product selectively in similar to 99 \% yield using Ce[N(SiMe3)(2)](3)(THF)(3) as a catalyst. This led to multigram scale isolation of methanol obtained from CO2 reduction via the hydrolysis of borylated methanol, this establishes the potential of Ce[N(SiMe3)(2)](3)(THF)(3) as an efficient homogeneous catalyst for the bulk scale methanol synthesis. A practical application of this catalytic system was also shown by reducing CO2-containing motorbike exhaust efficiently and selectively. Further, C-O bond activation of esters and epoxides using HBpin and 1-2 mol \% of Ce[N(SiMe3)(2)](3)(THF)(3) at 60 degrees C afforded the borylated alcohols in good to excellent yields, which can easily be hydrolysed to the eco-friendly corresponding alcohol. The stoichiometric experiments were performed to prove the formation of in-situ generated cerium hydride [Ce]-H as an active catalyst.

}, keywords = {Cerium, CO2 reduction, Epoxide, Ester, Hydroboration, Lanthanides}, issn = {0947-6539}, doi = {10.1002/chem.202403449}, author = {Hossain, Md Jabed and Shah, Brij Kumar and Dash, Soumya Ranjan and Vanka, Kumar and Khan, Shabana} } @article {49540, title = {Charge transfer effect on relaxation mechanism in hydrated pyrrole-water systems following N-2s ionization}, journal = {ChemPhysChem}, volume = {26}, year = {2025}, month = {APR}, type = {Article}, abstract = {

This study investigates the relaxation mechanisms of pyrrole and pyrrole-water clusters (C4H5N-(H2O)n, where n=0-3 \${n = 0 - 3}\$ ) following N-2s ionization of pyrrole. Using various theoretical methods, we focus on the influence of water molecules and charge transfer on these non-radiative relaxation pathways. Our simulations included pyrrole solvated in 494 explicit water molecules equilibrated at 300 K and also employed a polarizable continuum model (PCM) to make the system more realistic and gain additional insights. In hydrated environments, the hydrogen bonding network between pyrrole and surrounding water molecules facilitates enhanced non-radiative relaxation pathways following inner valence ionization. Since these are hydrogen bonding systems, we have explored the possibility of proton transfer, which could occur in conjunction with other electronic decay processes.

}, keywords = {ab initio-calculations, auger decay, charge transfer, proton transfer, pyrrole}, issn = {1439-4235}, doi = {10.1002/cphc.202400962}, author = {Kumar, Ravi and Bhattacharjee, Kankana and Ghosh, Aryya and Vaval, Nayana} } @article {49899, title = {(Chiro)optical Properties of π-Extended Spiro-Double Carbo[7]helicene}, journal = {Journal of Physical Chemistry Letters}, volume = {16}, year = {2025}, month = {NOV }, pages = {11657-11664}, type = {Article}, abstract = {

Helical nanographenes are a fascinating class of pi-extended chiral nanocarbons, where structural helicity imparts intrinsic chirality and unique optoelectronic properties to the rigid carbon framework. In this work, we synthesized a hexa-peri-hexabenzocoronene-based pi-extended spiro-double carbo[7]helicene. The helical distortion of the structure was unambiguously confirmed by X-ray crystallography. The optical properties were explored through UV-Vis absorption, fluorescence, and phosphorescence measurements, complemented by density functional theory (DFT) calculations. Remarkably, the pi-extended spiro-double carbo[7]helicene exhibited thermally activated delayed fluorescence (TADF) at room temperature and phosphorescence at low temperatures. Chiral HPLC successfully resolved the enantiomers into three fractions: (PP), (MM), and the meso forms (PM)/(MP), and chiroptical studies of the pure enantiomers revealed a moderately high g lum value of 1.58 x 10-3. Finally, the origin of the observed dissymmetry factors was rationalized by analyzing the transition electric dipole moments (TEDM) and transition magnetic dipole moments (TMDM) derived from time-dependent density functional theory (TD-DFT) calculations.

}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.5c02897}, author = {Kumar, Viksit and Dongre, Sangram D. and Vandhanam, Aparna and Jadhav, Ashok Badrinarayan and Kumar, Jatish and Babu, Sukumaran Santhosh} } @article {49607, title = {Chiroptical amplification of [7]-helicene nanographene by additional helical chirality}, journal = {Angewandte Chemie-International Edition}, volume = {64}, year = {2025}, month = {FEB }, pages = {e202420767}, type = {Article}, abstract = {

Nanographenes have captivated scientific interest since the pioneering discovery of graphene. Recently, attention has shifted towards exploring chiral and nonplanar nanographenes, for their distinct optical, chiroptical, and electronic properties. Despite the growing acceptance of helicenes, the research on inducing helical chirality on pi-extended derivatives to boost chiroptical properties remains unattended. In our study, we introduce a new pi-extended [7]-helicene resulting from the condensation of diamines with 3,6-dibromophenanthrene-9,10-dione, complemented by two hexabenzocoronene arms in the periphery. Notably, the nanographene containing binaphtho-[1,4]diazocine, compared to the corresponding phenazine, exhibits a remarkable average 2.5, 5, and 10-fold enhancements in quantum yield, dissymmetry factor, and brightness, respectively, when measured in five different solvents. These improvements underscore the significance of the induced helical chirality by the antiaromatic binaphtho-[1,4]diazocine in influencing the chiroptical properties of the helical nanographene. Our research represents a significant stride toward unlocking the potential of pi-extended helicenes and lays the groundwork for further exploration in designing and synthesizing new chiral nanomaterials.

}, keywords = {circularly polarised luminescence, dissymmetry factor, helicene, nanographene, quantum yield}, doi = {10.1002/anie.202420767}, author = {Dongre, Sangram D. and Venugopal, Geethu and Kumar, Viksit and Badrinarayan Jadhav, Ashok and Kumar, Jatish and Babu, Sukumaran Santhosh} } @article {49887, title = {Cocrystals of the green fluorescence protein chromophore analogue: coformer-induced switch between AIE and ACQ}, journal = {Crystal Growth \& Design}, volume = {25}, year = {2025}, month = {SEP}, pages = {7473-7488}, type = {Article}, abstract = {

Fluorescent organic solids hold great potential for advancing photonics applications. However, tuning their solid-state photoluminescent emissions remains a significant challenge. In this study, we report the synthesis and characterization of five cocrystals (two cocrystal polymorphs) derived from a pristine imidazolinone derivative (A) and the various coformer molecules, namely 1,2,4,5-tetrafluoro-3,6-diiodobenzene, 1,2,4,5-tetrafluoro-3,6-dibromobenzene, perfluoronaphthalene, and 3,4,5-trifluorobenzoic acid. The structural and optical properties of these cocrystals were examined by using single-crystal X-ray diffraction, absorption spectroscopy, photoluminescence spectroscopy, and photoluminescence decay spectroscopy. Cocrystals I, II, and III are isomorphous pairs and exhibit three-dimensional isostructurality, where the coformer molecules bridge adjacent helices of compound A, leading to aggregation-induced emission. In contrast, the cocrystal polymorphs IVA and IVB developed using coformer 3,4,5-trifluorobenzoic acid form two-dimensional sheet-like structures mediated by pi-stacking interactions between the coformers and molecule A, with interplanar distances ranging from 3.2 to 3.5 \& Aring;. These stronger pi-pi interactions promote nonradiative decay pathways, resulting in reduced or quenched fluorescence and an aggregation-caused quenching effect. To gain further insights into their electronic properties, theoretical analysis including frontier molecular orbitals, time-dependent density functional theory, Hirshfeld surface analysis, molecular electrostatic potential, and noncovalent interaction plots were performed.

}, issn = {1528-7483}, doi = {10.1021/acs.cgd.5c00559}, author = {Suresh, Sneha and Dabke, Niteen B. and Pandya, Rinu and Vanka, Kumar and Dutta, Madhusudan and Gonnade, Rajesh G.} } @article {49909, title = {Comprehensive in vitro and in silico assessment of eugenol glycoconjugates against azole and amphotericin B resistant Rhizopus spp.}, journal = {Molecular Biology Reports}, volume = {52}, year = {2025}, month = {JUN }, pages = {589}, type = {Article}, abstract = {

Background Rhizopus spp. is a major cause of mucormycosis, a severe infectious disease with high morbidity and mortality. Treatment is challenging due to rising antifungal resistance. Glycosylation is a crucial technique for enhancing the properties of phenolic compounds like eugenol. The present study aims to examine the antifungal efficacy of eugenol glycoconjugates against azole and amphotericin B-resistant Rhizopus isolates. Methods and results Out of 50 soil samples, 12 isolates belonging to Mucorales were obtained, of which 7 were identified as Rhizopus spp. via 18S ITS sequencing. Antifungal susceptibility testing (AST) revealed that all Rhizopus isolates were resistant to amphotericin B (MIC \> 1 mu g/mL). Most isolates also showed resistance towards posaconazole (MIC \> 1 mu g/mL) and itraconazole (MIC \> 2 mu g/mL). AST of eugenol glycoconjugate (coded 6g) showed efficacy against resistant Rhizopus isolates, with MIC values ranging from 6.25 mu g/mL to 25 mu g/mL. Flow cytometry confirmed its fungicidal activity, correlating with MIC data. Compound 6g significantly reduced conidial germination within 24 h and exhibited no cytotoxicity on A549 lung cancer cells. In-silico analysis revealed a negative binding affinity of compound 6g for the spore coat protein CotH3, which could be a potential antifungal target. Conclusion Compound 6g could be an potential antifungal molecule against resistant Rhizopus spp, which requires further studies.

}, keywords = {Antifungals, Eugenol, Glycoconjugates, Mucormycosis, Resistance, Virulence}, issn = {0301-4851}, doi = {10.1007/s11033-025-10673-2}, author = {Sen, Pooja and Gupta, Lovely and Chauhan, Aastha and Goswami, Lakshmi and Bhattacharya, Asish K. and Sengupta, Abhishek and Vijayaraghavan, Pooja} } @article {50015, title = {Comprehensive investigation on statistical approaches and classical strain improvement for penicillin V production by Penicillium rubens BIONCL P45 strain}, journal = {Systems Microbiology and Biomanufacturing }, volume = {5}, year = {2025}, month = {JAN}, pages = {1302 -1327}, type = {Article}, abstract = {

Media engineering and strain improvement are critical aspects of microbial biotechnology playing a vital role in enhancing microbial productivity, and ensuring cost-effective bioprocessing. In this investigation, we optimized the various medium components, nutritional condition, and fermentation parameters for the industrial production of phenoxymethylpenicillin or penicillin V (PenV). We have isolated, characterized\ Penicillium rubens\ BIONCL P45 strain which initially produced 100\ mg/L of PenV. Further, optimization using production medium 4 (PM4) comprising lactose, corn steep solids, sodium sulfate, calcium carbonate, and phenoxy acetic acid lead to a significant increase in production, reaching 430\ mg/L. Further improvements through response surface methodology (RSM) predicted a production of 646\ mg/L, which was experimentally validated at 685\ mg/L. Subsequently, mutagenesis studies using UV (ultraviolet) exposure resulted in the UV-65 mutant, which demonstrated a superior performance, achieving 934\ mg/L, surpassing the parental strain. ​These combined strategies lead to a tenfold increase in PenV titer, highlighting their effectiveness in bioprocess development and industrial-scale antibiotic production.

}, keywords = {Box-Behnken design, Classical strain improvement (CSI), Media optimization, Penicillin V, Penicillium rubens, Response surface methodology}, doi = {10.1007/s43393-025-00377-w}, author = {Sawant, Amol Muralidhar and Vamkudoth, Koteswara Rao} } @article {49724, title = {Coumarin hybrids: dual-target candidates for future antimicrobial and antitubercular therapies}, journal = {Future Medicinal Chemistry}, volume = {17}, year = {2025}, month = {MAY}, pages = {1131-1142}, type = {Article}, abstract = {

Aims: This study aimed to synthesize, characterize, and evaluate the antimicrobial and antitubercular activities of two novel series of coumarin-based derivatives (Series 5 and Series 9), focusing on their structure-activity relationship (SAR) and molecular docking interactions with key bacterial enzymes. Materials \& methods: Series 5 (5a-5j) and Series 9 (9a-9t) compounds were synthesized and characterized using spectroscopic techniques. Their antimicrobial and antitubercular activities were evaluated against Mycobacterium tuberculosis, Staphylococcus aureus, Bacillus subtilis, and E. coli. IC50 values were determined, and molecular docking studies were conducted to assess binding interactions with M. tuberculosis enoyl-ACP reductase (InhA) and E. coli DNA gyrase B. Results: Series 5 compounds exhibited moderate activity, with 5f, 5 g, 5i, and 5j showing notable inhibition. Series 9 derivatives displayed superior dual-target inhibition, with 9t, 9c, 9a, 9b, and 9p achieving \>90\% inhibition against S. aureus and B. subtilis. The lowest IC50 against M. tuberculosis was observed for 9c (1.50 mu g/mL), followed by 9a (2.84 mu g/mL) and 9b (2.73 mu g/mL). Molecular docking confirmed strong binding interactions, correlating with observed biological activities. Conclusions: Series 9 compounds, particularly 9t, 9c, and 9a, demonstrate high potential as dual-target antimicrobial drug candidates. Further optimization may enhance their therapeutic efficacy. [GRAPHICS]

}, keywords = {Antimicrobial activity, antitubercular agents, Coumarin derivatives, Molecular docking studies, structure-activity relationship (SAR), thiophene-based compounds}, issn = {1756-8919}, doi = {10.1080/17568919.2025.2504331}, author = {Bavishi, Abhay and Vala, Hardev and Thakrar, Shailesh and Swami, Sagar and Sarkar, Dhiman and Shukla, Rushit and Kamdar, Jignesh and Shah, Anamik} } @article {49869, title = {The critical helping hand of water: theory shows the way to obtain elusive, granular information about kinetic asymmetry driven systems}, journal = {Chemical Science}, volume = {16}, year = {2025}, month = {AUG }, pages = {14940-14955}, type = {Article}, abstract = {

Kinetic asymmetry is crucial in chemical systems where the selective synthesis of one product over another, or the acceleration of specific reaction(s) is necessary. However, obtaining precise information with current experimental methods about the behavior of such systems as a function of time, substrate concentration and other relevant factors, is not possible. Computational chemistry provides a powerful means to address this problem. The current study unveils a two-pronged computational approach: (i) full quantum chemical studies with density functional theory (DFT), followed by (ii) stochastic simulations with a validated Gillespie algorithm (GA) (using representative model systems where necessary), to study the behavior of a kinetic asymmetry driven unidirectional molecular motor (1-phenylpyrrole2,2 {\textquoteleft}-dicarboxylic acid) (Nature, 2022, 604 (7904), 80-85). Our approach allows us to understand what is really taking place in the system, underlining the crucial role played by water molecules in facilitating the rotation of the motor. It is seen that water lubricates the motion by increasing the rotation rate constant of the final step by, remarkably, more than ten orders of magnitude! These insights further serve to explain the efficient rotation of the very recently reported gel-embedded molecular motor (Nature, 2025, 637 (8046), 594-600), providing an upper limit for the allowed rotation barrier in such systems, and thus also casts light into the functioning of bio-molecular motors. The current work therefore provides a template for carefully and properly studying a wide variety of important, kinetic asymmetry driven systems in the future.

}, issn = {2041-6520}, doi = {10.1039/d5sc03256c}, author = {Bajpai, Priyam and Thulasiram, Shrivatsa and Vanka, Kumar} } @article {49587, title = {Deciphering the intricate mechanisms behind the selective oxidation of methane to C1 and C2 oxygenates over FeAu/γ-Al2O3 catalysts}, journal = {Chemical Engineering Journal}, volume = {512}, year = {2025}, month = {MAY}, pages = {162510}, type = {Article}, abstract = {

In this work, we demonstrate an eco-benign synthesis protocol for preparing gold nanoparticles and the role of the strong interaction between gold nanoparticles and iron oxide in FeAu/gamma-Al2O3 catalysts that render it an anionic (Au delta-) character while tailoring them in a smaller size. The multifunctional FeAu/gamma-Al2O3 catalyst selectively produces ethanol (95 \% selectivity, similar to 240 mu mol(-1) cat) at a mild temperature of 75 degrees C without the addition of co-reactants during liquid phase methane oxidation with molecular oxygen. Conversely, Au/gamma-Al2O3 and Fe/gamma-Al2O3 catalysts exhibited high selectivity for CH3OH and HCHO. A high dispersion accompanied by strong electronic interaction between the Au delta{\textendash}FeOx, as corroborated by diverse techniques, enables methane activation across the interface and coupling on the gold nanoparticles, which are responsible for the markedly improved formation of ethanol. Furthermore, in situ DRIFTS studies and DFT investigations point to a reaction mechanism of coupling of CH2OH and CH3 intermediates as the most likely route for ethanol formation.

}, keywords = {Anionic gold catalysts, Au-FeOx synergism, C-H bond activation, Ethanol, Methane oxidation, Methanol}, issn = {1385-8947}, doi = {10.1016/j.cej.2025.162510}, author = {Prabu, Marimuthu and Manikandan, Marimuthu and Rengam, B. Sathya Sai and Ramakrishnan, Archana and Raja, Abhishekram and Urkude, Rajashri R. and Ghosh, Biplab and Varghese, Jithin John and Raja, Thirumalaiswamy} } @article {49421, title = {Depolymerization of waste polycarbonates to value-added products}, journal = {ChemSusChem}, volume = {18}, year = {2025}, month = {JAN}, type = {Article}, abstract = {

Additive free aminolysis method developed for the depolymerization/upcycling of polycarbonates. We report here chemical recycling of polycarbonate under ambient conditions to get its monomer bisphenol A, monoaminocarbamate and biscarbamates in 1 : 2 : 1 ratio respectively. By employing the secondary amine as the aminating reagent, facilitates the depolymerization to work under additive/catalyst free conditions. The developed method deals with depolymerization of waste polycarbonates and works even with late-stage amine derivatives such as amoxapine and desloratadine which are drugs molecules known to treat neurotic disorders and allergies respectively. The reaction can be scaled up and works with similar efficacy which depicts the efficiency of the depolymerization of wasteend-of-life polycarbonate plastic waste. The biscarbamate and bisphenol-A was further subjected for the post functionalization to obtain amides and phenol in good yields. Developed additive/catalyst free aminolysis of waste polycarbonates to carbamates and monomer BPA at ambient conditions. Variety of secondary amines were screened including the late stage amine derivatives like amoxapine and desloratadine which delivered the expected products successfully. Later the developed methodology was even applied for the different end-of-life polycarbonates with the secondary amine and achieved the depolymerization without any obstacle. Further carried out the scale up reaction and derivatization of carbamates and BPA to amide and phenol synthesis. image

}, keywords = {Aminolysis, carbamates, depolymerization, End-of-life, Polycarbonate}, issn = {1864-5631}, doi = {10.1002/cssc.202400756}, author = {Padhi, Ganeshdev and Pansare, Vaibhav Ramachandra and Bajpai, Priyam and Krishna, Gamidi Rama and Vanka, Kumar and Barsu, Nagaraju} } @article {49945, title = {Design, fabrication and comprehensive testing of biodegradable 3D printable hybrid polymer airway splints}, journal = {Journal of Materials Chemistry B}, volume = {13}, year = {2025}, month = {AUG }, pages = {10249-10266}, type = {Article}, abstract = {

The trachea plays a critical role in respiration and airway protection but is susceptible to damage from pathological conditions such as stenosis, fistula, obstruction, and malacia. While existing treatment options are useful, they often have limitations, driving the need for innovative alternatives. This study introduces a novel approach using 3D printing technology to create hybrid degradable tracheal splints made of pectin-g-polycaprolactone (pec-g-PCL). We synthesized and characterized various compositions of pec-g-PCL to assess their physicochemical properties and tested their suitability for 3D printing. The resulting materials demonstrated the potential for use as tracheal splints. Using CAD software, we created two distinct designs, which were then fabricated according to those specifications. Micro-computed tomography (micro-CT) imaging revealed splint porosities ranging from 80\% to 90\%, highlighting their intricate internal microarchitecture. Design verification was conducted through numerical simulations, based on finite element modeling (FEM), to evaluate mechanical properties and computational fluid dynamics (CFD) for assessing the airflow dynamics of the fabricated tracheal splints. Degradation studies indicated that the 3D-printed scaffolds exhibited approximately 30\% degradation over a period of 35 days. In vitro, biocompatibility assessments confirmed the scaffold{\textquoteright}s compatibility with biological systems. These findings demonstrate the potential of pec-g-PCL-based tracheal splints as a promising solution to overcome limitations in current treatments. This research paves the way for advanced biomaterials that could revolutionize patient care by offering more effective solutions for managing tracheal disorders.

}, issn = {2050-750X}, doi = {10.1039/d5tb00891c}, author = {Naik, Sonali S. and Vongsvivut, Jitraporn and Dekiwadia, Chaitali and Abraham, Amanda N. and Dutta, Naba K. and Choudhury, Namita Roy and Nair, Kiran Sukumaran} } @article {50009, title = {Development of multiplex PCR assay for detection of mycotoxigenic Fusarium species contamination in stored maize grains, India}, journal = {The Microbe}, volume = {6}, year = {2025}, month = {MAR}, pages = {100240}, type = {Article}, abstract = {

This investigation aimed to improve the detection of key mycotoxigenic\ Fusarium\ species to address agricultural\ biosecurity\ and food safety threats in stored maize\ grains\ in India. We developed a multiplex polymerase chain reaction (mPCR) assay for the selective detection of\ Fusarium\ species producing\ mycotoxin,\ fumonisin\ B1\ (FB1),\ zearalenone\ (ZEA), and\ deoxynivalenol\ (DON) using their biosynthetic pathway genes viz., FUM1, FUM13, PKS4, PKS13 and TRI13, TRI7, respectively. The mPCR assay demonstrated a limit of detection (LOD) ranging from 1 {\texttimes} 103\ and 1 {\texttimes} 102\ spores/g maize grain in both naturally contaminated and\ Fusarium\ spores spiked samples, respectively. Maize grain samples were also evaluated for the assessment of mycotoxigenic\ Fusarium\ species contamination by mPCR which resulted in A total of 53 maize grain samples (75 \%) positive for\ mycotoxinchemotypes\ upon mPCR analysis. Among these, 40 sample tested positive for FB1, 39 for ZEA and 25 for DON. The levels of contamination ranged from 4 to 6456 {\textmu}g/kg for FB1, 30{\textendash}2192 {\textmu}g/kg for ZEA and 5{\textendash}1713 {\textmu}g/kg for DON as determined by high-performance liquid chromatography (HPLC). Furthermore, the developed mPCR results exhibited a significant correlation (\>95 \%) with HPLC data confirming this assays reliability. This finding infers developed mPCR assay is an expeditious, cost-effective, sensitive and selective tool for detecting toxigenic\ Fusarium\ species. This method can play a crucial role in assessing food safety and public health, particularly in regions where maize contamination by mycotoxins is a significant concern.

}, doi = {https://doi.org/10.1016/j.microb.2025.100240}, author = {Navale, Vishwambar Digambar and Vamkudoth, Koteswara Rao} } @article {49714, title = {Development of novel ssDNA aptamers for detection of receptor-binding domain of SARS-COV-2}, journal = {ACS Omega}, volume = {10}, year = {2025}, month = {JUN }, pages = {23981-23992}, type = {Article}, abstract = {

The highly virulent and transmissible SARS-CoV-2 causes COVID-19 and poses a global public health threat. Herein cloned, expressed, and the molecular weight of the receptor-binding domain (RBD) of the SARS-CoV-2 gene encoding protein was confirmed by SDS-PAGE electrophoresis and Western blot analysis. The pivotal aim is to develop single-stranded DNA (ssDNA) aptamers for the rapid detection of SARS-COV-2 infections in humans. In this investigation, a library of nine novel ssDNA aptamers was developed by several rounds of systematic evolution of ligands by an exponential enrichment approach and assessed by an enzyme-linked aptamer assay for binding affinity against RBD antigen (Ag). An in vitro assay resulted in a varied colorimetric signal that depends on the nature of aptamer. Quantitative determination of AptRBD3, AptRBD6, and AptRBD8 aptamers exhibited excellent binding affinity against Ag in the range of 5-10 ng/mL. The putative AptRBD3, AptRBD6, and AptRBD8 aptamers were converted into peptide sequences and docked against RBD, exhibiting good binding energy of -6.8, -6.3, and -7.1 kcal/mol respectively, which were recorded. Furthermore, docking studies of ssDNA aptamers were performed using HDOCK web server to ascertain the binding mechanism and docking score perceived as -389.74, -404.28, and -390.37. Despite this, we engineered a high-affinity AptRBD3.3 aptamer that formed a single and bulged loop, which improved binding affinity, resulted in a docking score of -361.56, and exhibited sensitivity at 4 ng of Ag of SARS-CoV-2. Moreover, computational modeling of AptRBD3.3 revealed an intriguing significant binding affinity with the RBD mutant SARS-CoV-2 S-UK variant (PDB ID: 7EDG) with a docking score of -350.21. In conclusion, the AptRBD3.3 aptamer can be used for the development of lateral flow device and electrochemical sensors for rapid, low-cost, and accurate detection of COVID-19 infection in humans for point of care diagnostics.

}, issn = {2470-1343}, doi = {10.1021/acsomega.4c03580}, author = {Auti, Amogh and Yadav, Pranay and Bodkhe, Rahul and Bhandari, Yogesh and Varma, Sanjana and Chaudhari, Bhushan and Rahi, Shraddha and Ghormade, Vandana and Vamkudoth, Koteswara Rao} } @article {49695, title = {Dopant and exfoliation induced simultaneous modification of charge density and C--C coupling sites for efficient CO2 photoreduction to ethylene}, journal = {Angewandte Chemie-International Edition}, volume = {64}, year = {2025}, month = {JUL}, pages = {e202423471}, type = {Article}, abstract = {

The photochemical conversion of CO2 into C2+ products has emerged as an attractive method for synthesizing valuable chemicals and fuels using abundant solar energy. However, the challenge lies in enhancing the efficiency and selectivity of C2+ product formation. In this study, we employed a heteroatom doping strategy to optimize the photocatalytic parameters and achieve excellent efficiency and selectivity in the photocatalytic CO2 reduction to C2+ product formation. Our experimental analysis revealed that the local electronic structure of the catalyst, modified by In-doping, enables enhanced efficiency. Additionally, the incorporation of Cu facilitates the coupling of C1 intermediates, resulting in excellent selectivity towards C2+ products. The CO2 reduction performance is further enhanced through exfoliation, which increases the exposure of active sites and extends the charge carrier lifetime by reducing the charge diffusion length. We report that the rate of formation of C2H4 reached 54.3 mu molh(-1)g(-1) with an outstanding selectivity of 91\% over the exfoliated CuIn-doped AgBiP2S6 catalyst. By elucidating the role of heteroatom doping and exfoliation in enhancing both the efficiency and selectivity of C2+ product formation, our study contributes to advancing the development of sustainable and efficient photocatalytic CO2 conversion technologies.

}, keywords = {C \& horbar, C coupling, CO2 reduction, Doping, Exfoliation, Photocatalysis}, doi = {10.1002/anie.202423471}, author = {Das, Kousik and Chakraborty, Subhajit and Kediya, Siddhi and Singh, Ashutosh Kumar and Das, Risov and Mondal, Soumi and Riyaz, Mohd and Goud, Devender and Dutta, Nilutpal and Vinod, Chathakudath P. and Peter, Sebastian C.} } @article {49614, title = {Double anchoring squaraine dye with triazatruxene amine donor for dye-sensitized solar cells: sequential cosensitization for panchromatic light-harvesting}, journal = {Journal of Photochemistry and Photobiology A-Chemistry}, volume = {462}, year = {2025}, month = {MAY}, pages = {116229}, type = {Article}, abstract = {

Dyes are firmly bound to a semiconducting TiO2 film using carboxylic acid anchoring groups for an efficient electron transfer from the excited state of dye to the conduction band (CB) of TiO2. Strong dye binding can be accomplished with multi-anchoring dye designs to improve photophysical characteristics, including high extinction coefficients, panchromatic absorption, post-sensitization modifications, and dark current suppression, besides enhancing the stability of the dye-TiO2 interface. Herein, a novel KV2D dye with double squaraine acceptor and double carboxylic acid anchoring groups is designed to achieve a high extinction coefficient (epsilon, 3.57 x 105M-1cm-1) and robust binding to the TiO2 film for an effective electron transfer. We systematically changed the amount of coadsorbent chenodeoxycholic acid (CDCA) to control the aggregation of dyes on the TiO2 surface that improves the power conversion efficiency (PCE, eta) for the devices based on the doubleanchoring KV2D. Out of these devices, KV2D: CDCA (1:10) based cell exhibited the best PCE of 5.26\% with VOC of 754 mV, JSC of 10.41 mA/cm2, and ff of 67\%. The sequential cosensitization studies were carried out with a far-red active dye to find the effect of the strong binding of the sensitizer to the TiO2 film. Interestingly, when di-anchoring, KV2D was sensitized first for 12 h and then sequentially cosensitized with far-red absorbing SQS4 for 5 h to achieve a PCE of 5.0\% with VOC of 697 mV, JSC of 10.23 mA/cm2, and ff of 70\% with panchromatic spectral response in IPCE upto 730 nm giving higher photocurrent generation.

}, keywords = {aggregation of dyes, Bulky donor unit, Double acceptor dye, Dye-sensitized solar cells, self-assembly of dye, squaraine dyes, triazatruxene}, issn = {1010-6030}, doi = {10.1016/j.jphotochem.2024.116229}, author = {Ingole, Kiran Balaso and Siby, Jesna and Pandya, Rinu and Vanka, Kumar and Krishnamoorthy, Kothandam and Nithyanandhan, Jayaraj} } @article {49544, title = {Early and advanced glycation end product analysis from women with PCOS on metformin}, journal = {Reproductive Biology}, volume = {25}, year = {2025}, month = {MAR}, pages = {100993}, type = {Article}, abstract = {

In this cross-sectional study, we have analyzed advanced glycation end products (AGEs) in the plasma and follicular fluid of women with polycystic ovary syndrome (PCOS) taking metformin during in vitro fertilization (IVF) and control women undergoing IVF. Glucose, fructose, fructosamine, carboxymethyl lysine/ arginine (CML/R) proteins, and pentosidine were measured in the plasma and paired follicular fluid. Glycated proteins were characterized by mass spectrometry. Fasting serum glucose and fructosamine were comparable; however, follicular fluid glucose and fructosamine were higher in the PCOS group, and other AGEs remained unaltered. Fructose was lower in both serum and follicular fluid from the PCOS group. A positive correlation between some of these AGEs and sugars estimated was observed. Glucose and fructosamine in the follicular fluid correlated with the antral follicle count. The number of glycated peptides identified in the PCOS group by mass spectrometry was more. Glycated K75, K402 amino acid residues of albumin were detected in the PCOS group only. Additionally, some proteins involved in steroidogenesis and oocyte maturation as well as transporters, and extracellular matrix proteins, were found to be glycated in the PCOS group, which may affect their function. Elevated glucose and fructosamine in the follicular fluid of the PCOS group may contribute to abnormal folliculogenesis. The glycation of albumin should be validated in more samples to be considered as a marker for PCOS diagnosis.

}, keywords = {Carboxymethyl lysine, Fructosamine, fructose, glucose, Pentosidine, Polycystic ovary syndrome}, issn = {1642-431X}, doi = {10.1016/j.repbio.2024.100993}, author = {Ambekar, Aditi S. and Naredi, Nikita and Malakar, Dipankar and Vashum, Y. and Misra, Pratibha and Kulkarni, Mahesh} } @article {49506, title = {Effect of doping on electrocatalytic dehydrogenation and hydrogenation of methyl decalin-methyl naphthalene system}, journal = {Journal of Physical Chemistry C}, volume = {129}, year = {2025}, month = {JAN}, pages = {2367-2380}, type = {Article}, abstract = {

The hydrogen economy can benefit from the use of liquid organic hydrogen carriers (LOHCs) for cross-continent hydrogen transportation in the future. However, dehydrogenation and hydrogenation of hydrogen require catalytic systems. Current research emphasizes selective Pt/Rh doping of Fe, Co, and Ni surfaces as catalysts for the dehydrogenation and hydrogenation of the methyl naphthalene-methyl decalin LOHC system, which has more than 7\% hydrogen weight capacity and meets the practical requirements established by the European Union and the United States Department of Energy. Density functional theory-based computational techniques demonstrate how the chemical modification of these surfaces with a Pt and Rh single-atom catalyst (SAC) can improve the efficiency of dehydrogenation and hydrogenation. With a sustainable method, electrochemical dehydrogenation and hydrogenation on these robust surfaces produce effective hydrogen storage for extended periods without losing hydrogen. Furthermore, optimal results for the hydrogenation of 2-methyl naphthalene on Fe-Rh SAC with path-determining step (PDS) = 0.98 eV and dehydrogenation of 1-methyl decalin on Fe-Pt SAC with PDS = 1.49 eV were obtained for the most effective active sites for the enhanced electrochemical process. This study offers new possibilities for the catalytic dehydrogenation and hydrogenation of LOHC systems by highlighting the impact of doping on transition-metal-based catalysts.

}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.4c07598}, author = {Verma, Tushar Singh and Selvaraj, Kaliaperumal and Krishnamurty, Sailaja} } @article {49881, title = {Efficient Copper-Catalyzed, One-Pot Synthesis of N2-Aryl Phosphoryl 1,2,3-Triazole 1-Oxides}, journal = {Asian Journal of Organic Chemistry}, volume = {14}, year = {2025}, month = {OCT}, pages = {e00162}, type = {Article}, abstract = {

A simple and facile one-pot process has been developed for the synthesis of N 2-aryl phosphoryl 1,2,3-triazole 1-oxide derivatives. This new approach utilizes simple and commercially available starting materials, operating under mild conditions. The method employs copper-catalyzed multicomponent reaction, involving the combination of arylhydrazines, beta-ketophosphonates, and tert-butyl nitrite. The developed protocol shows excellent functional group tolerance permitting an extensive range of substrate scope up to 92\% isolated yield.

}, keywords = {Copper-catalyzed, Phosphoryl triazoles N-oxides, Phosphorylated compound, Triazole N-oxides}, issn = {2193-5807}, doi = {10.1002/ajoc.202500162}, author = {Mujahid, M. and Bhavar, Akshay A. and Vara, Vijay and Gonnade, Rajesh and Muthukrishnan, M.} } @article {49697, title = {Engineered silk matrix as a substitute for acellular dermal matrix in breast reconstruction surgery}, journal = {International Journal of Biological Macromolecules}, volume = {312}, year = {2025}, month = {JUN}, pages = {144017}, type = {Article}, abstract = {

Implant-based breast reconstruction is a common standard of care for breast cancer patients following mastectomy. To support implant weight and placement, surgeons utilize autologous tissues, acellular dermal matrices (ADMs), or synthetic meshes. While ADMs provide structural support, they present significant risks, including infection transmission and seroma. Conversely, synthetic meshes exhibit poor cellular adhesion, leading to inadequate tissue integration. To address these challenges, there is a need for a matrix that enhances tissue integration while minimizing infection risks and other complications. Silk fibroin (SF), a natural biopolymer, possesses excellent biocompatibility and mechanical properties. This study introduces a novel engineered silk matrix (ESM) as an advanced solution for soft tissue regeneration, specifically in breast reconstruction surgery. The present study establishes the safety of ESM and evaluates its potential a tissue regeneration matrix through extensive in-vitro and in-vivo analyses. In-vitro assays demonstrated superior cellular adhesion, proliferation of human mammary fibroblast cells (HMFCs), collagen deposition and angiogenesis in ESM compared to collagen matrices and ADMs. Safety assessments, conducted in accordance with ISO 10993 guidelines, confirmed noncytotoxic nature of ESM. Furthermore, subcutaneous implantation revealed no systemic toxicity or adverse tissue reactions. In-vivo studies utilizing a Yorkshire pig model of simulated breast reconstruction surgery, demonstrated superior performance of ESM over collagen matrices in tissue regeneration. The findings showed enhanced fibroblast density, increased collagen deposition, and improved vascularization. These results suggest that ESM is a safer and more effective alternative to ADMs in breast reconstruction, with the potential to revolutionize post-mastectomy care for breast cancer patients.

}, keywords = {Biocompatibility, Breast reconstruction, ISO 10993, Polymer, Safety, Silk protein, tissue regeneration}, issn = {0141-8130}, doi = {10.1016/j.ijbiomac.2025.144017}, author = {Deshpande, Rucha and Shukla, Swati and Kale, Amod and Sayyad, Raeesa and Kewale, Bhawana and Deshmukh, Narendra and Nisal, Anuya and Venugopalan, Premnath} } @article {49764, title = {Engineered silk-dressing for acceleratedwound healing: biocompatibility and efficacy studies}, journal = {Macromolecular Bioscience}, volume = {25}, year = {2025}, month = {NOV}, pages = {e00323}, type = {Article}, abstract = {

Advanced wound care dressings are essential for improving clinical outcomes. The present study investigates the wound management potential of a unique dressing fabricated from silk proteins. The dressing was characterized for its physical and structural properties, including surface texture, porosity, fluid absorption capacity, and moisture vapor transmission rate. These parameters have been found to be critical for optimal wound healing. In vivo full thickness wound healing studies in a rat model validated the efficacy of the Silk-dressing compared to conventional cotton gauze and commercial polyurethane foam dressings. Histopathological analysis confirmed improved re-epithelialization, collagen deposition, angiogenesis, and formation of secondary follicles. Key advantages of Silk-dressing included non-adherence, absorption of exudate, maintenance of optimal moisture at wound site and acceleratedwound closure. Biocompatibility studies were also conducted in accordance with ISO 10993 guidelines, demonstrating no cytotoxicity, irritation, sensitization, or pyrogenicity. These findings highlight the potential of this uniquely designed Silk-dressing as a superior alternative for wound management, with a potential to improve clinical outcomes.

}, keywords = {Biocompatibility, biopolymer, ISO 10993, Silk protein, wound Healing}, issn = {1616-5187}, doi = {10.1002/mabi.202500323}, author = {Deshpande, Rucha and Pillai, Lakshmi R. and Sayyad, Raeesa and Shukla, Swati and Nisal, Anuya and Venugopalan, Premnath} } @article {49420, title = {Enhanced light-matter interaction in gas nitridation-derived TiNx thin films for potential plasmonic applications}, journal = {Journal of Materials Science}, volume = {60}, year = {2025}, month = {JAN}, pages = {178-194}, type = {Article}, abstract = {

Titanium nitride is a substitute material exhibiting improved opto-electrical characteristics suitable for plasmonic purposes with adjustable attributes. In this study, we have embraced an innovative methodology for the fabrication of titanium nitride thin coatings via the nitridation of RF magnetron-sputtered titanium metallic films for surface plasmon resonance utilisation. The augmented electrical and optical features of TiN thin coatings prepared through the nitridation procedure are reported for the first time. The metallic coatings underwent gas nitridation at diverse temperatures within the range of 450-600 degrees C. The titanium nitride phase evolution in the coatings was corroborated by x-ray diffraction and x-ray photoelectron spectroscopy examinations. The dielectric function is deduced from reflection spectra through Drude-Lorentz model fitting, and the manifestation of surface plasmon excitation in the visible region was confirmed by correlating with carrier concentration assessments and by ensuring the required negative permittivity in the region. The red shift of screened plasma wavelength was observed with the nitridation temperature, and the same is varied in the wavelength range 400-700 nm. Ultimately, surface plasmons were excited in coatings with optimised thickness using Kretschmann configuration in wavelength interrogation mode.

}, issn = {0022-2461}, doi = {10.1007/s10853-024-10520-y}, author = {Tony, Liya and Selvam, I. Packia and Vinod, C. P. and Potty, S. N.} } @article {49691, title = {Ethyl cellulose-based controlled-release atrazine nanoformulation for effective and long-term weed management in agriculture}, journal = {Industrial Crops and Products}, volume = {229}, year = {2025}, month = {JUL}, pages = {120992}, type = {Article}, abstract = {

Atrazine (ATZ) is the second most widely used herbicide. However, its widespread use is hazardous to the environment. We developed ethyl cellulose-based nanoformulated atrazine (nfATZ) to achieve slow and sustained release of ATZ for long-term weed control in crops such as maize. Maize or corn is used in several industrial applications, including the production of ethanol, corn syrup, adhesives, textiles, biodegradable plastics, etc. As broadleaf weeds significantly impact maize yields, we evaluated the effects of nfATZ and conventional ATZ on tomato as a representative of broadleaf weeds. Various concentrations of ATZ and nfATZ (1-10 mg per kg of soil) were evaluated in pre-emergence, post-emergence, and re-emergence studies. Several morphological, physiological, and biochemical parameters of weeds were assessed, and the efficacy of the herbicide formulations was evaluated. nfATZ outperformed conventional ATZ even at lower concentrations with prolonged herbicidal effectiveness beyond 30 days, while the main crop remained unaffected. The weed mortality in nfATZ treatment was \> 80 \%, while it was 35 \% - 45 \% in ATZ treatment. The chlorophyll and carotenoid contents decreased by similar to 65 \% in nfATZ-treated weeds, impacting their photosynthesis and overall health. ATZ and nfATZ also significantly impacted the activities of antioxidant enzymes, such as ascorbate peroxidase (similar to 57 \%), superoxide dismutase (similar to 67 \%), and peroxidase (similar to 77 \%) in weeds. Thus, we conclude that nfATZ performed significantly better than ATZ in controlling weeds over the long term and reducing its environmental impact. Therefore, we propose nfATZ for highly effective and long-term weed control in large-scale production of industrial crops like maize.

}, keywords = {Controlled-release, Herbicide, Nanoformulation, Oxidative stress, Weed management, Weed mortality}, issn = {0926-6690}, doi = {10.1016/j.indcrop.2025.120992}, author = {Gautam, Tripurari Rao and Vasmatkar, Pashupat and Gundloori, Rathna V. N. and Kadoo, Narendra} } @article {49409, title = {Evaluation of reaction kinetics for chemoselective hydrogenation of citral for intensification of citral intermediates using copper-based catalysts}, journal = {Indian Chemical Engineer}, volume = {67}, year = {2025}, month = {MAR}, type = {Article}, abstract = {

Citral intermediates{\textquoteright} formation kinetics is studied using non-noble metal catalyst (Cu/SiO2) to evaluate catalyst performance characteristics via chemoselective hydrogenation of citral. The catalyst is synthesised by the precipitation method and characterised using XRD, FESEM and BET surface area analyser. Hydrogenation experiments are carried out using an Autoclave reactor in the temperature range of 80{\textendash}120{\textdegree}C, pressure range of 10{\textendash}50 bar and for catalyst loadings of 0.5, 1 and 1.5 g. The intermediates product distribution comprises aldehyde and alcohol formation such as citronellal, nerol and citronellol formation. The performance of the Cu/SiO2\ catalyst is evaluated using the parameters such as citral conversion, citronellol selectivity and yield as 96.96\%, 95.30\% and 92.30\%, respectively under optimal conditions of 50 bar, 120{\textdegree}C and 1 g catalyst for the reaction time of 100 min. The absence of internal and external mass transfer limitations is verified using the Carberry number and Weisz-Prater modulus criterion. The intrinsic kinetics of the gas{\textendash}liquid phase hydrogenation of citral is determined using the Langmuir{\textendash}Hinshelwood-Hougen-Watson (LHHW) model for citral intermediates formation. The reaction kinetic parameters show that citronellol formation favours by the nerol route compared to citronellal conversion.

}, doi = {https://doi.org/10.1080/00194506.2024.2390068}, author = {Debtirtha, Banik and Kinage, Anil K. and Vasireddy, Satyam Naidu} } @article {49787, title = {Experimental investigation and lumped kinetic modeling studies for upcycling of polyolefins}, journal = {Journal of the Indian Chemical Society}, volume = {102}, year = {2025}, month = {NOV}, pages = {102127}, type = {Article}, abstract = {

The present work discusses on comparative kinetic analysis of the pyrolysis of polypropylene (PP), high-density polyethylene (HDPE), and low-density polyethylene (LDPE) using sophisticated lumped models. Unlike many previous studies that focused on single-polymer kinetic models or employed simplified reaction schemes, this study develops an enhanced multistep reaction network that explicitly considers both primary decomposition and secondary cracking pathways, thereby improving the accuracy of product distribution predictions. By integrating this detailed reaction framework with a robust nonlinear regression approach using LSQNONLIN and ODE45 solvers in MATLAB, the study achieved greater accuracy in estimating kinetic parameters than traditional curve-fitting methods. The findings reveal that HDPE exhibits the highest activation energy (222.97 kJ mol(-1)), indicating it is more thermally stable than LDPE (193.44 kJ mol(-1)) and PP (62.16 kJ mol(-1)). One of the highlights of the present work is that lower pyrolysis temperature (400 degrees C) is found to be optimum for liquid yield by reducing secondary cracking, which aligns with the sustainable fuel production principles. The study also emphasizes on the limitations of previous lumped models that overlooked wax decomposition pathways, which are crucial for optimizing the hydrocarbon distribution. Future research should investigate catalytic interventions and reactor design modifications to enhance the product selectivity and scalability. This study offers a more comprehensive kinetic framework for advancing the valorization of plastic waste through pyrolysis, aiding the development of efficient waste-to-fuel conversion strategies.

}, keywords = {Lumped kinetic modeling, Plastic pyrolysis, Rate constants, Reaction pathways, Secondary cracking reactions, Temperature-dependent product distributions}, issn = {0019-4522}, doi = {10.1016/j.jics.2025.102127}, author = {Kavade, Omkar G. and Dhepe, Paresh L. and Devi, Nandini R. and Vasireddy, Satyam Naidu} } @article {49914, title = {Exploring the electronic modulation in controlling the activity and selectivity of Ni-Au-In based catalyst in atmospheric pressure CO2 hydrogenation}, journal = {Chemical Engineering Journal}, volume = {520}, year = {2025}, month = {SEP }, pages = {165921}, type = {Article}, abstract = {

Nickel-based catalysts are widely used for the hydrogenation of CO2 but encounter stability challenges during prolonged reactions and at elevated temperatures. At atmospheric pressure, nickel primarily promotes methane formation in CO2 hydrogenation reactions. In this work, we demonstrate that the stability and activity of nickel can be significantly enhanced through gold (Au) modification. Furthermore, we achieve a near-complete selectivity switch from methane to CO by incorporating indium (In), mediated through the formation of Au-In alloy. This catalyst exhibits excellent CO2 conversion and CO selectivity at relatively lower temperatures (400 degrees C), addressing a major bottleneck in the Reverse Water-Gas Shifts (RWGS) reaction. XPS studies demonstrate an interesting electron transfer mechanism facilitated by gold, which involves the formation of electronrich Au species (Au delta-) and the development of Au-In alloys. This process improves the reducibility of nickel oxide while allowing a fraction of nickel to remain in its metallic form, managing a facile hydrogenation process and regulating the shift in selectivity from CH4 to CO.

}, keywords = {Alloy formation, Bimetallic catalyst, CO2 hydrogenation, RWGS, Selectivity switch, synergy, Trimetallic catalyst, XPS (X-ray photoelectron spectroscopy)}, issn = {1385-8947}, doi = {10.1016/j.cej.2025.165921}, author = {Bajpai, Jyotsna P. and Gupta, Sharad and Goud, Devender and Deka, Diku Raj and V. Jagtap, Anuradha and Kumar, Pawan and Ahamed, Momin and Peter, Sebastian C. and Vinod, C. P.} } @article {49729, title = {Facet dependence for solvent-modulated proton-coupled electron transfer in furfural acetalization on Pd nanostructures}, journal = {Chemical Engineering Journal}, volume = {514}, year = {2025}, month = {JUN}, pages = {163159}, type = {Article}, abstract = {

Furfural dialkyl acetals prepared via acetalization reaction of furfural and alcohols are promising biofuels. Using defined experiments and density functional theory (DFT) simulations, the structure-dependent activity and selectivity for furfural acetalization reaction in the presence of alcohols (methanol, ethanol, propanol and butanol) as solvents was studied over well-defined supported Pd nanostructures (octahedra (111), cubes (100) and spheres (both (111) and (100)). Pd cubes supported over TiO2 in the presence of ethanol as a solvent (at 303 K and balloon pressure H-2) exhibited 78 \% conversion and 100 \% selectivity for furfural diethyl acetal product in a short time (similar to 180 min). In contrast, Pd octahedra (111) and Pd spheres showed low conversions (18 \% and 6 \%) at the same reaction conditions. Interestingly, when used as a solvent, methanol showed the highest conversion (90 \%) and selectivity (100 \%) for furfural acetalization over Pd cubes. DFT simulations provided mechanistic insight into the reactivity of the two different Pd facets (111) and (100) in the presence of alcohol molecules towards furfural acetalization reaction. A three-step reaction mechanism was proposed for furfural acetalization with alcohols: (i) alcohol hydroxyl-dehydrogenation (ii) hydrogenation of furfural carbonyl oxygen, and (iii) formation of hemiacetal product. For all three steps, Pd (100) exhibited low activation barriers (51.6, 26.7 and 76.2 kJ/mol) compared to Pd (111) surface (78.6, 35.8 and 92.2 kJ/mol) in the presence of ethanol. The activation barriers for the above steps were further reduced to 47.8, 23.9 and 64.6 kJ/mol on Pd (100) in the presence of methanol, explaining the experimental high reactivity aided by methanol. DFT calculations elucidated the role of the hydrogen bonding network between the solvent molecules and adsorbate, enabling proton-coupled electron transfer for accelerated reactions.

}, keywords = {Acetalization, DFT, facet-dependent reactivity, furfural, Furfural dialkyl acetals, solvent effect}, issn = {1385-8947}, doi = {10.1016/j.cej.2025.163159}, author = {Porwal, Govind and Dandekar, Pallavi and Gorai, Twinkle and Khan, Tuhin Suvra and Haider, M. Ali and Gupta, Shelaka and Vinod, C. P.} } @article {49766, title = {Facile and eco-friendly synthesis of Mn2O3 nanoparticles via microwave-assisted glycerol-thermal method}, journal = {Journal of Chemical Sciences}, volume = {137}, year = {2025}, month = {NOV }, pages = {102}, type = {Article}, abstract = {

Microwave-assisted efficient synthesis of nanosized manganese oxide (Mn2O3) is reported using glycerol and manganese acetate. Glycerol in this reported methodology acts as an efficient solvent for this nanomaterial synthesis under microwave radiation. This reported method enables the synthesis of nanosized Mn2O3 without further use of additives, stabilizers, and bases other than glycerol and manganese precursor. Glycerol is a renewable biomaterial derived nonvolatile and nontoxic, safe solvent. It has a high boiling point and dielectric constant, which makes it an ideal solvent for microwave synthesis. The synthesized nanosized Mn2O3 was analyzed by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. We examined the catalytic properties of as-synthesized Mn2O3 for cinnamyl alcohol oxidation to cinnamaldehyde. In this oxidation activity experiment, nanosized Mn2O3 exhibits good conversion and selectivity towards the desired product. We also made an attempt to understand the probable mechanism of nanomaterial formation and found some conclusive evidence to support it. This research methodology is facile, energy efficient, and involves minimum chemicals for synthesis. It makes this reported methodology not only economically attractive but also environmentally friendly, which aligns well with green chemistry principles.

}, keywords = {Glycerol, green chemistry, Nanosized Mn2O3, nanostructured catalysis}, issn = {0974-3626}, doi = {10.1007/s12039-025-02429-z}, author = {Yadav, Akash and Jha, Ratnesh and Bhatkar, Akash and Gehlot, Bhavika and Kamble, Aditi and Manikandan, Marimuthu and Bhosale, Hritvik and Vaishnav, Vishal and Rathod, Rutik and Umbarkar, Shubhangi and Raja, Thirumalaiswamy and Bhatte, Kushal D.} } @article {49256, title = {The first enantioselective total synthesis of the eremophilane-type sesquiterpenoid (-)-peniroqueforin C}, journal = {Tetrahedron Letters}, volume = {154}, year = {2025}, month = {JAN }, pages = {155386}, type = {Article}, abstract = {

Herein, we report the first stereoselective total synthesis of the eremophilane-type sesquiterpenoid (-)-peniroqueforin C using a chiral-pool strategy. This synthetic route features the use of readily available (S)-(+)-carvone as a chiral building block, Robinson annulation to construct the decalin system, substrate-controlled stereoselective methylation, single-step annulative construction of a tricyclic gamma-ylidene-butenolide with concomitant alkene transposition, and direct lactone-to-lactam conversion as key transformations.

}, keywords = {annulation reactions, Eremophilanes, Peniroqueforin C, Sesquiterpenoids, Total synthesis}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2024.155386}, author = {Ingale, Sudhir R. and Vinodkumar, Ramavath and Kontham, Ravindar} } @article {49872, title = {From Delocalization to Disruption: The Role of Aromaticity in N-Heterocyclic Carbenes{\textquoteright} Reactions with Diazoalkane and Diazoester}, journal = {Journal of Organic Chemistry}, volume = {90}, year = {2025}, month = {SEP }, pages = {12409-12424}, type = {Article}, abstract = {

Aromaticity is a fundamental force shaping molecular stability and reactivity, yet its dynamic role along reaction coordinates remains poorly understood. In this study, we unveil how dynamic changes in aromatic character govern the reactivity of 5-ItBu with diazoalkanes and diazoesters through a multifaceted computational approach. By integrating electronic, magnetic, structural, and energetic aromaticity descriptors, we demonstrate that the retention of aromaticity along the reaction path markedly lowers activation barriers, while its disruption imposes significant energetic penalties. Activation strain model (ASM) and energy decomposition analysis (EDA) further underscore the role of aromatic stabilization in enhancing orbital interactions that drive reactivity. These insights establish a cohesive mechanistic framework, highlighting aromaticity not merely as a static structural feature but as a tunable lever in the design of selective transformations and next-generation catalysts.

}, issn = {0022-3263}, doi = {10.1021/acs.joc.5c01606}, author = {Sharma, Himanshu and Fernandez, Israel and Vanka, Kumar} } @article {49615, title = {Functionalized gold nanorods (GNRs) as a label for the detection of thyroid-stimulating hormone (TSH) through lateral flow assay (LFA)}, journal = { Emergent Materials}, volume = {8}, year = {2025}, month = {JAN}, pages = {601{\textendash}617}, type = {Article}, abstract = {

Thyroid-stimulating hormone (TSH) is an important biomarker of thyroid dysfunctions. Different types of nano biosensors have been developed to detect TSH. However, there is a lacuna in the development of sensitive paper-based nano biosensors due to less sensitivity and instability of the labels. Interestingly, the intense color and localized surface plasmon resonance (LSPR) property make gold nanorods (GNRs) an efficient lateral flow assay (LFA) label instead of spherical gold nanoparticles. The rapidity, simplicity and user-friendly functioning of LFAs make them a predominant technique compared to electrochemical techniques for point-of-care diagnosis. This proof-of-concept study underlines the role of stable GNRs as a novel label for LFAs. The TSH antibody functionalized GNRs can semi-quantitatively diagnose hyperthyroidism and hypothyroidism. The limit of detection (LOD) of the LFA is 0.3 {\textmu}IU/mL, determined by visually analyzing the color development at the test line without employing any quantification method. Moreover, the study provides a comprehensive understanding of seed-mediated synthesis and functionalization of GNRs, which would benefit the researchers in suitably designing the GNRs-based labels for LFAs. Considering their exceptional characteristics, GNR-based LFAs are expected to surpass other labelling nanomaterials in detecting various biological markers. This enhanced sensitivity could significantly improve the clinical utility of diagnostic kits.

}, doi = {https://doi.org/10.1007/s42247-024-00976-8}, author = {Varma, Sanjana and Burade, Dimpal K. and Chaudhari, Bhushan P.} } @article {49616, title = {Germylene mediated reductive C-C and C-N coupling of an isocyanide and its device application}, journal = {Angewandte Chemie-International Edition}, volume = {64}, year = {2025}, month = {FEB }, type = {Article}, abstract = {

We have demonstrated a unique reductive coupling of 4-iodophenyl isocyanide, facilitated by a perimidine-based N-heterocyclic germylene (NHGe), which yields a bis-spirogerma compound featuring simultaneous C-C and C-N bond formation. This reaction, which leads to the oxidation of germanium from +2 to +4, represents a significant departure from previously documented isocyanide-germylene interactions. The product exhibits extensive conjugation across its bicyclic C4Ge2N2 framework, conferring distinct photophysical properties, including prominent orange luminescence in both solution and solid states. The photophysical properties are supported by the TD-DFT calculations confirming an n -\>pi* transition. The potential application of this compound in optoelectronic devices, particularly as a hole transport layer in PbS quantum dot solar cells, is also explored, with promising preliminary results.

}, keywords = {Germylene, hole transport layer, Isocyanide, reductive coupling}, doi = {10.1002/anie.202417052}, author = {Gour, Kritika and Pramanik, Debjit and Dash, Soumya Ranjan and Shinde, Dipak Dattatray and Venugopal, Geethu and Vanka, Kumar and Rath, Arup K. and Sen, Sakya S.} } @article {49571, title = {Gold nanorods (GNRs): a golden nano compass to navigate breast cancer by multimodal imaging approaches}, journal = {Journal of Biomedical Materials Research Part B-Applied Biomaterials}, volume = {113}, year = {2025}, month = {FEB}, pages = {e35543}, type = {Review}, abstract = {

The ongoing rise in the incidences of breast cancer cases has concerned medical and scientific personnel around the world. Adequate treatment of cancer predominantly relies on the pertinent diagnosis of the type of cancer as well as other molecular and cellular details at the initial stage only. Surprisingly, up till now, there is no single, self-reliant imaging modality that helps to systematically find out the anatomical and functional events taking place inside the body. This resulted in the advent of the multimodal imaging concept, which encompasses the integration of complementary imaging modalities by designing multimodal imaging probes. Gold nanorods (GNRs) are extremely popular and effective nanoparticles for multimodal bioimaging due to their unique properties. Researchers have designed varieties of stable and biocompatible GNR-based probes for targeted and nontargeted multimodal imaging of breast cancer. However, there is a lack of investigations on the in vivo fate and the toxicity of GNRs. Thus, their preclinical to clinical translation can be attained by comprehensively determining the in vivo fate and toxicity of GNRs. The review provides details about the GNRs-based nanoprobes fabricated so far for breast cancer imaging, which, by consequent studies, can be taken up to clinical usage.

}, keywords = {Breast cancer, Gold nanorods, imaging probes, Multimodal Imaging}, issn = {1552-4973}, doi = {10.1002/jbm.b.35543}, author = {Varma, Sanjana and Bamb, Aagam Lalit and Haldar, Niladri and Gajbhiye, Virendra and Amalnerkar, Dinesh and Chaudhari, Bhushan Pradosh} } @article {50005, title = {Green synthesis and characterization of gold nanoparticles using pomegranate peel extract for inhibition of calcium oxalate crystals and uropathogenic bacteria}, journal = {BioNanoScience}, volume = {15}, year = {2025}, month = {AUG}, pages = {article number 500}, type = {Article}, abstract = {

This study explores the therapeutic potential of pomegranate peel extract (PPE) and its gold nanoparticle conjugate (PPE-AuNP) in the prevention and treatment of urolithiasis. Pomegranate peels collected from four agro-climatic zones of India exhibited consistent methanolic extract yields (10{\textendash}17\%) and total phenolic content, with the highest levels observed in the West zone. Green synthesis of PPE-AuNPs was confirmed through UV{\textendash}Vis spectroscopy (λmax = 522\ nm), DLS (38.2 {\textpm} 2.1\ nm), zeta potential (-33.66 {\textpm} 2.97\ mV), and TEM imaging, which showed uniform spherical nanoparticles. Characterization confirmed that PPE-AuNPs were crystalline and phytochemically capped. FTIR shifts in O{\textendash}H, C = O, and C{\textendash}O bands, along with a ~ 500\ cm-1\ Au{\textendash}O/N vibration, confirmed phytochemical-mediated reduction and stabilization. XRD revealed an FCC structure with a dominant (111) plane, indicating high crystallinity. The synthesized nanoparticles demonstrated antioxidant activity with an IC50 of 21.53\ {\textmu}g/mL, superior to PPE and AuNP alone. In vitro calcium oxalate crystallization assays revealed significant crystal inhibition by PPE-AuNPs, confirmed via E-SEM, EDAX, and XRD analyses. Antibacterial studies against\ E. coli,\ K. pneumoniae,\ S. aureus, and uropathogenic\ E. coli\ showed MIC values of 31.25{\textendash}62.5\ {\textmu}g/mL for PPE and PPE-AuNPs, with negligible activity from AuNP alone. In vivo studies in ethylene glycol-induced urolithiatic rats revealed significant improvement in urinary parameters, renal biochemistry (creatinine, urea, SGPT, SGOT), hematological markers, and histopathology, especially in the PPE-AuNP-treated group. PPE-AuNP treatment normalized urinary appearance, reduced serum creatinine and blood urea nitrogen (BUN), and restored renal architecture with minimal degeneration. The enhanced therapeutic effects of PPE-AuNPs are attributed to their bioactive phenolic surface ligands and colloidal stability. Overall, this study demonstrates the synergistic efficacy of PPE-AuNPs as a potent, green nanotherapeutic agent for urolithiasis, offering antioxidant, antibacterial, and nephroprotective effects with promising translational relevance.

}, doi = {https://doi.org/10.1007/s12668-025-02194-w}, author = {Mundhewadikar, Dhananjay M. and Bhalerao, Minal R. and Vairale, Shiva and Sabir, Safiya and Mote, Chandrashekhar and Chowdhury, Chiranjit and Agawane, Sachin B.} } @article {49789, title = {Harnessing AEM electrolyzer-level performance through strategically designing the electronic structure of electrocatalysts, enabling dynamic functional switching}, journal = {ACS Catalysis}, volume = {15}, year = {2025}, month = {DEC }, pages = {19968-19983}, type = {Article}, abstract = {

The anion exchange membrane water electrolyzer (AEMWE) is a promising technology for cost-effective hydrogen production. To promote its development and adoption, targeted efforts are focused on finding non-platinum group metal (non-PGM) electrocatalysts that efficiently facilitate the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Nickel sulfides (NiS) are effective OER catalysts; however, they suffer due to leaching-related instability at electrolyzer stack operational conditions. We introduce a rational non-PGM design that enhances stability during the OER while excelling at the HER, showcasing molecular-level insights for a scalable AEMWE zero-gap stack device. NiS coating is applied to the Al-metal-organic framework supported by 3D porous nickel foam (NSMA), leading to charge localization at the interface, which helps in OER by requiring only 322 millivolts at 100 mA cm-2. The main innovation in the NSMA design is a controlled electroreduction process that converts the Millerite phase into Ni3S2, a catalyst (rNSMA). This transformation leads to charge delocalization at the surface and a low overpotential of -80 mV at -100 mA cm-2 for the HER. In a full cell, this catalyst duo requires an overpotential of 1.49 V, outperforming the commercial Pt/Ru catalyst pair at 1.58 V. In a scaled-up 12.96 cm2 AEM electrolyzer single-cell stack, current density rose from 398 to 1062 mA/cm2, maintained for over 100 h at high temperatures, achieving 99\% Faradaic efficiency and 100\% hydrogen purity. The AEM electrolyzer cell shows a good energy efficiency of 45.50 kWh/kg and a cell efficiency of 86.59\%. Detailed studies, including DFT analyses, revealed that electronic structure modification enhances charge delocalization, driving its impressive performance on an industrially significant scale.

}, keywords = {anion exchangemembrane water electrolyzer (AEMWE), charge transfer, density functional theory(DFT), HER, nickel sulfide, OER}, issn = {2155-5435}, doi = {10.1021/acscatal.5c07117}, author = {Kumar, Sonu and Verma, Tushar Singh and Selvaraj, Kaliaperumal} } @article {50004, title = {Heterolytic cleavage of the B{\textendash}H bond in H3B{\textperiodcentered}L (L = THF, NMe2H) by an electrophilic Ir(iii) pincer complex [Ir(H)(PMe3)(tBu4POCOP)][BAr F4]}, volume = {55}, year = {2025}, month = {NOV}, pages = {476-491}, type = {Article}, abstract = {
Six- and five-coordinate iridium complexes, [Ir(H)Cl(PMe3)(tBu4POCOP)] (2) (tBu4POCOP = κ3-C6H3-2,6-(OPtBu2)2) and [Ir(H)(PMe3)(tBu4POCOP)][BArF4] (3), respectively, have been synthesized and characterized. The reactivity of the electrophilic 16-electron iridium(III) complex\ 3\ with H2, H3B{\textperiodcentered}THF, H3B{\textperiodcentered}NMe2H, and H3B{\textperiodcentered}NMe3\ was investigated. The reaction of complex\ 3\ with H2\ resulted in the formation of\ trans-[Ir(H)(η2-H2)(PMe3)(tBu4POCOP)][BArF4] complex\ 5. Complex\ 3\ was found to activate the B{\textendash}H bonds in H3B{\textperiodcentered}THF and H3B{\textperiodcentered}NMe2H (DMAB) in a heterolytic fashion. The reaction of complex\ 3\ with H3B{\textperiodcentered}THF at 298 K afforded\ trans-[Ir(H)2PMe3(tBu4POCOP)] complex\ 6\ and a boronium compound, [H2B(THF)2][BArF4]. Monitoring the reaction from 179 to 298 K by NMR spectroscopy revealed the formation of a σ-borane intermediate,\ trans-[Ir(H)(η1-HBH2{\textperiodcentered}THF)PMe3(tBu4POCOP)][BArF4] (3a-Int),\ en route\ to the final products observed at 298 K. The formation of this intermediate species was also investigated by density functional theory (DFT) calculations. The reaction of complex\ 3\ with H3B{\textperiodcentered}NMe2H at 298 K yielded a mixture of complexes\ 3\ and\ 5\ and a cyclic diborazane [H2BNMe2]2. The reaction was found to proceed\ via\ intermediates, a σ-borane complex,\ trans-[Ir(H)(η1-HBH2{\textperiodcentered}NMe2H)PMe3(tBu4POCOP)][BArF4] (3b), complex\ 6, [(NHMe2)2BH2][BArF4], and H2B[double bond, length as m-dash]NMe2. Complex\ 3\ exhibited no reactivity with H3B{\textperiodcentered}NMe3.

}, doi = {DOI https://doi.org/10.1039/D5DT01780G}, author = {Pradhan, Mitarani and Surati, Zeel Y. and Pal, Apurba Kumar and Vanka, Kumar and Jagirdar, Balaji R.} } @article {49965, title = {High performance and enhanced stability of Mn-Co3V2O8 coral-like structure for supercapacitor applications}, journal = {ACS Applied Energy Materials}, volume = {8}, year = {2025}, month = {JUN }, pages = {9419-9429}, type = {Article}, abstract = {

This study explores Mn-doped Co3V2O8 as a promising electrode material for high-performance supercapacitors. Mn doping significantly enhances the electrochemical properties of Co3V2O8, resulting in improved specific capacitance and cycling stability. Structural characterization reveals a coral-like morphology that increases the active sites and facilitates efficient charge transport and ion diffusion. Electrochemical tests show an impressive specific capacitance of 2352 F g(-1) in 2 M KOH at 1 A g(-1). For the assembled MCV5//AC asymmetric supercapacitor device, it has a high capacitance retention of 87.6\% and a high Coulombic efficiency of 96\% over 5000 cycles. The developed asymmetric MCV5/AC supercapacitor device achieved an energy density of 45 Wh kg(-1) and a power density of 750 W kg(-1). These findings establish Mn-doped Co3V2O8 as a durable and efficient electrode material, offering valuable insights into the relationship between the morphology and electrochemical performance. This work provides a foundation for the development of advanced materials for sustainable energy storage applications

}, keywords = {Co3V2O8, Electrode material, Energy storage, stability, supercapacitor}, issn = {2574-0962}, doi = {10.1021/acsaem.5c01055}, author = {Venkatesan, Sethuraman and Rajkumar, Palanisamy and Radhika, Govindaraju and Iyer, Maalavika S. and Manigandan, Ramadoss and Rajaiah, Dhilip Kumar and Radhakrishnan, S. and Raman, Sasikumar and Marimuthu, Senthilkumaran and Kim, Jinho} } @article {49596, title = {Hot injection assisted electronically modulated twin and grain boundary rich sub-2 nm pt3co alloy resistant to phosphate ion for PEMFCs}, journal = {Small}, volume = {21}, year = {2025}, month = {MAY}, type = {Article}, abstract = {

Modulation of the electronic d-band center, structural defects (line defects), and particle size of Pt3Co alloy electrocatalyst have huge significance in elevating its electrochemical oxygen reduction reaction activity. Deviating from traditional high-temperature strategies, the current work focuses on ripening these benefits by implying a simple economically viable hot-injection-assisted modified polyol process. A conclusive control over decrementing particle size starting from 2.7 to 1.3 nm, an increasing degree of strain (twin boundary), and shifting of the d-band center away from the Fermi level are obtained via varying the temperature to which the solution is injected. The catalyst prepared via the injection at 200 degrees C (Pt3Co(1.3 t,g-b)/fVC-200) has delivered an electrochemical surface area of 84 m(2) g(Pt)(-1) with the onset and half-wave potentials of 0.980 and 0.858 V, respectively, versus RHE and a limiting current of -6.0 mA cm(-2) with stability till 20k cycles. In the high-temperature proton exchange membrane fuel cell Pt3Co(1.3 t,g-b)/fVC-200-based cell has outperformed Pt/C rendering 600 mWcm(-2) under H-2-Air compared to 529 mWcm(-2) of Pt/C with 20\% lower Pt loading and double the stability due to enhanced resistance toward phosphoric acid for accelerated voltage cycling. A similar enhancement is seen while employing the catalyst for low-temperature fuel cells.

}, keywords = {electrocatalyst, grain boundary, hot injection synthesis, modified polyol process, oxygen reduction reaction, proton exchange membrane fuel cell, Pt3Co alloy, twin boundary, valance band X-ray photoelectron spectroscopy}, issn = {1613-6810}, doi = {10.1002/smll.202500954}, author = {Singh, Mayank U. and Jadhav, Swapnil D. and Shivankar, Bhavana R. and Pandikassala, Ajmal and Kumar, Yogesh and Krishnamurty, Sailaja and Vinod, C. P. and Kurungot, Sreekumar} } @article {49551, title = {Hybrid pincer (PNN)Ni(II) complex catalyzed selective C-H alkylation of pyridones using unactivated alkyl chlorides}, journal = {ACS Catalysis}, volume = {15}, year = {2025}, month = {FEB}, pages = {2987-2999}, type = {Article}, abstract = {

The use of readily accessible unactivated alkyl chlorides in the alkylation reaction to install valuable alkyl and methyl motifs into privileged heterocycles is an underdeveloped area. Herein, we report the regioselective C-H alkylation of diverse pyridones employing challenging unactivated alkyl chlorides as coupling partners, enabled by a strategically developed quinolinyl-based pincer (Ph2PNNQ)Ni(II) complex. The air-stable nickel catalyst is highly effective for the selective alkylation of functionalized 2-pyridones with both primary and secondary alkyl chlorides as well as for the unexpected C6 methylation, furnishing a wide range of 6-alkyl-2-pyridone scaffolds (78 examples). Remarkably, the alkyls bearing biologically and pharmacologically significant motifs, such as pterostilbene, nonyl phenol, sesamol, estrone, vitamin E, stigmasterol, cholesterol, and diosgenin, were compatible under this catalytic approach. The insights into the mechanism suggest that the alkylation reaction follows a Ni(II)/Ni(III)/Ni(IV) pathway involving the crucial two-step, one-electron oxidative addition of alkyl chloride. Several control studies, kinetics, and EPR analyses were performed to understand the detailed reaction pathway, further supported by density functional theory calculations.

}, keywords = {alkyl chlorides, C-H/C-Cl activation, hybrid pincer ligand, Mechanism, Nickel, pyridones}, issn = {2155-5435}, doi = {10.1021/acscatal.4c07173}, author = {Verma, Suryadev K. and Samal, Pragnya Paramita and Pradhan, Chandini and Pandey, Dilip K. and Krishnamurty, Sailaja and Punji, Benudhar} } @article {49908, title = {Hydrodeoxygenation of guaiacol to cyclohexanol using noble metal-supported Ni-based perovskite-derived catalysts}, journal = {ChemCatChem}, volume = {17}, year = {2025}, month = {AUG}, type = {Article}, abstract = {

This study focuses on the role of noble metal-doped Ni-based perovskites, specifically LaNiO3 and NiTiO3 catalysts in the hydrodeoxygenation (HDO) of guaiacol. The findings demonstrate that reduced Ru-LaNiO3 catalyst achieved superior performance with 100\% guaiacol conversion and a 75\% selectivity toward cyclohexanol, compared to reduced Ru-NiTiO3, which achieved only 43\% conversion and 25\% cyclohexanol selectivity under identical conditions (240 degrees C, 30 bar H2, and 4 h). High-resolution transmission electron microscopic (HR-TEM) analysis reveals that LaNiO3-supported catalysts exhibit better metal dispersion and smaller nickel nanoparticle sizes compared to NiTiO3-supported counterparts. X-ray photoelectron spectroscopy (XPS) analysis shows that the reduction of nickel and noble metals is more facile on LaNiO3. Additionally, the O 1s XPS profile for reduced Ru-LaNiO3 indicates a higher proportion of lattice oxygen (OLat similar to 79\%) and a lower proportion of oxygen vacancies (OVac similar to 21\%) compared to other catalyst systems. The optimized OLat/OVac ratio is shown to be critical for the effective HDO of guaiacol. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) demonstrates a high HDO reaction rate using reduced Ru-LaNiO3 than reduced Ru-NiTiO3, with cyclohexanol formation attributed to the keto-enol tautomerization pathway. Overall, this study underscores the critical roles of oxygen vacancies, metal dispersion, and metal-metal oxide interactions in the HDO of guaiacol.

}, keywords = {Cyclohexanol, Guaiacol, Hydrodeoxygenation, In-situ DRIFT, Ni-based perovskites}, issn = {1867-3880}, doi = {10.1002/cctc.202500577}, author = {Marimuthu, Prabu and Raja, Thirumalaiswamy and Vinu, Ravikrishnan} } @article {49573, title = {Hydrogel electrolyte-mediated in situ Zn-anode modification and the Ru-RuO2/NGr-coated cathode for high-performance solid-state rechargeable Zn-air batteries}, journal = {ACS Applied Materials \& Interfaces}, volume = {17}, year = {2025}, month = {JAN}, pages = {3188-3204}, type = {Article}, abstract = {

This work aims to deal with the challenges associated with designing complementary bifunctional electrocatalysts and a separator/membrane that enables rechargeable zinc-air batteries (RZABs) with nearly solid-state operability. This solid-state RZAB was accomplished by integrating a bifunctional electrocatalyst based on Ru-RuO2 interface nanoparticles supported on nitrogen-doped (N-doped) graphene (Ru-RuO2/NGr) and a dual-doped poly(acrylic acid) hydrogel (d-PAA) electrolyte soaked in KOH with sodium stannate additive. The catalyst shows enhanced activity and stability toward the two oxygen reactions, i.e., oxygen reduction and evolution reactions (ORR and OER), with a very low potential difference (Delta E) of 0.64 V. The computational insights bring out the electronic factors contributing to the enhanced catalytic activity of Ru-RuO2/NGr based on the charge density difference (CDD) between the interfaces. The disadvantages of the existing solid-state RZABs, such as their limited lifespan brought on by passivation, dendritic growth, corrosion, and shape change, have also been taken into account. The introduction of the stannate additive to the electrolyte induced an in situ Zn-anode modification, which subsequently improved the interfacial stability of the ZABs and, hence, the battery life cycles. The experimental observations reveal that, during the charging process, the Sn nanoparticles enable the homogeneous Zn deposition on the surface of the anode. Thus, the in situ Zn-anode surface modification assisted in achieving a high-rate cycle capability, viz., the homemade catalyst-based system exhibited continuous charge-discharge cycles for 20 h at a current density of 2.0 mA cm-2, with each cycle lasting for 5 min.

}, keywords = {Bifunctional Electrocatalyst, Core-ShellStructure, DFT study, electrolyte additive, Hydrogel, solid-state rechargeable zinc-airbattery, X-ray absorption spectroscopy}, issn = {1944-8244}, doi = {10.1021/acsami.4c14231}, author = {Kharabe, Geeta Pandurang and Verma, Tushar and Barik, Sidharth and Urkude, Rajashri R. and Ayasha, Nadeema and Ghosh, Biplab and Krishnamurty, Sailaja and Kurungot, Sreekumar} } @article {49721, title = {Hydrogenation of CO2 catalyzed by thermally decomposed cobalt-containing alkaline earth metal carbonates}, journal = {Energy \& Fuels}, volume = {39}, year = {2025}, month = {JUN}, pages = {12982-12991}, type = {Article}, abstract = {

CO2 hydrogenation over Co catalysts supported on alkaline earth metal oxides was investigated. The catalysts were prepared by thermally decomposing alkaline metal carbonates CoMCO3, where M = Mg, Ca, Sr, and Ba, in H2. During the thermal activation, contingent upon the thermal stability of the precursor, it transformed into a composite of metal oxides, metals, and undecomposed metal carbonates. The thermal activation temperature, the ratio of CO2 to H2, the composition, and the basicity of the catalyst all played a significant role in influencing the conversion of CO2 and the selectivity to CH4. Among the various Co-containing alkaline earth metal carbonate precursors, CoCaCO3 activated at 400 degrees C yielded the highest steady-state CO2 conversion of 54\% with a CH4 selectivity of 89.8\% throughout 28 h in the reaction stream containing a 1:4 ratio of CO2 and H2. Detailed characterization showed that the CaCo-400 catalyst contained metallic Co, CaO, and undecomposed CaCO3 phases. The study assumes significance in understanding the role of the composition of catalysts in the formation of CO2 hydrogenation.

}, issn = {0887-0624}, doi = {10.1021/acs.energyfuels.5c01793}, author = {Gupta, Sharad and Vinod, C. P. and Poupin, Christophe and Jagadeesan, Dinesh} } @article {49807, title = {Hypersilylsilylene-supported Ni(0) toluene and Ni(II) complexes with catalytic application}, journal = {Organometallics}, volume = {44}, year = {2025}, month = {NOV}, pages = {2646-2653}, type = {Article}, abstract = {

The reaction of Ni(COD)2 with [PhC(NtBu)2SiSi(SiMe3)3] (1) in toluene results in the formation of an 18-electron silylene-Ni(0) toluene complex (2). The analogous reaction with 1,3-DFB instead of toluene affords the C-H activation followed by ring walking leading to the allylic cyclooctene adduct, the (eta 3-C8H13)Ni(II) complex (3). DFT calculations were carried out to elucidate the mechanism as well as to gain insight into why 1,3-DFB undergoes C-H bond activation instead of C-F bond activation. The use of NiCl2DME permits access to 16-electron (tetrylene)2NiCl2 (Si(4) and Ge(5)) species, and 4 was later used as a catalyst for the C-N coupling reaction.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.5c00303}, author = {Ajithkumar, V. S. and Bisai, Milan Kumar and Ghanwat, Pratiksha B. and Raj, K. Vipin and Singh, Geetika and Vanka, Kumar and Sen, Sakya S.} } @article {49678, title = {In silico designing of electrocatalysts for hydrogen evolution reaction: a focus on titanium metal-based diboride monolayers}, journal = {International Journal of Hydrogen Energy}, volume = {133}, year = {2025}, month = {JUN }, pages = {91-100}, type = {Article}, abstract = {

Enhancing the efficiency of Hydrogen Evolution Reaction (HER) using chemically modified electrocatalytic titanium diboride surfaces with transition metal-based Single Atom Catalysts (SACs) is illustrated using Density Functional Theory (DFT) based methods employing solvent effects. With higher surface concentrations of nonmetal boron rather than titanium metal, these highly conductive, extremely hard, chemically, and thermally stable electrocatalysts are more cost-effective and superior to their MBene analogs. A systematic analysis of these transition metal-based SACs from the 3d, 4d, and 5d groups embedded in TiB2 monolayer for its HER activity reveals the reduction in limiting potential. As the most effective SAC for improved HER, Zn@TiB2 SAC has a limiting potential of 0.08 eV in acidic and 0.21 eV in alkaline media. The higher exchange current density of Zn@TiB2 (5.74 x 10-5 A cm-2), which exceeds most previously reported electrocatalysts, indicates exceptional HER performance. This work shows that transition metal boride electrocatalysts are economically viable for HER and pave a path for experimentalists.

}, keywords = {AIMD, D -band center, DFT, HER, SAC}, issn = {0360-3199}, doi = {10.1016/j.ijhydene.2025.04.482}, author = {Shivankar, Bhavana R. and Verma, Tushar Singh and Krishnamurty, Sailaja} } @article {49863, title = {An integrated paradigm to understand the antibacterial and antifungal potential of bimetallic core-shell platinum silver (Pt@Ag) nanoparticles: A one health approach}, journal = {Microbial Pathogenesis}, volume = {209}, year = {2025}, month = {DEC}, pages = {108120}, type = {Article}, abstract = {

The concurrent occurrence of various microbial infections escalates the need to develop new treatments that can tackle multiple microbes and improve clinical outcomes. This study reports the synthesis and comprehensive evaluation of core-shell platinum-silver nanoparticles (Pt@AgNPs) designed to elucidate the antimicrobial effects while ensuring biocompatibility. The synthesis protocol was meticulously optimized to investigate the impact of precursor concentrations and reagent conditions. High-end characterization confirmed the formation of a welldefined core-shell structure with spherical morphology, crystalline nature, a face-centred cubic (FCC) lattice, high monodispersity, and stability, with a mean size of 20.344 +/- 4.492 nm. The antimicrobial potential of Pt@AgNPs was validated through a minimum inhibitory concentration (MIC) assay, revealing potent activity with MIC values of 15.6 mu g/mL for Pseudomonas aeruginosa and Staphylococcus aureus and 3.9 mu g/mL for Escherichia coli. Antibiofilm assay demonstrated significant inhibition of biofilm formation by P. aeruginosa at concentrations as low as 3.9 mu g/ml. The nanoparticles also exhibited notable antifungal activity, as indicated by an inhibition of 65.19 \% for Aspergillus niger and 61.82 \% for Fusarium verticillioides. Furthermore, hemocompatibility was noticed with the hemolysis assay, and the antioxidant properties of nanoparticles, assessed through the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, underscored their potential to mitigate oxidative stress. This integrative study positions Pt@AgNPs as a promising platform for combating the occurrence of co-infections. The core-shell nanoparticle serves as a versatile tool in antimicrobial defence, exhibiting antibacterial, antifungal, antibiofilm, and antioxidant activity. Thus, it highlights their commercial translational potential as a next-generation antimicrobial intervention.

}, keywords = {Antibacterial, antibiofilm, antifungal, Antioxidant, Co-infections, Pt@Ag nanoparticles}, issn = {0882-4010}, doi = {10.1016/j.micpath.2025.108120}, author = {Bamb, Aagam Lalit and Varma, Sanjana and Gade, Tejas Subhash and Palaskar, Shahaji and Vamkudoth, Koteswara Rao and Vyawahare, Niraj and Chaudhari, Pallavi M. and Chaudhari, Bhushan P.} } @article {49552, title = {Investigating the visible range photoresponse of an organic single-crystal analogue of the green fluorescent protein}, journal = {Nanoscale}, volume = {17}, year = {2025}, month = {APR}, pages = {8614-8623}, type = {Article}, abstract = {

The growing demand for lightweight, flexible, semi-transparent and low-cost photodetectors (PDs) in wearable electronics and optical communication systems has prompted studies to investigate organic materials as feasible alternatives to conventional inorganic PDs. However, modern organic PDs often face responsivity, detectivity, and photoresponse speed limitations, particularly in the visible range. Here, we present the photoresponse of an organic single-crystal analogue of the green fluorescent protein (GFP) chromophore photodetector, fabricated on a silicon nitride substrate. A significant increase in photocurrent was detected upon illumination with visible wavelengths (532 nm, 630 nm, and halogen light). A remarkably consistent and repeatable photoresponse was obtained during the ON and OFF illumination cycles. The device showed the dependence of photocurrent on the applied bias voltages. The measured photocurrent, responsivity, detectivity, rise time, decay time, noise equivalent power and external quantum efficiency are studied for different wavelengths. Strikingly, the fabricated device demonstrates excellent performance in the visible region compared to several conventional organic and inorganic PDs. The observed responsivity and detectivity values for the device are 98 mA W-1 and 7.94 x 108 Jones, respectively. Furthermore, the device also exhibits rapid photoresponse dynamics with a rise time of 180 ms and a decay time of 152 ms. The excellent photodetection features indicate that the single crystal GFP could serve as a versatile broadband material for future applications in optoelectronics.

}, issn = {2040-3364}, doi = {10.1039/d4nr05252h}, author = {Virole, Vishal and Dabke, Niteen and Verma, Sahil and Kumar, Ajay and Pandya, Rinu and Husale, Sudhir and Vanka, Kumar and Gonnade, Rajesh and Kanawade, Rajesh} } @article {49597, title = {Iron-catalyzed chemoselective reduction of enimines to N-Allylic amines via hydrosilylation}, journal = {Asian Journal of Organic Chemistry}, volume = {14}, year = {2025}, month = {MAY}, type = {Article}, abstract = {

Chemoselective hydrosilylation of unsaturated imines is challenging as the two double bonds compete for the reaction. Here in, we report an iron-catalyzed chemoselective hydrosilylation of enimines leading to the generation of allyl amines in the presence of phosphine ligand. A low-valent Fe(0) complex [(BDA)Fe(CO)3] catalyzed the hydrosilylation of enimine at room temperature and exhibited broad substrate scope including a variety of enimine (cinnamylimine, allylimine) and ketimine. Mechanistic investigations revealed that the reaction proceeds through an oxidative addition of the silane compound, leading to the formation of an iron hydride intermediate. Subsequently, a two-electron pathway facilitates the hydrosilylation of the enimine substrate. This has been supported by preparing a well-defined Fe(II)-silane complex and using it as a catalyst control. Based on experimental and computational investigations, a plausible Chalk-Harrod-type mechanism is proposed.

}, keywords = {Cinnamyl amine, Imine hydrosilylation, iron catalysis, Iron hydride, Phosphine}, issn = {2193-5807}, doi = {10.1002/ajoc.202400762}, author = {Tewari, Tanuja and Shaikh, Maulali H. and Sharma, Himanshu and Vanka, Kumar and Chikkali, Samir H.} } @article {49581, title = {Low-cost gelatin/collagen scaffolds for bacterial growth in bioreactors for biotechnology}, journal = {Applied Microbiology and Biotechnology}, volume = {109}, year = {2025}, month = {MAY}, pages = {113}, type = {Article}, abstract = {

A wide array of pharmaceutical and industrial products available in today{\textquoteright}s market stems from bioreactors. Meeting the escalating demand for these products necessitates significant enhancements in biotechnological processes. This study focuses on developing cost-effective scaffolds designed explicitly for use within bioreactors, employing commonly used polymers such as gelatin and collagen. Bacterial proliferation assays involving Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa were conducted to assess the effectiveness of these scaffolds. The scaffolds were produced by electrospinning polymeric solutions with varying concentrations of gelatin and collagen and were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Results revealed that scaffolds with 15\% gelatin increased the 24-h proliferation of S. aureus, P. aeruginosa, and E. coli by 52\%, 35\%, and 20\%, respectively. In the case of E. coli, scaffolds with lower gelatin concentrations (1-10\%) were more effective, leading to 35-55\% proliferation growth. These findings highlight the potential application of gelatin/collagen scaffolds in fabricating industrial products derived from these bacteria.

}, keywords = {Bacterial cell proliferation, collagen, gelatin, Polymeric electrospinning, scaffolds}, issn = {0175-7598}, doi = {10.1007/s00253-025-13491-5}, author = {Pompa-Monroy, Daniella Alejandra and Vera-Graziano, Ricardo and Dastager, Syed G. and Perez-Gonzalez, Graciela Lizeth and Bogdanchikova, Nina and Iglesias, Ana Leticia and Villarreal-Gomez, Luis Jesus} } @article {49693, title = {Magnesium-catalyzed primary, secondary, and tertiary amide hydroboration}, journal = {Inorganic Chemistry}, volume = {64}, year = {2025}, month = {JUN}, pages = {13405-13414}, type = {Article}, abstract = {

Catalytic hydroboration of amides is highly important because the resultant amines are commonly found in natural products, pharmaceuticals, agrochemicals, dyes, and other applications. In comparison to the conventional reduction of amides using (over)stoichiometric reductants, hydroboration of amides using magnesium compounds represents a green and sustainable approach because magnesium is both Earth abundant and environmentally benign. However, there is only one report on magnesium-catalyzed deoxygenative hydroboration of secondary and tertiary amides. Here, we describe the synthesis and structural authentication of two new magnesium compounds (1 and 2) featuring a flexible PNP ligand and the utilization of 2 as a catalyst for the pinacolborane-mediated reduction of primary, secondary, and tertiary amides to amines. The reaction scope is explored, and a mechanism is proposed based on experimental and theoretical insights.

}, issn = {0020-1669}, doi = {10.1021/acs.inorgchem.5c01787}, author = {Mahata, Biplab and Devaraj, V. and Dash, Soumya Ranjan and Gonnade, Rajesh G. and Vanka, Kumar and Sen, Sakya S.} } @article {49518, title = {Magnesium-ligand cooperation in breaking the O-H and C-H bonds of water and diazoalkane}, journal = {Organometallics}, volume = {44}, year = {2025}, month = {MAR}, pages = {875-881}, type = {Article}, abstract = {

In our previous paper, we reported that the reaction of a tridentate nacnac ligand with a pendant picolyl group, with KHMDS and MgI2, resulted in the formation of a homoleptic hexacoordinate magnesium compound. Here, we show that the analogous reaction of the ligand with CH3MgBr led to a heteroleptic magnesium bromide species (1). Attempts to generate the magnesium hydride species from 1 led to the dearomatization of the pyridine ring, and the resulting product was a magnesium hydroxide (3) presumably generated due to an adventitious amount of water. The reaction of the ligand with nBu2Mg afforded a unique dearomatized magnesium species (2) in high yield. Theoretical calculations reveal the presence of a nonbonding orbital on the magnesium, susceptible to nucleophilic attack. Indeed, the reaction of 2 with H2O/D2O cleaves the O-H/D bond via magnesium-ligand cooperation and generates a magnesium hydroxide (4 and 5). In addition, 2 reacts with Me3SiCHN2 and cleaves the C-H bond to generate another unusual, well-defined magnesium compound with a bridging isocyanide moiety (6) via migration of the SiMe3 group from the carbon to the nitrogen atom. The latter can be described as a dimer of magnesium isocyanamide. DFT calculations were performed to understand the electronic structures of the synthesized molecules.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.5c00031}, author = {Sharma, Vishal and Dash, Soumya Ranjan and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {49399, title = {Manganese-mediated cascade radical oxidative cyclization/1,6-conjugate addition of unsaturated oximes with p-quinone methides: facile access to β,β-diarylmethine substituted isoxazolines}, journal = {Chemistry-An Asian Journal}, volume = {20}, year = {2025}, month = {JAN}, type = {Article}, abstract = {

A simple and efficient strategy for the synthesis of structurally diverse beta,beta-diarylmethine substituted isoxazoline derivatives have been developed. This approach employs a manganese-promoted oxidative cyclization coupled with a 1,6-conjugate addition of unsaturated oximes to p-quinone methides. The key features of this study include the formation of C-O and C-C bonds through intramolecular and intermolecular interactions, facilitated by in situ generated iminoxyl radicals. beta,beta-diarylmethine substituted isoxazolines, bearing a wide range of functional groups, were isolated in high yields.

}, keywords = {p-Quinone methide, diarylmethine substituted isoxazolines, Iminoxy radical, Manganese catalyzed}, issn = {1861-4728}, doi = {10.1002/asia.202401079}, author = {Vara, Vijay and Thete, Kishor R. and Ghotekar, Ganesh S. and Muthukrishnan, M.} } @article {49704, title = {Manganese(i)-catalyzed dehydrogenative borylation of terminal alkynes}, journal = {Dalton Transactions}, volume = {54}, year = {2025}, month = {JUL}, pages = {10426-10432}, type = {Article}, abstract = {

Compounds containing carbon-boron bonds serve as valuable intermediates for constructing more complex molecules by transforming these bonds into other carbon-element bonds. The catalytic dehydrogenative borylation of carbon-hydrogen bonds using HBpin presents an appealing method for synthesizing carbon-boron bonds. While this approach has been extensively explored with noble metals for various types of carbon-hydrogen bonds, its application with manganese-based catalysts remains rare. This study explores a dehydrogenative borylation process employing an Earth-abundant transition metal catalyst, FcbpyMn(CO)3Br (Mn(i)), in combination with HBpin under mild conditions. Arylalkynes featuring electron-withdrawing, electron-donating, and heteroaryl substituents yielded good to excellent results. Thorough DFT calculations were performed to understand the mechanism.

}, issn = {1477-9226}, doi = {10.1039/d5dt00577a}, author = {Ghanwat, Pratiksha B. and Bora, Debashree and Pandya, Rinu and Vanka, Kumar and Saha, Biswajit and Sen, Sakya S.} } @article {49534, title = {Metal deficiency tuned charge transfer in intermetallic Ni2-xSn (x =0.37-0.65) enhances selective conversion of furfural to furfuryl alcohol towards the theoretical limit}, journal = {Journal of Materials Chemistry A}, volume = {13}, year = {2025}, month = {FEB}, pages = {6042-6048}, type = {Article}, abstract = {

Heterogeneous catalysis facilitated by intermetallic nanoparticles has recently been the subject of increased scrutiny, given the enhanced selectivity and stability they bestow on many chemical reactions compared to their monometallic components. This paper explores a series of Ni-Sn (Ni2-xSn, where x = 0.65, 0.5, 0.37) intermetallic compounds supported on a high-surface-area support, SBA-15, as catalysts for the selective hydrogenation of furfural to furfuryl alcohol. Rietveld refinements of the X-ray diffraction data show catalysts with mixed intermetallic phases that assist in the catalysis. At the same time, X-ray photoelectron spectroscopy (XPS) studies and X-ray absorption studies indicate the role played by charge transfer from Sn to Ni for the catalysis. Selectivity to the desired furfuryl alcohol in all the intermetallic samples was high (\>97\%), but Ni1.35Sn had a relatively lower conversion than the other intermetallic compounds.

}, issn = {2050-7488}, doi = {10.1039/d4ta06383j}, author = {Cherevotan, Arjun and Singh, Ashutosh Kumar and Yadav, Anish and Maligal-Ganesh, Raghu V. and Raj, Jithu and Pulparambil, Anu and Goud, Devender and Vinod, Chathakudath P. and Peter, Sebastian C.} } @article {49532, title = {MH-PCTpro: a machine learning model for rapid prediction of pressure-composition-temperature (PCT) isotherms}, journal = {Iscience}, volume = {28}, year = {2025}, month = {APR }, pages = {112251}, type = {Article}, abstract = {

We present a machine-learning powered Metal Hydride{\textquoteright}s Pressure-Composition-Temperature isotherm Predictor (MH-PCTpro) for metal compositions. To train the MH-PCTpro, an experimental database of PCT isotherms is built from published literature. The database comprises over 14,000 data points extracted from 237 PCT isotherms representing 138 distinct compositions. The dataset encompasses more than 25 elements and spans a broad spectrum of absorption temperatures (263-653 K) and hydrogen pressures (0.001-40 MPa). The model is validated on a wide range of alloy families and its predictions are consistent with experimental results. The model also captures temperature-dependent variations in plateau pressure, enabling determination of enthalpy and entropy of hydride formation through Van{\textquoteright}t Hoff plots. Hence, MH-PCTpro can be used as an ML tool for guiding PCT experiments, offering PCT isotherm predictions and valuable thermodynamic insights into materials suitable for solid-state hydrogen storage.

}, doi = {10.1016/j.isci.2025.112251}, author = {Verma, Ashwini and Joshi, Kavita} } @article {49619, title = {Mimicking characteristics of cast iron for enhanced electrocatalytic dehydrogenation of methane}, journal = {Fuel}, volume = {381}, year = {2025}, month = {FEB}, pages = {133674}, type = {Article}, abstract = {

Enhancing the efficiency of methane dehydrogenation through chemical modification of electrocatalytic iron surfaces with impurities that resemble cast iron properties is demonstrated computationally using Density Functional Theory methodologies. Investigating methane dehydrogenation on thermally stable Fe surfaces with discrete planes and anchoring impurities such as Al, C, and Si minimized reduction barriers. Electrochemical treatment of methane on these robust surfaces yields clean hydrogen and carbon-based compounds, such as carbon nanomaterials and carbon black. As for the most efficient active sites for enhanced methane dehydrogenation, the active plane 100 with 5.5 \% C impurities and 0.51 eV reduction barrier is determined to be the most dependable, followed by the active plane 110 with 5.5 \% Si impurities and the lower 0.98 eV reduction barrier. Utilizing CI-NEB (Nudged Elastic Band), the dissociation barrier investigation established the electrolytic catalysts{\textquoteright} performance. This work paves the way for experimentalists and demonstrates the economic viability of Fe-based catalysts for the Catalytic Dehydrogenation of Methane.

}, keywords = {carbon black, Density Functional Theory (DFT), Dry methane reforming (DMR), Electrochemical methane dehydrogenation, Fe surface catalyst}, issn = {0016-2361}, doi = {10.1016/j.fuel.2024.133674}, author = {Verma, Tushar Singh and Devi, R. Nandini and Krishnamurty, Sailaja} } @article {49985, title = {Molecular determinants of Neu5Ac binding to a tripartite ATP independent periplasmic (TRAP) transporter}, journal = {Elife}, volume = {13}, year = {2025}, month = {FEB}, type = {Article}, abstract = {

N\ -Acetylneuraminic acid (Neu5Ac) is a negatively charged nine-carbon amino sugar that is often the peripheral sugar in human cell-surface glycoconjugates. Some bacteria scavenge, import, and metabolize Neu5Ac or redeploy it on their cell surfaces for immune evasion. The import of Neu5Ac by many bacteria is mediated by tripartite ATP-independent periplasmic (TRAP) transporters. We have previously reported the structures of SiaQM, a membrane-embedded component of the\ Haemophilus influenzae\ TRAP transport system, (Currie et al., 2024). However, none of the published structures contain Neu5Ac bound to SiaQM. This information is critical for defining the transport mechanism and for further structure-activity relationship studies. Here, we report the structures of\ Fusobacterium nucleatum\ SiaQM with and without Neu5Ac. Both structures are in an inward (cytoplasmic side) facing conformation. The Neu5Ac-bound structure reveals the interactions of Neu5Ac with the transporter and its relationship with the Na+\ binding sites. Two of the Na+-binding sites are similar to those described previously. We identify a third metal-binding site that is further away and buried in the elevator domain. Ser300 and Ser345 interact with the C1-carboxylate group of Neu5Ac. Proteoliposome-based transport assays showed that Ser300-Neu5Ac interaction is critical for transport, whereas Ser345 is dispensable. Neu5Ac primarily interacts with residues in the elevator domain of the protein, thereby supporting the elevator with an operator mechanism. The residues interacting with Neu5Ac are conserved, providing fundamental information required to design inhibitors against this class of proteins.

}, doi = {10.7554/eLife.98158.}, author = {Goyal, Parveen and Dhanabalan, KanagaVijayan and Scalise, Mariafrancesca and Friemann, Rosmarie and Indiveri, Cesare and Dobson, Renwick C. J. and Vinothkumar, Kutti R. and Ramaswamy, Subramanian} } @article {49866, title = {A Molecular View of Lipid Nanoparticles: Insights into their Morphology and Structural Plasticity}, journal = {Small}, volume = {21}, year = {2025}, month = {OCT}, pages = {e05404}, type = {Review}, abstract = {

Lipid nanoparticles (LNPs) have emerged as versatile delivery vehicles for nucleic acid-based therapeutics. Despite their increasing importance, the molecular structure and physico-chemical characteristics of LNPs still remain unclear. In this review, the structural features and phase behavior of LNPs are highlighted. First, the various compositional elements, such as cationic lipids, helper lipids and sterols are discussed, illustrating their functional roles in the self-assembly and stability of LNPs. Molecular models derived from experimental and computational approaches are discussed to provide insights into the structural organization of the LNP components. The influence of sterols and helper lipids in modulating LNP architectures, including membrane fluidity and phase separation, which are key factors for both fusion potential and endosomal escape, is discussed. Variations in sterol content and headgroup chemistry can induce transitions from lamellar to non-lamellar structures, thereby influencing gene transfection outcomes. Further, how cationic lipids induce structural phase transitions, such as lamellar-to-hexagonal and inverse cubic rearrangements under physiological and acidic pH, mimicking extracellular and endosomal conditions, are described. These transitions play a pivotal role in ribonucleic acid (RNA) release and membrane fusion events. This comprehensive review allows to reconcile molecular and structural dynamics that would be necessary for rational design of RNA delivery systems.

}, keywords = {drug delivery, lipid nanoparticles, phase separation, vaccine delivery}, issn = {1613-6810}, doi = {10.1002/smll.202505404}, author = {Porte, Sudha and Vadhana, V. and Sengupta, Durba} } @article {49944, title = {Morphology rearrangement by mixing of internally hydrogen-bonded nanoparticles comprising triazine-based amphiphilic diblock copolymers}, journal = {Macromolecules}, volume = {58}, year = {2025}, month = {NOV }, pages = {11611-11620}, type = {Article}, abstract = {

The self-assembly of block copolymers holds significant potential for designing functional nanoparticles in materials science, nanomedicine, and nanotechnology. While the self-assembly of amphiphilic diblock copolymers is relatively well understood, the influence of specific supramolecular interactions, particularly hydrogen bonding, in directing their morphological behavior remains largely unexplored. In this study, it was demonstrated that nanoparticles self-assembled in water/DMSO (75/25 vol/vol; 2 mg/mL) comprising amphiphilic diblock copolymers with a small amount of triazine-based guanine-cytosine (GCB) motifs incorporated in the hydrophobic block can undergo spontaneous rearrangement into new morphologies on mixing. For example, mixing spheres with vesicles resulted in spontaneous transformation into worms (nanofibers), and this transformation was accelerated at elevated temperature. The hydrogen bonding motif features three complementary hydrogen bonding sites on either side of the nucleobase unit, thereby having a Janus character. Amphiphilic diblock copolymers comprising dimethyl acrylamide (hydrophilic segment) and n-butyl acrylate (hydrophobic segment) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization with a variable content of acrylate monomer functionalized with the Boc-protected form of the GCB motif as part of the hydrophobic segment. The present work represents a completely new approach for controlling self-assembly processes, paving the way for the design of functional nanoparticles for a range of applications.

}, issn = {0024-9297}, doi = {10.1021/acs.macromol.5c01472}, author = {Haque, Farah and Thompson, Steven W. and Ishizuka, Fumi and van der Tol, Joost J. B. and Singh, Dharmendra and Sanjayan, Gangadhar J. and Zetterlund, Per B.} } @article {49677, title = {Nickel-catalyzed regioselective C--H alkynylation of pyridones and isoquinolinones using alkynyl bromides}, journal = {ChemCatChem}, volume = {17}, year = {2025}, month = {JUN}, type = {Article}, abstract = {

A straightforward and efficient protocol for the regioselective C \& horbar;H alkynylation of 2-pyridones and isoquinolinones with bromoalkynes under nickel catalysis is described. The alkynylation reaction is enabled by a simple and inexpensive Ni(OTf)2/tBubpy catalyst system and uses easily accessible bromoalkynes. The protocol demonstrates a broad substrate scope with up to 95\% yield (42 examples) and accommodates synthetically valuable functionalities, such as halides, trifluoromethyl, nitrile, ether, thioether, alkyl silanes, and alkene, as well as heteroarene moieties like pyridinyl, furanyl, and thiophenyl. The pyridinyl directing group on alkynylated 2-pyridones can be smoothly removed to give C6-alkynylated free NH-pyridone. Preliminary mechanistic studies suggest that the alkynylation proceeds via a 2e- oxidative addition pathway involving crucial C \& horbar;H activation.

}, keywords = {alkynylation, C \& horbar, H Activation, Mechanism, Nickel, pyridones}, issn = {1867-3880}, doi = {10.1002/cctc.202500338}, author = {Verma, Suryadev K. and Patil, Harshal R. and Punji, Benudhar} } @article {49882, title = {Optimisation of metallic bismuth nanoparticle supported Pt-Bi(x\%)/C hybrid electrocatalyst for cost effective and efficient hydrogen production in alkaline media}, journal = {International Journal of Hydrogen Energy}, volume = {161}, year = {2025}, month = {AUG}, pages = {150699}, type = {Article}, abstract = {

The present study employed a simple mechanochemical method followed by 24-h ultrasonication to synthesize oxide-free metallic bismuth (Bi) nanoparticles. This was further used to synthesize a Pt-Bi(x\%)/C (NC-x) hybrid electrocatalyst for the hydrogen evolution reaction in alkaline media. X-ray photoelectron spectroscopy and contact angle measurements reveal, Bi modifies the electronic structure and surface morphology of the Pt/C electrocatalyst, thus enhancing reaction kinetics and active site availability. The relative three-electrode study reveals that optimised NC-20 electrocatalyst reduces the overpotentials by 10.44 \% and enhances the current density by 53 \% compared to commercial Pt/C. The practical applicability of the NC-20 electrocatalyst was studied with the 13 cm2 single cell anion exchange membrane electrolyser. The catalyst demonstrates promising performance where the current density of NC-20//IrO2 relatively increases by 22.6 \% compared to standard Pt/ C//IrO2, and shows continuous production and stable performance when monitored for 30 h.

}, keywords = {AEM, Bismuth nanoparticles, electrocatalyst, Full cell electrolysis, hydrogen evolution reaction, water electrolysis}, issn = {0360-3199}, doi = {10.1016/j.ijhydene.2025.150699}, author = {Dokhe, Revati and Ugale, Atul and Dube, Onkar and Varpe, Vaibhav and Galave, Chaitanya and Hattale, Gangadhar and Kadam, Rutuja and Virole, Vishal and Kumar, Ajay and Husale, Sudhir and Natu, Varun and Shevate, Rahul and Kanawade, Rajesh} } @article {49549, title = {Optimization and mechanistic insights of zinc ascorbate catalyst for ring-opening polymerization of caprolactone using RSM methodology and DFT calculations}, journal = {Polymers for Advanced Technologies}, volume = {36}, year = {2025}, month = {APR}, pages = {e70182}, type = {Article}, abstract = {

Polycaprolactone (PCL) is an aliphatic polyester recognized for its exceptional versatility and biodegradability, which has garnered significant attention for a wide range of applications. This study presents an innovative methodology for the synthesis of PCL through the ring-opening polymerization (ROP) of epsilon-caprolactone (CL). The approach employs a biocompatible and environmentally benign organometallic zinc ascorbate complex as a catalyst. Derived from ascorbic acid, a well-established reducing agent, zinc ascorbate serves as a sustainable alternative to conventional tin-based catalysts, thereby mitigating environmental impact and enhancing safety measures. The catalyst operates effectively under solvent-free conditions and does not require initiators, achieving a high polymer conversion rate of approximately 79\%. The optimization of the reaction parameters was conducted using response surface methodology (RSM) employing a central composite design (CCD). The structural and chemical characterization of the catalyst as well as the resulting polymers was performed using proton nuclear magnetic resonance (1H NMR), Fourier-transform infrared spectroscopy (FTIR), and x-ray diffraction (XRD) analyses. Additionally, density functional theory (DFT) calculations elucidated a four-step coordination-insertion mechanism for the polymerization of cyclic lactones, with findings supported by Gibbs free energy, electrostatic potential, and non-covalent interactions. This study underscores the potential of zinc ascorbate as a reliable, nontoxic, and cost-effective catalyst, fulfilling the increasing demand for sustainable and efficient polymerization processes in commercial and biomedical applications.

}, keywords = {density function theory, Polycaprolactone, Response surface methodology, ring-opening polymerization, zinc ascorbate}, issn = {1042-7147}, doi = {10.1002/pat.70182}, author = {Naik, Sonali S. and Vedpathak, Shantanu and Nair, Kiran Sukumaran} } @article {49602, title = {Pair of dinuclear Fe(II) enantiomers: syntheses and structures of ΛΔ/ΔΛ-Bis(Dihydridoborate) complexes}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {31}, year = {2025}, month = {FEB }, type = {Article}, abstract = {

In our effort to establish a direct synthetic approach for bis(dihydridoborate) complexes of first-row transition metals, we have investigated the reactivity of [Cp*Fe(dppe)Cl] (dppe =1,2-bis(diphenylphosphino)ethane) with Na[BH3L] (L =2-mercaptopyridine (mp) and 2-mercaptobenzothiazole (mbz)) that led to the formation of iron(II) dihydridoborate complexes, [Cp*Fe{kappa 3-S,H,H-(H2BH(L))}] 1 a-b (L=mp (1 a) and L=mbz (1 b)). Further, in an attempt to isolate the bis(dihydridoborate) complex of iron by the insertion of borane into the kappa 2-N,S-chelated iron complex, [(dppe)Fe{kappa 2-N,S-(mp)}2] (2), we have isolated and structurally characterized a rare example of dimeric iron bis(dihydridoborate) complex, [Fe{kappa 3-S,H,H-(H2BH(mp))}2]2, Lambda Delta/Delta Lambda-3 as pair of enantiomers. Interestingly, these enantiomers Lambda Delta/Delta Lambda-3 have two trans-[Fe{kappa 3-S,H,H-(H2BH(mp))}2] moieties bridged through sulfur atoms of 2-mercaptopyridinyl ligands, where the iron centres are hepta-coordinated. The natural bond-orbital (NBO) analyses of Lambda Delta-3 and Delta Lambda-3 show considerable electron donation from the filled sigma B-H bonding orbital to vacant dz2 \${{d}_{{z}\<\^\>{2}}}\$ orbital of iron with a substantial contribution from the hydrogen atoms. The localized orbital bonding analysis (LOBA) method suggests that all the iron centres are in +2 oxidation state.

}, keywords = {B-H activation, Bis(dihydridoborate), Enantiomer, Heptacoordinate, iron}, issn = {0947-6539}, doi = {10.1002/chem.202404469}, author = {Kaur, Urminder and Gayen, Sourav and Sharma, Himanshu and Vanka, Kumar and Ghosh, Sundargopal} } @article {49411, title = {Palladium-catalyzed regioselective C(4)-H fluoroalkoxylation of indoles through weak chelation assistance}, journal = {ChemCatChem}, volume = {17}, year = {2025}, month = {JAN}, type = {Article}, abstract = {

Installing fluoroalkyl motifs into biorelevant indoles is particularly interesting due to their ubiquitous presence in drug molecules. Herein, we demonstrate the regioselective C4 fluoroalkoxylation of indoles using fluoroalcohols via palladium-catalyzed chelation-assisted C \& horbar;H activation. The weak chelating benzoyl moiety at the C3 position acts as a directing group for remote C(4)\& horbar;H fluoroalkoxylation of diversely substituted indoles. This methodology demonstrates a high level of regioselectivity and tolerates a range of crucial functional groups, yielding diverse trifluoroalkoxylated indoles in moderate to good yields. Removal of directing/protecting groups and further functionalization established the synthetic utility of the methodology. A preliminary mechanistic investigation is conducted by isolating the palladacycle intermediate and performing the deuterium scrambling study. The regioselective C4 fluoroalkoxylation of indoles with various fluoroalcohols is achieved by the palladium-catalyzed weak chelation assistance strategy. The reaction is compatible for a range of important functionalities and proceeds via the intermediacy of a six-membered palladacycle following a Pd(II)/Pd(IV) pathway. image

}, keywords = {C-H activation, indoles, Palladium, Regioselective, Trifluoroalkoxylation}, issn = {1867-3880}, doi = {10.1002/cctc.202401188}, author = {Vijaykumar, Muniyappa and Gonnade, Rajesh G. and Punji, Benudhar} } @article {49834, title = {Palladium(II)-catalyzed desymmetrization of 2-alkynylbenzoate-tethered cyclohexadienones for the synthesis of polycyclic compounds}, journal = {Organic Letters}, volume = {27}, year = {2025}, month = {MAY}, pages = {5429-5434}, type = {Article}, abstract = {

Pd-catalyzed cascade cyclization of 2-alkynylbenzoate-tethered cyclohexadienone was developed for the single step synthesis of isocoumarin-fused dihydrochromenones. This highly atom economical method proceeds via 6-endo-dig cyclization of tert-butyl benzoate with a tethered alkyne. By modulating the reaction solvent and metal catalyst, the methodology was diverted for the purposeful synthesis of either of the E/Z tetra-substituted alkenes.

}, issn = {1523-7060}, doi = {10.1021/acs.orglett.5c01396}, author = {Rai, Archana and Bajpai, Priyam and Gamidi, Rama Krishna and Vanka, Kumar and Das, Utpal} } @article {49790, title = {Phosphine-catalyzed nucleophilic ring opening of cyclopropenones with sulfoximines to access N-α,β-unsaturated acyl sulfoximines}, journal = {Journal of Organic Chemistry}, volume = {90}, year = {2025}, month = {AUG}, pages = {10643-10653}, type = {Article}, abstract = {

Herein, we describe the formation of biologically relevant N-alpha,beta-unsaturated acyl sulfoximines via phosphine-catalyzed C-C bond activation of cyclopropenones with weakly nucleophilic sulfoximines. The new process does not require a transition metal or external oxidant and displays high regioselectivity and exclusive E-selectivity. Other salient features of the method are a broad substrate scope, high compatibility with various functional groups, and high atom economy.

}, issn = {0022-3263}, doi = {10.1021/acs.joc.5c00883}, author = {Thete, Kishor R. and Vara, Vijay and Khan, Akram A. and Muthukrishnan, M.} } @article {49971, title = {Precision integrated identification of predictive first-trimester metabolomics signatures for early detection of gestational diabetes mellitus}, journal = {Cardiovascular Diabetology}, volume = {24}, year = {2025}, month = {NOV }, pages = {434}, type = {Article}, abstract = {

Background and aimGestational diabetes mellitus (GDM), a common pregnancy-related metabolic disorder, often goes undiagnosed until the second trimester, limiting early intervention opportunities. Given the higher prevalence of GDM in India, there is a critical need to investigate metabolomic biomarkers among Asian Indians, who exhibit greater insulin resistance and are predisposed to developing type 2 diabetes at an earlier age. This study aimed to identify early pregnancy metabolomic signatures predictive of GDM. MethodsAmong 2115 pregnant women from the STratification of Risk of Diabetes in Early pregnancy (STRiDE) study, we performed untargeted metabolomic profiling using UPLC-MS/MS at early pregnancy (\< 16 weeks) plasma samples from 100 women-comprising 50 with GDM and 50 normal (without GDM) based on oral glucose tolerance test (OGTT) at 24-28 weeks. Statistical and machine learning approaches, including logistic regression and random forest (RF), were applied to identify GDM-associated metabolites and construct predictive models. Pathway enrichment analysis was conducted using KEGG database annotations. ResultsA total of 49 metabolites were significantly associated with GDM, primarily involving lipid classes such as phosphatidylcholines, sphingomyelins, and triacylglycerols. RF analysis identified a panel of eight metabolites that achieved best predictive performance (AUC 0.880; 95\% CI: 0.809-0.951) for GDM. When combined with conventional clinical risk factors, the integrated model showed comparable prediction of GDM with AUC 0.88;: 95\% CI: 0.810-0.952). Enrichment analysis highlighted dysregulated pathways including glycerophospholipid and sphingolipid metabolism, autophagy, and insulin resistance. ConclusionThis study demonstrates the utility of early-pregnancy metabolomic profiling for predicting GDM in Indian women. The eight-metabolite panel offers a promising tool for early risk stratification of GDM, warranting validation in diverse populations.

}, keywords = {First trimester, Gestational diabetes mellitus, Indian women, Mass spectrometry, Metabolomics, Prediction}, doi = {10.1186/s12933-025-02978-0}, author = {Sharma, Sapna and Subrahmanyam, Yalamanchili Venkata and Gupta, Payal and Vadivel, Sangeetha and Deepa, Mohan and Tandon, Ansh and Sreedevi, Sreekumar and Ram, Uma and Narad, Priyanka and Parmar, Dharmeshkumar and Anjana, Ranjit Mohan and Raghunathan, Anu and Balasubramanyam, Muthuswamy and Mohan, Viswanathan and Sengupta, Abhishek and Adamski, Jerzy and Saravanan, Ponnusamy and Panchagnula, Venkateswarlu and Usharani, Dandamudi and Gokulakrishnan, Kuppan} } @article {49862, title = {A Pt-Based Carbon-Free Cathode with Embedded Oxygen Nanoreservoirs: A Promising Approach for Oxygen Buffering to Aid Oxygen Reduction Reactions of PEMFCs}, journal = {ACS Catalysis}, volume = {15}, year = {2025}, month = {NOV}, pages = {19677-19694}, type = {Article}, abstract = {

For practical applications of proton exchange membrane fuel cells (PEMFCs), the system needs to be operated by employing air in the cathode instead of pure oxygen (O2). This makes it necessary to develop innovative electrode engineering solutions so that the system can function well even in oxygen-lean environments under the realistic working conditions of PEMFCs. Taking this into account, we introduce Pt/SiO2@CeO2-30\%, an engineered electrocatalyst with potentially generated oxygen vacancies (Ov), which can immensely contribute toward the enhancement in the O2 availability in oxygen-lean conditions like the air feed conditions, allowing an effective control of the overpotential related to the oxygen reduction reactions (ORRs) at the electrode level. The meticulously crafted Pt-CeO2 interface serves as one of the appreciable structural attributes of the present catalyst, facilitating oxygen spillover toward the Pt environment, aided by the creation of the immense Ov along the nano CeO2 phase of the catalyst. In addition to the benefit of addressing the oxygen-lean conditions and overcoming the limitations of the state-of-the-art catalysts, usage of a noncarbonaceous support like SiO2 to house the Pt and CeO2 nanoparticles has been anticipated to lessen the corrosion problems, a major drawback associated with the carbon-based ORR catalysts. Apart from this, a significant contribution of SiO2 to the self-humidification of the ionomer interface plays a crucial role in enabling the MEA to work under low relative humidity conditions, which can be attributed to an additional benefit of the current composition of the catalyst. The catalyst demonstrated a promising ORR performance with a substantial improvement in H2-air feed circumstances and better corrosion resistance when tested with a membrane electrode assembly (MEA) in a single-cell configuration, illustrating the practical feasibility in a realistic system-level validation.

}, keywords = {carbon corrosion, carbon-free electrocatalyst, oxygen buffering, oxygen reductionreaction, oxygen spill over, protonexchange membrane fuel cell}, issn = {2155-5435}, doi = {10.1021/acscatal.5c06455}, author = {Yoyakki, Athira and Kumar, Sachin and Pandikassala, Ajmal and Jadhav, Swapnil D. and Vinod, C. P. and Kurungot, Sreekumar} } @article {49840, title = {Pushing the boundaries of pnictogen-bonding organocatalysis: a clash of Sb(III) versus Bi(III)}, journal = {ChemPhysChem}, volume = {26}, year = {2025}, month = {AUG }, pages = {e202500265}, type = {Article}, abstract = {

The sigma-hole-mediated noncovalent organocatalysis involving the pnictogen (Pn) elements has thus far been explored mostly from nitrogen to antimony, with antimony identified as the most effective catalyst. Herein, density functional theory calculations have been carried out to demonstrate that tri-aryl (Ar)-substituted bismuth(III) complexes can outperform their antimony counterparts in both anion (Cl-) binding and catalytic activity. Using a range of computational methods, a good correlation between the sigma-hole strength, chloride binding affinity, and the reaction barrier is established. Notably, the findings reveal that dispersion interactions are the dominant force in catalysts with weaker sigma-holes, while electrostatic interactions prevail in catalysts with stronger sigma-holes (for the anion abstraction step). In all cases, Bi(III) catalysts emerge as the winner over the Sb(III) analogues. Additionally, beyond the primary Pn. . .Cl interactions, several secondary interactions such as Cl. . .H/F-C(Ar) and Cl-. . . H-C(Si-TBS) also play a significant role in stabilizing the transition states.

}, keywords = {Antimony, Bismuth, organocatalysis, pnictogen, sigma (sigma) holes}, issn = {1439-4235}, doi = {10.1002/cphc.202500265}, author = {Sharma, Jyoti and Dash, Soumya Ranjan and Vanka, Kumar} } @article {49791, title = {Rational design of hydrophobic Cu/CuO electrodes for electrochemical oxygenation of tetralin: a strategic approach}, journal = {ChemSusChem}, volume = {18}, year = {2025}, month = {AUG }, type = {Article}, abstract = {

Electro-organic synthesis presents a sustainable and practical alternative to traditional organic synthesis methods, which typically utilize harsh reagents and require energy-intensive conditions. Nevertheless, the challenge of achieving satisfactory conversion and selectivity rates in electrocatalytic oxidation using a non-platinum group metal (PGM) catalyst pair still needs to be addressed. This study demonstrates the application of a non-PGM-based catalyst pair for the electrocatalytic oxidation of tetralin to 1-tetralone, a highly demanded raw material in the pharma industry. Copper electrodeposited on teflonated carbon paper combined with copper foam as the electrocatalyst pair has demonstrated impressive conversion and selectivity ratios to electro-synthesize 1-tetralone at room temperature and atmospheric pressure. The optimal choice of a non-PGM catalyst, ideal mass loading, and a unique electrode configuration resulted in an ultimate conversion of about 99\% of tetralin and 1-tetralone selectivity -93.7\%, yield -92.6\%. The reaction pathway associated with the electrochemical phenomena is supported by first principles-based density functional theory calculations and X-ray photoelectron spectroscopy of the electrocatalyst. This process has exceptional performance that can be adapted for a wide range of substrates and is straightforward, ambient, reagent-free, scalable, and therefore beneficial for industrial use. Therefore, initiatives have been taken in this direction.

}, keywords = {C-H activation, Copper, electrochemical oxidation, non-PGM electrocatalysts, tetralin, Tetralone}, issn = {1864-5631}, doi = {10.1002/cssc.202501184}, author = {Cherukuthota, Sri Vidya and Mathew, Elizabeth and Verma, Tushar Singh and Joshi, Krati and Selvaraj, Kaliaperumal} } @article {49921, title = {Regio selective synthesis of pyrazole derivatives of 5-chloro-2-methoxy phenyl hydrazide and their biological evaluation}, journal = {Journal of Heterocyclic Chemistry}, volume = {62}, year = {2025}, month = {APR}, pages = {325-329}, type = {Article}, abstract = {

Present study involves synthesis of derivatives of (5-chloro-2-methoxyphenyl) (5-alkyl-3-(substituted) (phenyl/alkyl)-1H-pyrazol-1-yl) methanones. Structural elucidation of the synthesized compounds was depicted by the data of 1H and 13C NMR, IR, and Mass spectral analysis. The newly synthesized compounds 1a-1d and 2a-2i were screened in vitro against Mycobacterium tuberculosis H37Ra using an established XRMA protocol. Among the screened compounds, 2d, 2f, and 2h showed good percent inhibition against the active stage of M. tuberculosis H37Ra 80.77, 55.70, and 79.54, respectively, at 30 mu g/mL of inhibitor concentration. Further in secondary screening, compound 2d exhibited significant antitubercular activity on the active stage of M. tuberculosis H37Ra with IC50 of 0.208 mu g/mL. The synthesized compounds were also screened for antibacterial activity and found no significant activity against Gram-positive Bacteria Bacillus subtitles and Staphylococcus aureus and Gram negative bacteria Pseudomonas aeruginosa and Escherichia coli at 30 mu g/mL, which confirms the specificity of inhibitory activity against M. tuberculosis and more selectively against the active stage. The present study will be helpful for the further development of these molecules into antitubercular lead candidates.

}, keywords = {5-chloro-2-methoxy phenyl hydrazide, antibacterial activity, Antitubercular activity, Biological evaluation, H37Ra, hydrazide, Pyrazole}, issn = {0022-152X}, doi = {10.1002/jhet.4941}, author = {Bavishi, Abhay and Vala, Hardev and Swami, Sagar and Thakrar, Shailesh and Shah, Anamik and Sarkar, Dhiman} } @article {49568, title = {Regioisomeric π-extended nanographene with long-lived phosphorescence afterglow}, journal = {Angewandte Chemie-International Edition}, volume = {64}, year = {2025}, month = {FEB}, pages = {e202422125}, type = {Article}, abstract = {

The cutouts of graphene sheets, particularly those with a nonplanar topology, present vast opportunities for advancement. Even a slight deviation from the planar structure can lead to intriguing (chiro)optical features for helically twisted nanographenes. In this context, we introduce two regioisomeric pi-extended nanographenes that exhibit distinct excited-state characteristics. The helicene structure and the photophysical features can be easily tuned by changing the connecting position of the nanographene to the carbazole core (2,7- and 3,6-). Single-crystal X-ray diffraction analysis confirmed the formation of nanographenes with bent and helical conformations. Both derivatives exhibited thermally activated delayed fluorescence at room temperature and phosphorescence at low temperatures. Notably, the nanographene with the bent structure displayed an impressive red afterglow lasting over 30seconds, in contrast to the very weak afterglow observed in the helical structure. DFT calculations revealed the existence of an isoenergetic higher triplet state (T-8) and comparatively weak spin-orbit coupling (T-1-S-0), thereby enabling the bent nanographene to exhibit a long-lived component and strong afterglow. Our findings highlight the significance of regioisomeric nanographenes with exceptional optical properties and offer a deeper understanding of the structure-property relationship in nonplanar nanographenes.

}, keywords = {Afterglow, CPL, Helicenes, nanographene, Phosphorescence, TADF}, doi = {10.1002/anie.202422125}, author = {Kumar, Viksit and Venugopal, Geethu and Jadhav, Ashok Badrinarayan and Dongre, Sangram D. and Gonnade, Rajesh and Kumar, Jatish and Ruer, Paul C. and Hupp, Benjamin and Steffen, Andreas and Babu, Sukumaran Santhosh} } @article {49728, title = {Relativistic extended-coupled-cluster calculations of P , T -odd sensitivity parameters for diatomic molecules}, journal = {Journal of Chemical Theory and Computation}, volume = {21}, year = {2025}, month = {MAY}, pages = {5481-5489}, type = {Article}, abstract = {

We demonstrate the first application of the four-component relativistic extended-coupled-cluster (ECC) method, a variational approach, to determine the P , T -odd molecular electronic structure parameters necessary for high-precision spectroscopic measurements on ultracold molecules. We calculate the P , T -odd sensitivity parameters for two moderately heavy, laser-coolable diatomic molecules (SrH and SrF), as well as two relatively lighter open-shell molecules (CaH and CaF) in their ground electronic state, 2 Sigma 1/2. The hyperfine structure constants of 87Sr in the SrF and SrH molecules are also computed and compared with available experimental results to assess the accuracy of our calculations. Furthermore, we examine the roles of electron correlation, relativity, basis set, and virtual spinors in ECC calculations of the sensitivity parameters. Our study reveals that the ECC method is a reliable technique for studying P , T -odd properties of diatomic molecules such as CaH, CaF, SrH and SrF, yielding results in very good agreement with those obtained using two widely employed analytic approaches: the Z-vector technique and the linear expectation-value method within the relativistic single-reference coupled-cluster singles and doubles framework.

}, issn = {1549-9618}, doi = {10.1021/acs.jctc.5c00329}, author = {Talukdar, Kaushik and Nayak, Malaya K. and Vaval, Nayana and Pal, Sourav} } @article {49675, title = {Retrieval augmented generation for building datasets from scientific literature}, journal = {Journal of Physics-Materials}, volume = {8}, year = {2025}, month = {JUL}, pages = {035006}, type = {Article}, abstract = {

In this work, we show that employing retrieval augmented generation (RAG) with a large language model (LLM) enables us to extract accurate data from scientific literature and construct datasets. The rapid growth in publications necessitates the automation of extraction of structured data as it is crucial for training machine learning(ML) models. The pipeline developed is simple and can be adjusted accordingly with natural language as input. Quantization enables us to run LLMs on consumer hardware and remove the reliance on closed-source models. Both Llama3-8B and Gemma2-9B with RAG give structured output consistently and with high accuracy as compared to direct prompting. Using the newly developed protocol, we created a data set of metal hydrides for solid-state hydrogen storage from paper abstracts. The accuracy of the generated dataset was \>88\% in the cases tested. Further, we demonstrate that the generated dataset is ready-to-use for ML models by testing it with HYST to predict the H(2)wt\textbackslash\% at a given temperature. Thus, we demonstrate a pipeline to create datasets from scientific literature at minimal computational cost and high accuracy.

}, keywords = {dataset building, Hydrogen storage, LLM, materials, RAG}, doi = {10.1088/2515-7639/ade1fa}, author = {Maharana, Piyush Ranjan and Verma, Ashwini and Joshi, Kavita} } @article {49798, title = {Selective hydrogenation of furfural to furfuryl alcohol over Pd supported on ternary oxide in aqueous medium under mild conditions}, journal = {ChemCatChem}, volume = {17}, year = {2025}, month = {AUG}, type = {Article}, abstract = {

We report palladium (Pd) supported on a mixed CuO/ZnO/Al2O3 catalyst for the synthesis of furfuryl alcohol (FA) from furfural (FF) using hydrogen under near atmospheric pressure (balloon pressure) conditions. A systematic study of various metal oxide combinations revealed that the best support for Pd nanoparticles is a CuO/ZnO/Al2O3 mixed system, which results in excellent catalytic performance. A series of control experiments highlighted the essential role of mixed Cu-Zn-Al oxide support in facilitating the adsorption and activation of FF. Our results demonstrate that under optimal conditions (40 degrees C, balloon pressure H2), the catalyst yields FF conversion exceeding 98\%, with remarkable selectivity for FA reaching up to 99\% with water as solvent. The catalyst exhibited almost comparable activity up to three catalytic cycles without extra catalyst treatment or reactivation with negligible Pd leaching. These findings shed insight into the design of mixed metal oxide-based support for active metal interactions in optimizing catalytic performance in furfural hydrogenation under mild conditions.

}, keywords = {Biomass conversion, Furfural hydrogenation, Furfuryl alcohol, mixed metal oxides, Pd catalyst}, issn = {1867-3880}, doi = {10.1002/cctc.202402092}, author = {Nehra, Pooja and Betsy, K. J. and Vinod, C. P.} } @article {49868, title = {Silylene-copper(i) catalysis: regioselective protoboration of terminal alkynes}, journal = {Chemical Communications}, volume = {61}, year = {2025}, month = {DEC}, pages = {19652-19655}, type = {Article}, abstract = {

Herein, we report an efficient regioselective protoboration of the terminal alkynes catalyzed by newly synthesized silylene-copper(i)-aryl complexes. This method offers a broad substrate scope, good functional-group compatibility, and a gram-scale synthetic ability. The insight into the mechanistic cycle is also provided with the support of experimental and theoretical studies.

}, issn = {1359-7345}, doi = {10.1039/d5cc06125c}, author = {Kaulage, Sandeep H. and Shah, Brij Kumar and Panday, Rishukumar and Sharma, Himanshu and Vanka, Kumar and Khan, Shabana} } @article {49507, title = {Studies on the stereoselective synthesis of sacubitril via a chiral amine transfer approach}, journal = {Chemistry-An Asian Journal}, volume = {20}, year = {2025}, month = {MAR }, type = {Article}, abstract = {

We present a comprehensive account of our efforts directed towards the synthesis of sacubitril, a neprilysin inhibitor used in combination with valsartan and marketed as Entresto (TM). Our initial approach to the formal synthesis of sacubitril employed a chiral pool strategy, utilizing (S)-pyroglutamic acid as a key building block and Cu(I)-mediated Csp2-Csp3 cross-coupling as a key transformation. Further investigations led to the development of chiral amine transfer (CAT) reagents-based stereoselective synthesis. This involved the E-selective construction of gamma-ylidene-butenolide from readily available biphenyl bromide and 4-pentynoic acid, the conversion of this butenolide to its ene-lactam using chiral amine, and substrate-controlled diastereoselective reduction of ene-lactam using Et3SiH or Pd/C, H2 (overall chiral amine transfer) as key transformations. Antipodal lactam intermediates were synthesized using corresponding chiral amines, and the stereochemical outcomes during the ene-lactam reduction with Et3SiH were rationalized by DFT studies.

}, keywords = {Chiral Amine Transfer (CAT) approach, Chiral pool approach, Sacubitril, stereoselective synthesis}, issn = {1861-4728}, doi = {10.1002/asia.202401223}, author = {Sadanande, Megha V. and Thorat, Sagar S. and Sharma, Himanshu and Singh, Geetika and Vanka, Kumar and Gonnade, Rajesh G. and Kontham, Ravindar} } @article {49527, title = {Synthesis and concomitant polymorphs of green fluorescence protein chromophore-anthracene-based fluorescent analogue}, journal = {Crystal Growth \& Design}, volume = {25}, year = {2025}, month = {FEB}, pages = {1011-1022}, type = {Article}, abstract = {

Controlled variations in fluorescence properties hold significant promise for applications in optical sensors, bioimaging, and advanced display devices. However, constructing multicolor fluorescent systems remains a challenge. In this study, we demonstrate the development of multicolor fluorescence by generating polymorphs of a novel green fluorescent protein chromophore analogue, which exhibits distinct photoluminescence emissions in the solid state. The observed emission variations are attributed to differences in molecular conformation due to variations in pi-stacking interactions between the polymorphs. This offers a novel approach to designing materials with tunable fluorescence properties.

}, issn = {1528-7483}, doi = {10.1021/acs.cgd.4c01347}, author = {Mali, Bhupendra P. and Dabke, Niteen B. and Dash, Soumya R. and Biswas, Anupam and Vanka, Kumar and Manoj, Kochunnoonny and Gonnade, Rajesh G.} } @article {49558, title = {Synthesis, biological screening, and molecular docking of hybrid pyrazole scaffolds for antitubercular and antimicrobial activity}, journal = {ChemistrySelect}, volume = {10}, year = {2025}, month = {JAN}, pages = {e202404830}, type = {Article}, abstract = {

This study reports the synthesis, characterization, and docking analysis of 21 novel compounds, including asymmetric dihydropyridines (4a-4o) and chalcones (6a-6f), derived from coupling 1,3-(substituted)-diphenyl-1H-pyrazole-4-carbaldehyde with active methylene compounds and 3-acetyl-4-hydroxycoumarin, respectively. Structural confirmation was achieved through 1H and 13C NMR, IR, and mass spectrometry. Biological screening against mycobacterium tuberculosis H37Ra identified compounds 4b, 4d, 4f, 4g , 4i, 4k, 6e, and 6f as significant antitubercular agents. Antibacterial evaluation at 30 mu g/mL showed selective inhibition of gram-positive bacteria, with compound 6e active against Staphylococcus aureus and Bacillus subtilis, and 6f showing activity specifically against S. aureus. Docking studies indicated effective InhA binding (Delta G = -3.52 to -7.27 kcal/mol) and inhibition constants ranging from 2640 to 4.71 mu M. Key binding interactions with residues TYR156 and ILE192 were observed, enhancing affinity, particularly for compound 6e. The SAR analysis emphasized the enhanced antitubercular potency of 2-chloroacetyl and 2,4-dichlorobenzoyl substitutions in the dihydropyridine series, while in the chalcone series, specific substitutions, such as the 3-nitro substitution in 6e, enhance antitubercular and antimicrobial potency due to stronger hydrogen bonding and increased polar surface area, while the 4-fluoro substitution in 6f confers selective activity against S. aureus.

}, keywords = {1, 4-dihydropyridine, 4-hydroxy coumarin, Biological activity, In silco studies, Pyrazole}, issn = {2365-6549}, doi = {10.1002/slct.202404830}, author = {Bavishi, Abhay and Vala, Hardev and Radadiya, Ashish and Swami, Sagar and Thakrar, Shailesh and Sarkar, Dhiman and Shah, Anamik} } @article {49720, title = {Synthesis, crystal structure, DFT calculation and catalytic activity of a polymer complex of zinc(II) succinate with 2-amino-1,3,4-thiadiazole}, journal = {Journal of Molecular Structure}, volume = {1338}, year = {2025}, month = {AUG}, pages = {142274}, type = {Article}, abstract = {

A polymer complex of zinc(II) succinate with a 2-amino-1,3,4-thiadialole ligand, denoted as [Zn2L2(suc)2]n, was synthesized and characterized by NMR, ESI-MS, FTIR, and FT-Raman spectroscopy, TGA, and X-ray crystallography. The polymer complex crystallizes in the orthorhombic noncentrosymmetric Pna21 space group and features a five-coordinate zinc ion in a distorted spherical square pyramidal geometry. The Hirshfeld surface analysis was carried out to evaluate the intermolecular interactions. Additionally, computational studies were also conducted to assess the stability of the Zn polymer complex and analyze the electron density distribution of the HOMO and LUMO. The catalytic activity of our complex was tested, interestingly, that showed good results for Biginelli reactions with distinct substrate scope in good to high yield at mild reaction conditions.

}, keywords = {DFT, Dihydropyrimidinones, Polymer complex, succinate, Thiadiazole, zinc}, issn = {0022-2860}, doi = {10.1016/j.molstruc.2025.142274}, author = {Nuralieva, Guzal and Alieva, Mushtariy and Torambetov, Batirbay and Leslee, Denzil Britto Christopher and Senthilkumar, Beeran and Kaur, Simranjeet and Dabke, Niteen B. and Vanka, Kumar and Ashurov, Jamshid and Kadirova, Shakhnoza and Gonnade, Rajesh G.} } @article {49856, title = {Synthesis of 5-hydroxymethylfurfural from glucose using a tert-butoxyapatite catalyst}, journal = {DALTON TRANSACTIONS}, volume = {54}, year = {2025}, month = {SEP}, pages = {13574-13587}, type = {Article}, abstract = {

In this study, 5-hydroxymethylfurfural (5-HMF) was obtained from glucose using tert-butoxyapatite, a heterogeneous catalyst. The tert-butoxyapatite catalyst was prepared and characterized by several techniques, such as XRD, SEM, TEM, EDS, elemental mapping HR-TEM, N2-adsorption/desorption, XPS, and FT-IR. Several parameters were studied, such as temperature, catalyst loading, and glucose concentration. The tert-butoxyapatite catalyst having both acidic and basic sites gave a maximum glucose conversion of 87\% with a 48\% yield of HMF at 160 degrees C using 20 wt\% catalyst in 12 h. Reusability studies of the catalyst are also presented.

}, issn = {1477-9226}, doi = {10.1039/d5dt01450f}, author = {Kulkarni, Hemant S. and Kamble, Paresh A. and Vinod, Chathakudath P. and Rathod, Virendra K. and Kantam, Mannepalli Lakshmi} } @article {49683, title = {Synthesis of diamido N-heterocyclic imines (DAC = NH) via staudinger or reductive N-N bond cleavage approach}, journal = {Organometallics}, volume = {44}, year = {2025}, month = {MAY}, pages = {1129-1133}, type = {Article}, abstract = {

This report communicates the first examples of N-heterocyclic imines based on electrophilic diamido carbenes (DACs). While 2 is prepared by classical Staudinger synthesis, 4 is obtained via an unusual reductive N-N bond cleavage of an azine by HCl. The exocyclic C=N bond lengths in 2 and 4 are substantially shorter than those based on N-heterocyclic carbenes and cyclic (alkyl)(amino)carbene reflecting the electrophilic character of DACs.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.5c00120}, author = {Balayan, Kajal and Sharma, Himanshu and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {49696, title = {Synthesis of glycolic acid from glyoxal by using hydrotalcite catalyst and kinetic studies}, journal = {ChemCatChem}, volume = {17}, year = {2025}, month = {JUN}, type = {Article}, abstract = {

In this work, Mg-Al hydrotalcite catalysts with different molar ratios were prepared using the co-precipitation method for the synthesis of glycolic acid (GA) from glyoxal. Various reaction parameters such as catalyst molar ratio, time, temperature, catalyst loading, and catalyst poisoning were studied and optimized for better conversion of glyoxal selectively to glycolic acid. Hydrotalcite catalyst with a 2:1 molar ratio of Mg: Al gives 98\% conversion of glyoxal with 96\% selectivity of glycolic acid at 100 degrees C temperature, 40\% catalyst loading, and water as solvent in 8 h. Different characterization methods were used such as XRD, XPS, SEM-EDX, nitrogen adsorption desorption, and CO2-TPD for hydrotalcite catalyst. A kinetic study was also performed to observe the reaction order and activation energy required for the reaction.

}, keywords = {Glycolic acid, Glyoxal, hydrotalcite, kinetics}, issn = {1867-3880}, doi = {10.1002/cctc.202500321}, author = {Pandya, Harmitkumar N. and Kamble, Paresh A. and Vinod, Chathakudath P. and Rathod, Virendra and Kantam, Mannepalli Lakshmi} } @article {49225, title = {Tailoring the electrochemical properties of ZnS electrodes via cobalt doping for improved supercapacitor application}, journal = {JOURNAL OF ELECTRONIC MATERIALS}, volume = {54}, year = {2025}, month = {JAN}, pages = {451-461}, type = {Journal Article}, keywords = {capacitance, Co-doped, supercapacitor, ZnS}, issn = {0361-5235}, doi = {10.1007/s11664-024-11535-6}, author = {Tom, Emmanuel and Velluva, Abhijai and Joseph, Anit and Thomas, Tiju and Sha, Mizaj Shabil and Jithin, V, P. and Thomas, Deepu and Sadasivuni, Kishor Kumar and Kurian, Joji} } @article {49986, title = {Thin-film approach for scalability and enhancement of solar hydrogen production with CNT integrated Ce-doped-TiO2 composite in direct sunlight}, journal = {Materials Today Catalysis}, volume = {10}, year = {2025}, month = {SEP}, pages = {100115}, type = {Article}, abstract = {

Solar hydrogen production by photocatalysis has long been considered as an important energy option. Whichever photocatalyst succeeds, methods should be available to scale-up in a most sustainable and cost-effective manner, and the present work addresses this specific issue. In the present study, Ce-doped in the TiO2\ lattice (Ce-TiO2) and the same integrated with CNT (CNT-Ce-TiO2; (CCT)) composite was synthesized and characterized. Current study demonstrates the synergistic integration of Ce-TiO$_{2}$ as a light absorber and charge generator with CNTs as efficient charge separation at heterojunctions as well as charge transporter in a thin-film configuration (lab-scale (4.7 cm2), bench-scale (500 cm2)). Improved H2\ generation under direct sunlight demonstrated in thin film form, than in particulate suspension, is attributed to efficient light absorption, particularly for electron-hole pair separation and their dispersion to redox sites. Additionally, the role of the binder is highlighted for improving H2\ yield and the sustainability of the thin-film form of photocatalyst. \~{}200 mg (1 g) CCT coated over 500 cm2\ (2500 cm2) photocatalyst produced 21.6 mmol/h (102 mmol/h) H2\ in sunlight. Present results provides a proof of concept that the thin film form of photocatalyst displays, at least 10 times, higher H2\ yield than its powder counterpart, depending on the measurement conditions. A non-linear enhancement in H2\ yield with small and large area thin-film indicates complex underlying factors and highlights the scope for further improvements.

}, doi = {https://doi.org/10.1016/j.mtcata.2025.100115}, author = {Vijayarengan, Preethi and Maria, Anthony Raja and Ashadevi, K. S. and Nalajala, Naresh and Gopinath, Chinnakonda S.} } @article {49967, title = {Towards improved activity and stability in RWGS reaction: Dispersed copper in mesoporous alumina matrix as a strategy for enhanced performance}, journal = {Chemical Engineering Journal}, volume = {525}, year = {2025}, month = {DEC }, pages = {169863}, type = {Article}, abstract = {

The development of highly performing Cu-based catalysts with high dispersion of Cu species in nanocrystalline form on a suitable oxide support is significant in reverse water gas shift (RWGS) reaction. We report a simple and robust one-pot sol-gel synthesis of mesoporous Al10-xCuxOy (m gamma-Al10-xCux-SG) catalysts with Cu species in a highly dispersed nanocrystalline form in the gamma-Al2O3 matrix and its high catalytic performance in RWGS reaction. The lack of long range structural order of copper species in m gamma-Al10-xCux-SG catalysts evidenced from Cu-K edge extended X-ray absorption fine structure (EXAFS) studies illustrates the fine distribution of copper species in mesoporous gamma-Al2O3 lattice. Activity study revealed that m gamma-Al10-xCux-SG catalysts showed significantly high CO2 conversion to CO and excellent catalytic stability compared to gamma-Al10-xCux-I prepared by conventional impregnation method. Mesoporous Al9Cu1 (m gamma-Al9Cu1) displayed a CO2 conversion of 45 \% at 500 degrees C, which is about 2.8 times higher activity than conventional gamma-Al9Cu1-I catalyst with almost same Cu loading as that of m gamma-Al9Cu1 catalyst. Stability study at 500 degrees C over a period of 50 h revealed that m gamma-Al10-xCux-SG catalysts at low Cu loading (m gamma-Al9.9Cu0.1) showed excellent catalytic stability. The strong copper-alumina interaction in m gamma-Al10-xCux-SG catalysts with enhanced number of active sites at the copper-alumina interface as evidenced from field emission scanning electron microscope (FESEM), high-resolution transmission electron microscope (HRTEM), H2-temperature programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), electrochemical characterization, and Cu-K edge EXAFS analysis enhances the activity and stability of the catalyst. Density functional theory (DFT) studies and the Operando DRIFTS-MS analysis of RWGS over m gamma-Al9Cu1 catalyst revealed that the mechanism of RWGS reaction to CO formation on m gamma-Al10-xCux-SG catalysts is preceded through the formation of a hydroxycarbonyl (OCOH) intermediate. The present synthesis strategy provides an opportunity for producing Cu-based catalysts with further enhanced activity and stability in RWGS reaction by suitable modification of the catalyst.

}, issn = {1385-8947}, doi = {10.1016/j.cej.2025.169863}, author = {Saju, Simi and Rajendran, Sivaraj and Oztas, Ulviye and Ruiz, Sergio Carrasco and Reina, Tomas Ramirez and Ghosh, Biplab and Sree, Sreeprasanth Pulinthanathu and Meena, Raghavendra and Li, Guanna and Bobadilla, Luis F. and Vinod, Chathakudath P. and Mathew, Thomas and Shiju, N. Raveendran} } @article {49585, title = {Transit of NEAT1 and MTP11 to the plasma membrane and co-localization to vesicles support a role for exocytosis-mediated export in metal homeostasis}, journal = {Physiologia Plantarum}, volume = {177}, year = {2025}, month = {JAN}, pages = {e70067}, type = {Article}, abstract = {

Understanding the role and mode of action of nutrient transporters requires information about their dynamic associations with plant membranes. Historically, apoplastic nutrient export has been associated with proteins localized at the plasma membrane (PM), while the role of endomembrane localization has been less explored. However, recent work on the PHOSPHATE 1 (PHO1) inorganic phosphate (Pi) exporter demonstrated that, although primarily localized at the Golgi and trans-Golgi network (TGN) vesicles, PHO1 does associate with the PM when clathrin-mediated endocytosis (CME) was inhibited, supporting a mechanism for Pi homeostasis involving exocytosis. We explored whether CME inhibition can identify other transporters that, although primarily localized at Golgi/TGN at steady-state level, also transit via the PM and are potentially involved in export via exocytosis. We found that, similar to PHO1, Golgi-localized transporters NA EFFLUX TRANSPORTER1 (NAET1) and METAL TOLERANCE PROTEIN11 (MTP11) relocate to the PM when CME is inhibited, both transiently in Nicotiana benthamiana and conditionally in Arabidopsis thaliana. Such PM re-localization of transporters upon CME inhibition is specific, since it does not occur with several other Golgi-associated transporters, including MTP5 and BIVALENT CATION TRANSPORTER 3 (BICAT3), as well as resident Golgi/TGN membrane proteins, such as alpha-1,2-MANNOSIDASE I (Man1) and VESICLE TRANSPORT V-SNARE 12 (VTI12). Additionally, we observed that NAET1, MTP11 and PHO1 all partially co-localize to vesicles. Overall, our study supports a role for synaptic-like vesicle-mediated exocytosis for both NEAT1 and MTP11 in nutrient transport in plants and highlights the importance of assessing the transient localization of Golgi/TGN proteins to the PM.

}, issn = {0031-9317}, doi = {10.1111/ppl.70067}, author = {Vetal, Pallavi V. and Jaskolowski, Aime and Poirier, Yves} } @article {49793, title = {Tunable, amine-functionalized porous silica catalyst for CO2 transformation into cyclic organic carbonates at atmospheric pressure}, journal = {Chemistry-A European Journal}, volume = {31}, year = {2025}, month = {AUG }, type = {Article}, abstract = {

A silica catalyst with characteristic features of broad pore size distribution, large pore width and tunable basic sites was synthesized by a one-step green co-condensation synthesis method analogous to SBA-15 synthesis. The surface chemical features of the above catalyst were explored by XPS, N-2 and CO2 adsorption and desorption experiments. The catalyst showed 90\% conversion of styrene oxide (SO) with nearly complete selectivity toward styrene carbonate (SC) in 7 hours under a solvent-free condition at a temperature of 120 degrees C with the aid of co-catalyst tetrabutylammonium bromide (TBAB). Moreover, the catalyst demonstrates versatility with various epoxide substrates, providing valuable insights into the cycloaddition reaction under ambient pressure conditions involving carbon dioxide. The mechanistic details of the catalytic conversion were investigated by the in-situ DRIFT studies and reported here.

}, keywords = {CO2 fixation, cyclic organic carbonates, heterogeneous catalysis, in-situ FTIR}, issn = {0947-6539}, doi = {10.1002/chem.202500873}, author = {Gorai, Twinkle and Thanasekar, Chandragopal and Kumar, Pawan and Babu, Athira and Kurungot, Sreekumar and Vinod, C. P.} } @article {49627, title = {Ultra-small Pd nanoparticles on SBA-15: an efficient catalyst for one-pot reductive alkylation of nitrobenzene with size-dependent activity}, journal = {Topics in Catalysis}, volume = {68}, year = {2025}, month = {FEB}, pages = {414-429}, type = {Article}, abstract = {

One-pot reductive alkylation of nitrobenzene with alcohol is an important organic synthesis reaction to form 2 degrees amines. In the present work, we have demonstrated that Pd/SBA-15 can be an effective catalytic system for this reaction. We have designed ultra-small Pd nanoparticles supported on SBA-15 for the synthesis of secondary amine, N-ethylaniline, through one-pot reductive alkylation of nitrobenzene with ethanol under ambient conditions. Ethanol functions both as the alkylating agent and the solvent in this process. The reaction is driven by the simultaneous hydrogenation of nitrobenzene to aniline, dehydrogenation of ethanol to aldehyde, and condensation of aniline and acetaldehyde to form N-ethylaniline. The size of the Pd nanoparticles plays a decisive role in the product selectivity. The undercoordinated sites present on ultra-small Pd NPs can facilitate ethanol dehydrogenation to acetaldehyde, thereby enhancing the selectivity towards N-ethylaniline compared to larger Pd nanoparticles. We have also studied the effect of different mesoporous supports such as SBA-15, MCM-41, and KIT-6 on the N-ethylaniline selectivity and found that SBA-15 was most selective. We have demonstrated that by carefully designing the catalyst such as controlling the Pd NPs size to obtain the maximum quantity of undercoordinated sites and choosing suitable support, the aliphatic alcohols can also be used for reductive alkylation of nitrobenzene in one-pot with optimum yields of N-alkylaniline.

}, keywords = {KIT-6, MCM-41, Modified deposition precipitation, nitrobenzene, Pd nanoparticles, Reductive alkylation, SBA-15, secondary amines, Undercoordinated Pd sites}, issn = {1022-5528}, doi = {10.1007/s11244-024-02042-3}, author = {Soni, Yogita and Philip, Milda C. and Vinod, Chathakudath P.} } @article {49974, title = {Understanding the antimicrobial and antioxidant potential of bioinspired platinum nanoparticles synthesized using ocimum tenuiflorum}, journal = { BioNanoScience}, volume = {15}, year = {2025}, month = {JAN}, pages = {1789}, type = {Article}, abstract = {

The emergence of infectious diseases has highlighted the need for novel and effective antimicrobial agents. Platinum nanoparticles (PtNPs) could act as a potent antimicrobial agent due to their unique physicochemical properties. However, the chemical or physical synthesis methods of PtNPs have drawbacks, like irregular shape and use of toxic chemicals. These drawbacks can be effectively overcome by using the biological method synthesis. Thus, this study presents the green synthesis of platinum nanoparticles (PtNPs) using\ Ocimum tenuiflorum\ leaf extract as a bio-reductant. The study also comprehensively encompasses the role of multiple process parameters for the green synthesis of PtNPs. The high-resolution transmission electron microscopy (HR-TEM) revealed spherical PtNPs with an average size of 2.36 {\textpm} 0.5 nm that exhibits excellent stability (zeta potential, -45.67 {\textpm} 2.57 mV). Phytochemical analysis of aqueous\ O. tenuiflorum\ leaf extract was performed to assess the bioactive compounds like saponins, phenols, and tannins, reducing sugars and flavonoids. The PtNPs demonstrated significant antioxidant activity of 86.9 {\textpm} 0.12\% at 10 {\textmu}g/mL. Further, the biosynthesized PtNPs showed efficient antimicrobial activity with a minimum inhibitory concentration (MIC) of 6.25 {\textmu}g/mL against\ Escherichia coli\ and 1.5 {\textmu}g/mL against\ Staphylococcus aureus. These findings highlight the therapeutic potential of eco-friendly PtNPs for pharmaceutical and biotechnological applications.

}, author = {Varma, Sanjana and Bamb, Aagam Lalit and Tambe, Sayali A. and Burade, Dimpal K. and Jagdale, Swati and Pande, Bharat and Vamkudoth, Koteswara Rao and Chaudhari, Bhushan P.} } @article {49775, title = {Unified photoredox-catalyzed aerobic oxidative dynamic kinetic asymmetric transformation for C-N atropoisomers mediated by chiral organophosphites}, journal = {Organic Letters}, volume = {27}, year = {2025}, month = {AUG }, pages = {8171-8177}, type = {Article}, abstract = {

The synthesis of anilides with a chiral C(=O)-N axis has relied on direct installation of the chiral C(sp2)-N(sp2) bond or enantioselective modification of the peripheral groups. However, these methods are constrained by the size and type of functional groups compatible with each strategy. Herein, we report a dynamic kinetic asymmetric transformation (DYKAT) for the aerobic oxidation of iminium ions to access C(=O)-N axial chirality that addresses those limitations. Furthermore, it eliminates the need for any auxiliary functional groups, which enables us to develop a unified method for the synthesis of atroposelective isoquinolone, lactam, and amide.

}, issn = {1523-7060}, doi = {10.1021/acs.orglett.5c02273}, author = {Saikia, Pinku and Aarthika, M. and Bhattacharjya, Ayantika and Maity, Susmita and Bajpai, Priyam and Bera, Asish and Saha, Arindam and Gonnade, Rajesh G. and Vanka, Kumar and Maity, Pradip} } @article {49495, title = {Unlocking enhanced redox dynamics: the power of a bifunctional catalytic zinc phosphide interface in full cell and pouch lithium-sulfur batteries}, journal = {ACS Applied Materials \& Interfaces}, volume = {17}, year = {2025}, month = {JAN}, pages = {7657-7669}, type = {Article}, abstract = {

Lithium-sulfur (Li-S) batteries face significant challenges, such as polysulfide dissolution, sluggish reaction kinetics, and lithium anode corrosion, hindering their practical application. Herein, we report a highly effective approach using a zinc phosphide (ZnP2) bifunctional catalyst to address these issues. The ZnP2 catalyst effectively anchors lithium polysulfides (LiPSs), catalytically reactivates them, and enhances lithium-ion diffusion. Utilizing a ZnP2-modified separator in a Li-S half-cell achieves an impressive initial capacity of 1145.4 mAh g-1, retaining 954 mAh g-1 and 99.8\% Coulombic efficiency after 100 cycles, compared to the pristine separator. The underlying reaction mechanisms are thoroughly investigated through post-mortem analyses and density functional theory (DFT) calculations. Moreover, a Li-S full cell with an E/S ratio of 10 mu L mg-1 demonstrates stable cycling performance, achieving an initial capacity of 797.5 and 534 mAh g-1 after 100 cycles at 0.1C, with a negative-to-positive mass ratio of 3:1. Additionally, the real-world feasibility of lightweight and flexible Li-S pouch batteries with ZnP2-modified separators is explored, showing a stable performance over 100 cycles at 0.1C with 80\% capacity retention. This engineered separator can be integrated with advanced sulfur cathodes to create high-energy-density, stable Li-S batteries for commercial applications.

}, keywords = {catalytic interlayer, full cell, lithium dendrite, lithium sulfur battery, polysulfide shuttling, pouchcell}, issn = {1944-8244}, doi = {10.1021/acsami.4c17192}, author = {Das, Anoushka K. and Yadav, Poonam and Verma, Tushar S. and Marulasiddappa, Thripuranthaka and Krishnamurty, Sailaja and Shelke, Manjusha V.} } @article {49272, title = {Unlocking the potential of lactococcus lactis subsp. lactis BIONCL17752 strain on fumonisin B1 production by fusarium verticillioides}, journal = {Food Control}, volume = {168}, year = {2025}, month = {FEB}, pages = {110910}, type = {Article}, abstract = {

Mycotoxins are the potent toxic chemical agent{\textquoteright}s linked to food safety, pose a serious risk to human and animal health globally. The management of toxigenic fungi is a challenging task in food and feed industries. The present investigation aimed to use probiotic potentials of lactic acid bacteria (LAB), and fermented cell-free broth as antifungal agents and neutralization of carcinogenic mycotoxin, fumonisin B1 (FB1) in food and feed considered as {\textquoteleft}{\textquoteleft}turned waste into treasure{\textquoteright}{\textquoteright}. We strived to investigate the probiotic potential of Lactococcus lactis subsp. lactis BIONCL17752 strain on prevention of growth and neutralization of FB1 produced by Fusarium verticillioides BIONCL4 strain to emulate as as a food grade bio-preservative. The BIONCL17752 strain exhibited excellent inhibitory activity against BIONCL4 strain. It was cultivated in MRS medium, and obtained cells pellet (CP) and cell-free supernatant (CFS) was lyophilized, and used for their antifungal activity against BIONCL4 strain. The minimum fungicidal concentration (MFC) determined as 12.5 mu g/mL. Nevertheless, CFS assessed for neutralization of FB1 production which exhibited complete inhibition and downregulation of FB1 encoding FUM1 gene expression using quantitative real-time PCR (qPCR). Furthermore, CFS induced transcriptomic studies against BIONCL4 strain endorsed a significant downregulation of virulence, FB1, fusaric acid, fusarin, and chitin biosynthetic pathway genes. The CFS and cells reticent spore germination and FB1 production in the range of 40-61\% and 74-85\%, respectively under stored maize for 60 days. The current findings suggest BIONCL17752 strain apprehend the fungal growth and inhibit the FB1, and other toxigenic molecules biosynthesis, and can be employed as food grade preservative in the food industries to ensure the food safety and human health.

}, keywords = {Food grade preservative, Food safety, Fumonisin B-1, Fusarium verticillioides, lactis, Lactococcus lactis subsp., Maize}, issn = {0956-7135}, doi = {10.1016/j.foodcont.2024.110910}, author = {Navale, Vishwambar D. and Vamkudoth, Koteswara Rao} } @article {49599, title = {Unlocking thermodynamic enolate for kinetically controlled desymmetrizing vinylogous (4+1) carbospiroannulation}, journal = {Chemistry-A European Journal}, volume = {31}, year = {2025}, month = {MAY}, type = {Article}, abstract = {

An unprecedented thermodynamically unfavorable (4+1) deysmmetrizing spiroannulation through a thermodynamic enolate intermediate, enabling a single-step synthesis of ubiquitous scaffolds such as all-carbon chiral spirocycles, is disclosed. In this spiroannulation, we present a vinylogous organocatalytic enantioselective desymmetrizing (4+1) cycloaddition approach involving alkylidene malononitrile and cyclopent-1,3-dienone. This carbospiroannulation method produces functionally enriched spiro[4,4]nonane structures with three stereocenters, has presented good-to-high yields and enantiomeric ratios. Detailed DFT calculations reveal an intriguing reaction mechanism, which validates our observations.

}, keywords = {3-diones, alkylidene malononitrile, cyclopent-1, quaternary stereocenters, spiro compounds, thermodynamic enolate}, issn = {0947-6539}, doi = {10.1002/chem.202500671}, author = {Singh, Sanjay and Singh, Abhijeet and Pandya, Rinu and Vanka, Kumar and Singh, Ravi P.} } @article {49565, title = {Unravelling the Cu-Co nanoparticle synergy over Ceria-Zirconia support toward efficient reverse water gas shift (RWGS) conversion under H2 lean conditions}, journal = {Chemical Engineering Journal}, volume = {508}, year = {2025}, month = {MAR}, pages = {160705}, type = {Article}, abstract = {

CO2 emissions leading to global warming and environmental and socio-economic issues have propelled the research community to develop technologies capable of capturing and converting CO2 into valuable products. Controlling the selectivity toward platform molecules like CO, methanol, or methane is a fundamental challenge in CO2 hydrogenation. Supported cobalt nanoparticles are known for hydrocarbon production through FischerTropsch (FT) reaction, and Cu-based catalysts are known for reverse water gas shift (RWGS) reaction. Here, we show that d-band centre can be carefully modulated by making bimetallic combinations of Cu and Co for a highly active RWGS catalyst. An oxygen vacancy-rich nanostructured ceria-zirconia (CZ) support with Cu nanoparticles (2 wt\%) modified with as low as 0.05 wt\% Co shows excellent conversion for CO2 hydrogenation and selectivity for CO below 500 degrees C. The optimized catalyst shows CO2 conversion even under hydrogen lean conditions (H2/ CO2 ratio 0.5:1), with a breakthrough rate of 206023 mmol/gmetal/h for CO at 600 degrees C, having H2 utilization of 80\% for the RWGS process.

}, keywords = {Bimetallic catalyst, Ceria-zirconia, CO 2 hydrogenation, Cobalt catalyst, Copper catalyst, Reverse water gas shift (RWGS), synergistic effect}, issn = {1385-8947}, doi = {10.1016/j.cej.2025.160705}, author = {Jagtap, Anuradha Vijay and Bamnia, Mahesh Kumar and Maibam, Ashakiran and Bajpai, Jyotsna Paliwal and Gupta, Sharad and Thomas, Sharon K. and Dabke, Niteen B. and Vinod, C. P.} } @article {49460, title = {Valorization of avocado peel waste: extraction and characterization of cellulose nanofibers for multifunctional applications}, journal = { Biomass Conversion and Biorefinery}, volume = {15}, year = {2025}, month = {APR}, pages = {12789-12800}, type = {Article}, abstract = {

This study explored the utility of underutilized avocado peels for extracting cellulose nanofibers (CNFs). Mild oxalic acid hydrolysis assisted by steam explosion was employed after alkali hydrolysis and chlorine-free bleaching to prepare cellulose nanofibers. The structural, atomic, and elemental features of the extracted fibers were studied using Fourier transform infrared spectroscopy (FTIR),\ 13C solid-state nuclear magnetic resonance (13C NMR) spectroscopy, and energy dispersive X-ray (EDAX) analysis, respectively. The crystallinity index of the nanofibers was 87\%, which was 53\% greater than that of the crude sample. The elution of hemicellulose and lignin was evident from the scanning electron microscopy (SEM) images, and the nanofibers had a fiber diameter of 30{\textendash}82\ nm according to the transmission electron microscopy (TEM) analysis. The applied chemical treatment also elevated the thermal stability of the fibers. The extracted fibers can be applied in numerous fields, including electronics, packaging, automobiles, biomedicine, and cosmetics.

}, doi = {https://doi.org/10.1007/s13399-024-06065-4}, author = {Varsha, P. V. and Neenu, K. V. and Begum, P. M. Sabura and Hounfodji, Jean Wilfried and Sankar, Sameera and Muraleedharan, Sneha and Kamath, Anjali N. and Ajithkumar, T. G. and Parameswaranpillai, Jyotishkumar and Midhun, Dominic C. D.} } @article {49824, title = {Visible-light active π-extended unsymmetrical squaraine dyes for dye-sensitized solar cells: steric effects for controlling the aggregation of dyes}, journal = {ACS Applied Energy Materials}, volume = {8}, year = {2025}, month = {OCT}, pages = {15459-15470}, type = {Article}, abstract = {

The dye-anchored TiO2 photoanode plays a vital role in the light harvesting and charge separation processes in dye-sensitized solar cells. Aggregation of dyes (H- and J-type) on the TiO2 surface is a facile process due to the presence of a periodical dye anchoring sites on the exposed facet of titania, and such self-assembled dye structures help broadening the absorption profile. However, photocurrent generation from such aggregated structure is a challenging task in dye-sensitized solar cell devices. Hence, controlling the dye aggregation on the TiO2 surface is an important aspect. Controlling the aggregation of dyes by which (i) an enhanced photocurrent generation (J SC) and (ii) enhanced V OC can be achieved by including the steric factors to the dye design principles, the steric factor in the sensitizer may help passivate the TiO2 surface to avoid the charge recombination process between electrons present in TiO2 and the oxidized electrolyte. On the other hand, extension of pi-conjugation in a sensitizer helps enhance the light absorption in the visible region besides modulating the HOMO and LUMO energy levels. Hence, synergizing both pi-extensions along with features that control the dye aggregation has been considered in designing visible active squaraine dyes. A thiophene pi-spacer was inserted in between a visible-light active unsymmetrical squaraine unit and a cyanoacetic acid acceptor unit to provide the AJ1 and AJ2 dyes. Though both the dye molecules possess a similar pi-framework, the AJ2 dye was functionalized with both in-plane and out-of-plane alkyl groups to decrease the aggregation of dyes on the TiO2 surface compared to AJ1. The AJ1 and AJ2 dyes absorbed at 560 nm with shoulder peaks appeared at 528 nm, which can be assigned to vibronic progression (1082 cm-1), and additional characteristic peaks of thiophene appeared at 392 nm with the molar extinction coefficient of 1.16-1.19 x 105 M-1 cm-1 in CH3CN. The LUMO and HOMO energy levels are well aligned with the conduction band of TiO2 and the redox potential of iodolyte (I-/I3 -) electrolyte with sufficient overpotentials for charge injection and dye regeneration processes, respectively. The highest DSSC device efficiency of 7.37\% (J SC 14.44 mA/cm2, V OC 0.771 V, ff 67.1\%) was achieved for the AJ2 dye with iodolyte (I-/I3 -) electrolyte in the presence of 2 equiv of optically transparent coadsorbent chenodeoxycholic acid (CDCA), which showed a good IPCE response in between 400 and 700 nm. Further, cosensitization of visible-light active AJ1, AJ2, and SQA10 dyes with a complementary far-red active SQS4 dyes showed the device efficiencies of 5.53\% (AJ1:SQS4:CDCA), 7.14\% (AJ2:SQS4:CDCA), and 7.18\% (SQA10:SQS4:CDCA) with a good IPCE response in the 400-720 nm region.

}, keywords = {cosensitization, Dye aggregation, Dye-sensitized solar cells, pi-extended squaraine dye, visible-lightactivedyes}, issn = {2574-0962}, doi = {10.1021/acsaem.5c02553}, author = {Jadhav, Avinash P. and Siby, Jesna and Pandya, Rinu and Vanka, Kumar and Krishnamoorthy, Kothandam and Nithyanandhan, Jayaraj} } @article {49855, title = {W/HAP catalyzed terpenic alcohols oxidation: kinetic studies}, journal = {Reaction Chemistry \& Engineering}, volume = {10}, year = {2025}, month = {OCT }, pages = {2696-2710}, type = {Article}, abstract = {

The selective oxidation of natural alcohols into carbonyl derivatives is a pivotal transformation in synthetic organic chemistry and industrial applications. This study focuses on the oxidation of borneol, a bicyclic secondary terpenic alcohol, into camphor using a tungsten-exchanged hydroxyapatite (W/HAP) catalyst and hydrogen peroxide as a green oxidant. Hydroxyapatite was synthesized via co-precipitation and functionalized with sodium tungstate to create the W/HAP catalyst, which was characterized using techniques such as SEM, EDS, TPD, XPS, and N2 adsorption-desorption to evaluate its surface morphology, porosity, and chemical composition. Oxidation reactions were conducted under optimized conditions, employing dimethylacetamide (DMA) as a solvent to achieve maximum conversion and selectivity. The W/HAP catalyst demonstrated superior performance, achieving nearly 99\% conversion of borneol with 100\% selectivity for camphor. Reaction parameters, including temperature, reactant stoichiometry, solvent choice, and catalyst loading, were systematically investigated. Higher reaction temperatures and oxidant concentrations favoured rapid conversion while maintaining high selectivity. Solvent effects revealed that DMA stabilized peroxo-tungstate intermediates, enhancing reaction efficiency compared to other solvents. Kinetic studies confirmed a first-order reaction mechanism with respect to borneol, and the activation energy was determined to be 44.23 kJ mol-1, highlighting the catalytic efficiency of W/HAP. Reusability tests confirmed the stability of the W/HAP catalyst over multiple cycles with minimal tungsten leaching. The methodology was extended to other terpenic alcohols, with varying degrees of success, emphasizing the substrate-specific activity of the catalyst. This work underscores the potential of tungsten-based heterogeneous catalysts in sustainable alcohol oxidation and highlights the industrial relevance of camphor synthesis as a renewable and eco-friendly approach to produce fine chemicals, fragrances, and pharmaceuticals.

}, issn = {2058-9883}, doi = {10.1039/d5re00132c}, author = {Poman, Aishwarya and Kamble, Paresh and Vinod, Chathakudath P. and Rathod, Virendra and Kantam, Mannepalli Lakshmi} } @article {49963, title = {Zincke-derived viologen covalent organic framework as a high-performance cathode for aqueous zinc-iodine batteries}, journal = {Small}, volume = {21}, year = {2025}, month = {DEC }, type = {Article}, abstract = {

Aqueous zinc-iodine (Zn-I2) batteries are among the most promising energy storage technologies, offering high energy density, low cost, and intrinsic safety. However, their practical deployment is hindered by the polyiodide shuttle effect, leading to rapid capacity fading and poor cycling performance. This work demonstrates the application of a crystalline viologen-based covalent organic framework (TAB-DNP-BP COF), synthesized via a one-pot Zincke reaction, as an efficient iodine host material. The cationic backbone of the TAB-DNP-BP COF effectively confines iodine (I2) species and electrostatically traps polyiodides, suppressing their migration and protecting the zinc anode. Zinc-iodine batteries assembled with an I2-enriched TAB-DNP-BP COF (TAB-DNP-BP COF@I2) cathode deliver a high specific capacity of 337 mAh g-1 at 0.5 C, surpassing the performance of most reported COF-, MOF-, and cage-based systems, while exhibiting excellent cycling stability over 5000 cycles. This work highlights the potential of ionic COFs for stabilizing iodine chemistry and offers a promising strategy toward the development of high-performance, durable aqueous Zn-I2 batteries.

}, keywords = {iCOF, iodine confinement, viologen, zinc-iodine batteries, Zincke reaction}, issn = {1613-6810}, doi = {10.1002/smll.202506012}, author = {Das, Gobinda and Shivade, Rajkiran and Pandey, Priyanshi and Varghese, Sabu and Rajput, Nitul and Matouk, Zineb and Martinez, Jose Ignacio and Straubinger, Rainer and Benyettou, Farah and Gandara, Felipe and Olson, Mark A. and Aouad, Samer and Shelke, Manjusha V. and Trabolsi, Ali} } @article {49788, title = {Auxiliary triazatruxene donor-based squaraine dyes for dye-sensitized solar cells: cis- and trans- configuration of dyes for modulating photophysical and electronic properties}, journal = {Chemistry-an Asian Journal}, volume = {21}, year = {2026}, month = {JAN}, type = {Article}, abstract = {

In DSSCs, dye regeneration efficiency and dye aggregation on the TiO2 surface can be modulated by using bulky aromatic donors wrapped with alkyl groups. Introduction of rigid aromatic rings around the donor unit of a dye will directly impact the driving force for electron injection and dye regeneration of a dye. In this work, we designed and synthesized KNS dyes with an auxiliary TAT donor integrated with a visible active squaraine dye. Here, octupolar-structured auxiliary TAT wrapped with alkyl groups is used as a strong donor and shelter to reduce the dye aggregation and charge recombination process. Further, to improve the light-harvesting efficiency and incident photon-to-current conversion efficiency of DSSC devices fabricated with KNS dyes, the central squaric acid unit has been modified by appending the electron-withdrawing dicyano group at the central squaric unit, and the trans-configured KNS1 dye was converted to cis-configured KNS2 dye. The power conversion efficiency of devices based on the KNS dyes was studied with and without 3 equivalents of CDCA by using the I-/I3 - electrolyte. Out of these devices, the KNS1: CDCA (1:3) based cell exhibited the best PCE of 6.25\% with V OC of 793 mV, J SC of 11.08 mA cm-2, and ff of 71\%.

}, keywords = {Bulky donor unit, Dye-sensitized solar cells, self-assembly of dye, squaraine dyes, triazatruxene}, issn = {1861-4728}, doi = {10.1002/asia.70455}, author = {Ingole, Kiran Balaso and Siby, Jesna and Pandya, Rinu and Vanka, Kumar and Krishnamoorthy, Kothandam and Nithyanandhan, Jayaraj} } @article {50057, title = {Direct conversion of methane to formic acid over Au-Fe-NaZSM-5 at ambient pressure using H2O2}, journal = {Catalysis Science \& Technology}, volume = {16}, year = {2026}, month = {MAR}, pages = {1797-1805}, type = {Article}, abstract = {

Direct conversion of methane to value-added products is a long-standing challenge. This report presents the one-step conversion of methane to oxygenates using H2O2 as an oxidant over an Au and Fe supported on NaZSM-5 (0.1Au0.1FeNZ) catalyst, which produces 4264 mu mol of oxygenates with 89\% selectivity toward formic acid at 10 bar and 60 degrees C within 30 min in a batch process. The catalyst also produces 26.5 mu mol of oxygenates with 70\% selectivity for formic acid at atmospheric pressure and 80 degrees C in a continuous flow process over 9 h of reaction time, making it the first report of such a process. The synergistic interaction of Au and Fe, with the crucial role of Na ions in the zeolite framework in driving the reaction, is revealed through various characterization tools like TEM, XPS, and XAS. Theoretical studies elucidate the active sites responsible for lowering the activation barrier for the crucial C-H activation step. Thus, the catalyst enables the conversion of methane into formic acid with high activity and selectivity, offering new possibilities for harnessing this potent greenhouse gas under process-friendly conditions that were previously unexplored.

}, issn = {2044-4753}, doi = {10.1039/d5cy01422k}, author = {Kumar, Pawan and Ahangar, Iqra and Kesarwani, Srishti and Urkude, Rajashri and Patil, Nita A. R. and Niphadkar, Prashant and Bokade, Vijay V. and Haider, M. Ali and Vinod, C. P.} } @article {50078, title = {Kekule diradicaloid with a naphthalene spacer}, journal = {Organometallics}, volume = {45}, year = {2026}, month = {MAR }, pages = {624-627}, type = {Article}, abstract = {

The availability of a diverse array of carbenes led to the generation of a catalog of carbene based Kekule diradicaloids, but the linker in such molecules is mostly limited to phenylene or biphenylene. Here we have prepared a closed-shell Kekule diradicaloid (2) separated by a naphthalene moiety and stabilized by two capping 5-SIDipp [5-SIDipp = 1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene] from the reduction of the corresponding dication (1). The combined experimental and computational studies confirm that 2 is in a closed-shell singlet state exhibiting a singlet-triplet energy difference (Delta ES-T) of 18.7 kcal/mol, which is considerably lower than Thiele{\textquoteright}s version (29.1 kcal/mol).

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.5c00508}, author = {Kundu, Gargi and Pramanik, Debjit and Dash, Soumya Ranjan and Kumar, Ravi and Tothadi, Srinu and Ghosh, Aryya and Vanka, Kumar and Sen, Sakya S.} } @article {50026, title = {Lattice dynamics and electron-phonon coupling in geometrically distorted halide double perovskites}, journal = {Journal of Physical Chemistry C}, volume = {130}, year = {2026}, month = {MAR }, pages = {3486-3503}, type = {Article}, abstract = {

Electron-phonon coupling is a critical factor in regulating the photophysical behavior of halide double perovskites (HDPs), influencing their emission broadening through lattice softness and exciton dynamics. In this work, we investigate four structurally distorted compounds, such as Cs2Ag0.4Na0.6InCl6, Cs2NaIn0.9Bi0.1Cl6, Cs2AgIn0.9Bi0.1Cl6, and Cs2Ag0.4Na0.6In0.9Bi0.1Cl6, prominent for their broad emission characteristics. Our combined experimental analysis and numerical models demonstrate that the electron-phonon coupling is dictated by the interplay between the sublattice distortion and the bonding nature between the metal and halide atoms, which vitally modulates the overall lattice softness and the resulting spectral broadening. The introduction of more ionic Na-Cl bonds in the HDP structure softens (weaker bonding) the lattice and enhances the phonon population, resulting in strong coupling between the electron and phonon, as quantified by the Huang-Rhys factor for Cs2NaIn0.9Bi0.1Cl6 (18.88), Cs2Ag0.4Na0.6InCl6 (17.64), and Cs2Ag0.4Na0.6In0.9Bi0.1Cl6 (14.46). Raman analysis further evidences Na-induced lattice softness with a 5 cm-1 red shift of the A1g mode in Cs2NaIn0.9Bi0.1Cl6, compared to Ag-containing HDPs. These findings highlight that Na-based compounds have stronger electron-phonon coupling than Cs2AgIn0.9Bi0.1Cl6. Furthermore, temperature-dependent phonon dynamics using the cubic anharmonic model and the three-phonon anharmonicity theory demonstrate that the distorted structures involve a phonon anharmonicity due to the thermal disorder. We show that strong coupling between the electron and the energetic phonon broadens the emission spectrum but suppresses the PL intensity. This quenching may arise from the excessive phonon-intervened nonradiative relaxations in the Na-rich compounds. By contrast, the temperature-dependent PL of Cs2Ag0.4Na0.6In0.9Bi0.1Cl6, a compound with maximum PL intensity, reveals the major contribution of optical phonon to electron-phonon coupling, which facilitated the efficient STE formation. This study highlights the significance of lattice softness to regulate the optoelectronic properties of the halide double perovskites, providing a design approach for compositional engineering towards high-performance optoelectronic devices.

}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.5c07577}, author = {Kanapathi, Prakash and Ravi, Nalini and Mohan, Subramaniam and Vijayan, Viswanathan and Appadurai, Tamilselvan} } @article {50020, title = {Metal films from a single source and their application in nanoporous filtration synthesis, electromagnetic interference shielding, and electroadhesion}, journal = {ACS Omega}, volume = {11}, year = {2026}, month = {MAR}, pages = {14203-14211}, type = {Article}, abstract = {

Electroless metal depositions are carried out by a series of reduction steps involving multiple metal ions to obtain a film on synthetic and natural substrates. Herein, we report the use of metal ions from a single element to deposit metal films on various substrates. In a typical metal deposition procedure, Pd2+ ions are anchored on a polycarbonate membrane with vertically aligned pores of 0.6 mu m, which was reduced to its nanoparticles by sodium borohydride. The Pd nanoparticle-modified membrane was then immersed in a Pd plating bath. The Pd2+ ions are reduced by the reducing agent present in the plating bath. The reaction is catalyzed by the Pd nanoparticles. The Pd-modified membrane with vertically aligned Pd tubes were used to convert p-nitrophenol to p-aminophenol, which is an important molecule in the production of acetaminophen. While filtering the reactants through the Pd tubes, due to increased collision between the reactants and the catalyst Pd tubes, 100\% conversion is achieved within 5 min. On the contrary, the conversion is only 10\% if the membrane is placed in a vessel comprising the reactants. Due to the versatile nature of the metal deposition procedure, nickel was deposited on cotton substrates by a similar procedure. The nickel film-coated cotton cloth showed an impressive electromagnetic shielding interference efficiency of -60 dB while the uncoated cotton cloth did not shield electromagnetic radiation. To demonstrate the versatility of the approach, Pd-coated synthetic polymeric substrates are used to electroadhere gels and gel-like substances. Nickel-coated substrates are not suitable for electroadhesion; hence, a conjugated polymer was deposited on the substrate to electroadhere gel-like substances.

}, issn = {2470-1343}, doi = {10.1021/acsomega.4c07730}, author = {Veerasubash, Muthupandi and Birajdar, Sarika Hanamant and Kika, Sharmin Percy and Senthilkumaran, Marimuthu and Deshpande, Karan and Shevate, Rahul and Krishnamoorthy, Kothandam} } @article {49960, title = {(NHC-olefin)-nickel(0) nanoparticles: an efficient and selective catalyst for hydrogenation reactions at low temperature and pressure}, journal = {Journal of Catalysis}, volume = {453}, year = {2026}, month = {JAN}, pages = {116487}, type = {Article}, abstract = {

The reduction of a NHC-cinnamyl nickel(II) organometallic complex through the use of different MeMgBr or MeMgCl reagents led to two types of NHC-olefin-coordinated nickel nanoparticles. Both of these unsupported nickel-NHC based nanomaterials behaved under hydrogen pressure as effective and selective catalysts operating at low temperature (\<= 80 degrees C), pressure (\<= 20 bar) and loading (\<= 6 mol\%) for the reductions of broad scopes of alkenes, alkynes, imines and heterocycles, including a challenging tetra-substituted alkene. Among these two nickel-NHC nanocatalysts, the one generated with MeMgCl showed a significant high catalytic activity with high yields and could stand the comparison with Raney nickel and state-of-the-art nickel nanocatalysts. For example, by studying the hydrogenation of 1-phenylcyclohexene in ethanol at 60 degrees C under 10 bar of H2, 3 mol\% of this catalyst achieved the reaction within a single hour on a 5 mmol/0.8 g substrate scale with a yield of 96 \%, a turnover number (TON) of 32 and a turnover frequency (TOF) of 32. Characterizations confirmed the coordination of the NHC-olefin ligands to the nickel nanoparticles, the reduced state of the nickel and the (poly-) crystallinity of the nanoparticles.

}, keywords = {alkenes, Alkynes, heterocycles, Hydrogenation, imines, N -heterocyclic carbene ligand, nanocatalysis, Nickel}, issn = {0021-9517}, doi = {10.1016/j.jcat.2025.116487}, author = {Avello, Marta G. and Singh, Geetika and Truong-Phuoc, Lai and Vidal, Loic and Papaefthimiou, Vasiliki and Chesse, Matthieu and Gruber, Nathalie and Chetcuti, Michael J. and Vanka, Kumar and Ritleng, Vincent and Pham-Huu, Cuong and Michon, Christophe} } @article {50043, title = {Novel prodrug-inspired eugenol derivatives with enhanced bioavailability, anti-diabetic and anti-glycation efficacies}, journal = {Journal of Molecular Structure}, volume = {1357}, year = {2026}, month = {APR}, pages = {145175}, type = {Article}, abstract = {

In this study, we present the design, synthesis, and evaluation of novel eugenol analogs aimed to overcome its limited bioavailability due to insolubility in aqueous media. Thus, we re-engineered eugenol using prodruginspired structural modifications to improve pharmacokinetic properties. First, we structurally modified eugenol and synthesized its natural amino acid conjugates as esters and carbamates. These were prepared in NBoc protected, free amine, and HCl salt forms. These modifications are expected to improve the polarity and solubility of eugenol congeners in biological systems. They can also release the parent eugenol through enzymatic hydrolysis, enhancing its therapeutic potential. Next, we comprehensively screened for these derivatives through in silico studies followed by in vitro and in vivo assays. These include DPPH radical scavenging (IC50 range: 37.7 to 103.7 mu M), inhibition of (i) alpha-amylase (IC50 23.1 to 67.3 mu M), (ii) alpha-glucosidase (IC50 43.6 to 50.4 mu M), (iii) glycation (IC50 31.9 to 110.3 mu M) along with pharmacokinetic profiling and toxicity assessments. These experiments collectively demonstrated improved activity of eugenol analogs for several important parameters. Specifically, six analogs-epoxy eugenol (39), hydroxy eugenol (43), aspartate eugenol (26), isoleucinate eugenol (24), glutamate eugenol (37), and glutamate-salt eugenol (27) exhibited superior bioavailability, absorption, and distribution over to the parent compound eugenol. These analogs were found to be non-toxic and safe for oral administration. Overall, the study establishes a mechanistic and rational framework for modifying eugenol to overcome its inherent biopharmaceutical limitations, positioning them as promising candidates for treating diabetes and glycation-related conditions.

}, keywords = {Amino acid conjugates, Antidiabetic activity, Bioavailability enhancement, Drug design and synthesis, Eugenol analogs, In silico and in vitro studies}, issn = {0022-2860}, doi = {10.1016/j.molstruc.2025.145175}, author = {Kataria, Priyanka and Vairale, Shiva and Mote, Chandrashekhar and Joshi, Kaustubh and Joshi, Rakesh and Kulkarni, Mahesh J. and Giri, Ashok P. and Kontham, Ravindar and Agawane, Sachin B.} } @article {49814, title = {Orthogonally Engineered Redox-Active Polyimide-Carbon Nanotube Hybrids for Long-Life Lithium-Ion Battery Cathode}, journal = {Small}, volume = {22}, year = {2026}, month = {JAN}, type = {Article}, abstract = {

The diverse structural tunability and engineered electronic properties of organic polymers have sparked significant interest in their use as cathode materials for lithium-ion storage. Recent advances suggest that organic cathodes can serve as promising alternatives to conventional metal oxide counterparts due to their elemental abundance, safety, and high theoretical capacity. However, developing cathode materials that simultaneously exhibit high specific capacity, long cycle life, and excellent rate performance remains a critical challenge. In this study, the synthesis and application of a redox-active polyimide based on orthogonally positioned, active site-rich mellitic trianhydride (MTA) and naphthalene diimide (NDI), integrated with multi-walled carbon nanotubes (MWCNTs), referred to as MTA-NDI@CNT are reported. The pristine MTA-NDI polymer demonstrates a specific capacity of 60 mAh g-1 at a current density of 200 mA g-1 and exhibits remarkable cycling stability over 20 000 cycles. Upon hybridisation with CNT (10 wt.\%), the composite (MTA-NDI@CNT) delivers a nearly threefold enhancement in specific capacity, reaching 170 mAh g-1 at 500 mA g-1, along with stable cycling performance over 1300 cycles and 60.5\% capacity retention.

}, keywords = {cathode, CNT, lithium-ion battery, orthogonality, Polyimide}, issn = {1613-6810}, doi = {10.1002/smll.202509881}, author = {Thanasekar, Chandragopal and Javaregowda, Bharathkumar H. and Veer, Sairam Dnyaneshwar and Devasia, George and Krishnamurty, Sailaja and Krishnamoorthy, Kothandam and Babu, Sukumaran Santhosh} } @article {50037, title = {Phenylpropanoid-specific glycosyltransferases from mango and their potential role in defense}, journal = {Plant Physiology and Biochemistry}, volume = {232}, year = {2026}, month = {MAR}, pages = {111137}, type = {Article}, abstract = {

Alphonso mango (Mangifera indica cv. Alphonso) is a cornerstone of India{\textquoteright}s fruit industry due to its distinct aroma and shelf-life characteristics. The uridine diphosphate-dependent glycosyltransferases (UGTs) play a crucial role in stabilising aroma and defense-related specialised metabolites in fruits. The present study explores the potential role of UGTs during mango ripening and Colletotrichum gloeosporioides infection. Gene expression analysis indicated that UGTs showed dynamic expression in skin and pulp during ripening. Phylogenetic analysis revealed substrate-driven divergence of UGTs, with MiUGT92A14 and MiUGT95B15 forming distinct clades associated with flavonoid glycosylation. Recombinant UGTs showed a higher preference for UDP-glucose, which is corroborated by the high accumulation of UDP-glucose during ripening. Furthermore, it was observed that MiUGT92A14 prefers phenolic acids as substrates, while MiGT95B15 shows flavonoid specificity. Spore germination assays demonstrated that both aglycones and their glycosylated derivatives suppressed early fungal morphogenesis, supporting a role for UGT-mediated glycosylation in maintaining defense-related metabolites in a bioactive yet non-toxic form during fruit ripening. Additionally, Colletotrichum gloeosporioides inhibition assays demonstrated that glycosylated products of selected UGTs exhibited equal or enhanced antifungal activity compared with their aglycone forms, indicating that glycosylation promotes the safe accumulation of antifungal compounds by reducing aglycone toxicity to the plant. These findings suggest that glycosylation of specific metabolites is a key for ripening process and to potentiate defence against fungal pathogen.

}, keywords = {Anthracnose, defense, Flavonoid, Glycoconjugates, Uridine diphosphate-dependent glycosyl-transferase}, issn = {0981-9428}, doi = {10.1016/j.plaphy.2026.111137}, author = {Vare, Tejas and Joshi, Rakesh and Liao, Jieren and Hoffmann, Thomas and Schwab, Wilfried and Giri, Ashok} } @article {49954, title = {Photoluminescence decay lifetime study of hydrothermally synthesized highly porous ruthenium-silica composite for optical dissolved oxygen sensing application}, journal = {ACS Applied Nano Materials}, volume = {9}, year = {2026}, month = {JAN}, pages = {937-949}, type = {Article}, abstract = {

Pore size and surface area of photoluminescence (PL)-based transition metal composites play crucial roles in facilitating oxygen diffusion, thereby enhancing the response and sensitivity of optical dissolved oxygen (DO) sensors. In this study, we successfully applied the hydrothermal method to synthesize a porous ruthenium composite embedded in a silica matrix, demonstrating its effectiveness for optical DO sensing applications. The ruthenium-silica (Ru-Si) composites were synthesized using Ru(bpy)3 2+ and tetraethyl orthosilicate (TEOS) as precursors, with reaction temperatures ranging from 120 degrees C to 200 degrees C over a fixed duration of 4 h. The structural, morphological, and compositional characterization techniques confirmed the successful synthesis and evaluated the porosity, surface features, and chemical structure of the resulting composites. The optimized Ru-Si composite exhibited the highest porosity, characterized by a specific surface area of 996.78 m2 g- 1, and exhibited the highest decay lifetime of 8.14 mu s in deionized (DI) water, compared to other composites. Importantly, we demonstrate an excellent linear response of the synthesized Ru-Si composite to DO concentrations ranging from 2.58 to 11.16 mg L-1, with a Stern-Volmer constant of 0.12. Furthermore, a density functional theory study was conducted to investigate the electronic transitions and to elucidate the oxygen quenching mechanism of the excited Ru composite with molecular oxygen. The calculated photophysical parameters of the composite show good agreement with the experimental results. Preliminary results suggest that the synthesized Ru-Si with high pore size and surface area could be an efficient and effective composite for use in DO sensing applications.

}, keywords = {Hydrothermal method, opticalDO sensor, oxygen quenching, photoluminescent, ruthenium composite}, doi = {10.1021/acsanm.5c04307}, author = {Hattale, Gangadhar and Kadam, Rutuja and Virole, Vishal and Pandya, Rinu and Paul, Aditya and Kumar, Ajay and Shevate, Rahul and Vanka, Kumar and Saha, Avishek and Kanawade, Rajesh} } @article {50050, title = {Polysulfone-based polymer carbon dot membrane for optical dissolved oxygen sensing application}, journal = {Chemistry-An Asian Journal}, volume = {21}, year = {2026}, month = {MAR}, pages = {e70685}, type = {Article}, abstract = {

The precise monitoring of dissolved oxygen (DO) is essential across industrial, environmental, and biomedical applications. However, the state-of-the-art DO sensing methods often suffer from inherent limitations, which hinder their effectiveness for real-time and long-term DO monitoring. Optical DO sensing, despite its advantages, utilizes expensive metal complexes and is prone to photobleaching and slow response time. Here, we introduce a novel polymer carbon dot (PCD) as a promising candidate for lifetime-based optical DO sensing. The PCD is a metal-free, nontoxic, fluorescent, long decay-lifetime material that is synthesized through hydrothermal method. Our fluorescent PCD exhibits high emission quantum yield (24.32\%), long decay-lifetime (10.43 \& micro;s), and a linear response to DO concentrations ranging from 0.7 to 12.7 mg/L, with a Stern-Volmer constant of 0.1115. Further, to obtain better oxygen diffusion, high porosity, optical transparency, and high flexibility, PCD was embedded into a polysulfone matrix (PSF_PCD). The PSF_PCD membrane shows better results for the decay lifetime (9.4 \& micro;s), surface energy (40.26 mN/m), and average pore diameter of 5 nm. Hence, the obtained results demonstrate the applicability of the PCD in optical DO sensors for real-time and long-term monitoring of DO levels.

}, keywords = {decay lifetime, dissolved oxygen, Hydrothermal method, polymer carbon dots, polysulfone-based membrane}, issn = {1861-4728}, doi = {10.1002/asia.70685}, author = {Kadam, Rutuja and Hattale, Gangadhar and Virole, Vishal and Pal, Sanjivani and Abraham, Athira and Paul, Aditya and Kumar, Ajay and Shevate, Rahul and Banpurkar, Arun and Kanawade, Rajesh and Saha, Avishek} } @article {49801, title = {Potential tuneable glucose oxidation to selective C6 molecules and CC cleavage, and parallel green H2 production: sustainable high current density electrolysis}, journal = {Chemical Engineering Journal}, volume = {529}, year = {2026}, month = {FEB}, pages = {172633}, type = {Article}, abstract = {

Current study elucidates the electrocatalytic efficacy of palladium-nanocubes (Pd-NCs) for the selective oxidation of glucose to value-added chemicals with concomitant hydrogen evolution. The Pd-NC catalyst demonstrated exceptional activity and product selectivity, achieving nearly quantitative glucose conversion (\>99 \%) with high gluconic and glucaric acid yield at low anodic overpotential (0.6 V vs. RHE) in alkaline electrolyte. At not-so-high elevated potentials (1.2 V vs. RHE), oxidative CC scission prevails, yielding shorter-chain carboxylates along with C6-acids. Reaction products are thoroughly characterized and quantitatively estimated by NMR spectral methods; NMR methods also provide CC cleavage and mechanistic pathways of glucose to various products. Complementary DFT calculations delineate the thermodynamic favorability of glucose adsorption on Pd-NC surfaces (-1.83 eV) and the exergonic oxidation pathway under applied bias, corroborating experimental product distributions. In a two-electrode electrolyzer, Pd-NC anode paired with Pt/C and Ni2P cathode demonstrates 100 mA/cm(2) at 0.99 V and 1.37 V, respectively, with 48 \% reduction in energy input (26.6 kWh/kg H-2) compared to conventional alkaline electrolysis; critically, H-2 production energy is lower than the usable energy (33.3 kWh/kg H-2). Sustainable chronopotentiometric assays confirm sustainability (similar to 140 h) in alkaline as well as saline electrolytes, underscoring the system{\textquoteright}s resilience against chloride-mediated corrosion. Present work establishes a proof of concept for integrated biomass-component valorization and carbon-negative green hydrogen production, merging atomic-level mechanistic insights with scalable reactor design. Optimization of reaction parameters, including potential tuning, reaction temperature and electrolyte engineering, offers a compelling strategy to further enhance C6 and fragmented product selectivity and overall system efficiency.

}, keywords = {biomass valorization, electrocatalysis, energy conversion, Sustainability}, issn = {1385-8947}, doi = {10.1016/j.cej.2026.172633}, author = {Chauhan, Inderjeet and Patra, Kshirodra Kumar and Vijay, Pothoppurathu M. and Nalajala, Naresh and Mehta, Shweta and Joshi, Kavita and Ravindranathan, Sapna and Gopinath, Chinnakonda S.} } @article {50022, title = {Radical-promoted cyclization of 3-allyl-2-arylquinazolinones mediated by silver(i) salts to access SCF3/SCN-enriched dihydroisoquinolino[1,2-b]quinazolinones}, journal = {Organic \& Biomolecular Chemistry}, volume = {24}, year = {2026}, month = {FEB}, pages = {1263-1267}, type = {Article}, abstract = {

Herein, we describe an efficient approach for the synthesis of SCF3- and SCN-functionalized polycyclic dihydroisoquinolino[1,2-b]quinazolinones through radical-mediated thio-functionalization of allylic alkenes followed by intramolecular cyclization. The transformation proceeds through sulfur-radical-triggered C-S and C-C bond formation, providing an efficient route to sulfur- and fluorine-enriched polycyclic quinazolinones. Moreover, this strategy offers high atom economy, operational simplicity, and broad substrate compatibility.

}, issn = {1477-0520}, doi = {10.1039/d5ob01755f}, author = {Vara, Vijay and Thete, Kishor R. and Khan, Akram A. and Muthukrishnan, M.} } @article {50031, title = {Reaction kinetics for dehydrogenation of decahydroquinoline to quinoline for hydrogen generation}, journal = {Chemical Engineering \& Technology}, volume = {49}, year = {2026}, month = {FEB}, pages = {e70177}, type = {Article}, abstract = {

Catalytic dehydrogenation of decahydroquinoline (DHQ) to quinoline is a promising pathway for hydrogen release in liquid organic hydrogen carrier systems. In this work, solvent-free DHQ dehydrogenation over Pd/Al2O3 is systematically investigated to evaluate hydrogen release performance and reaction kinetics. High DHQ conversion (83.9\%) and degree of dehydrogenation (82.7\%) are achieved at optimal reaction conditions. A power-law kinetic model based on a simplified reaction mechanism is developed and simulated using a Markov Chain Monte Carlo (MCMC) approach for estimation of rate constants and validation of concentration profiles with experimental data. The apparent activation energies are determined to be 45.85 kJ/mol for DHQ to 5,6,7,8-tetrahydroquinoline (bz-THQ) and 185.43 kJ/mol for bz-THQ to quinoline formation, identifying latter as the rate-limiting step. This framework provides mechanistic insight and supports the potential of DHQ as an efficient hydrogen carrier.

}, keywords = {Decahydroquinoline (DHQ), degree of dehydrogenation, Dehydrogenation, rate-limiting step, Reaction kinetics, Weisz-Prater criterion}, issn = {0930-7516}, doi = {10.1002/ceat.70177}, author = {Bagwan, Farahanaz M. and Dadkar, Sarthak S. and Kinage, Anil K. and Vasireddy, Satyam Naidu} } @article {50030, title = {Switchable solid-state emission in GFP chromophore analogue cocrystals via competing AIE and ACQ pathways}, journal = {CrystEngComm}, volume = {28}, year = {2026}, month = {MAR}, pages = {1775-1780}, type = {Article}, abstract = {

We present a crystal-engineering approach enabling switchable solid-state emission (green -\> orange -\> quenched) in GFP-chromophore analogue cocrystals. The coformer{\textquoteright}s electronic and supramolecular effect shifts the photophysical pathway: intramolecular CT in cocrystal-I (green) and cocrystal-III (quenched) and intermolecular CT in cocrystal-II, yielding orange emissions and highlighting cocrystallization{\textquoteright}s power for tunable luminophores.

}, doi = {10.1039/d6ce00041j}, author = {Mali, Bhupendra P. and Dabke, Niteen B. and Sharma, Himanshu and Dash, Soumya Ranjan and Manoj, Kochunnoonny and Vanka, Kumar and Gonnade, Rajesh G.} } @article {50081, title = {Targeted genomic surveillance unveils genetic variations linked to regional malaria drug resistance dynamics in India}, journal = {Open Forum Infectious Diseases}, volume = {13}, year = {2026}, month = {MAR}, pages = {ofag106}, type = {Article}, abstract = {

Background India has made substantial progress in reducing Plasmodium falciparum malaria cases and has set a target to eliminate malaria by 2030. Although artemisinin-based combination therapy (ACT) treatment remains effective, tracking regional differences in genetic variants associated with antimalarial resistance is required for effective drug policy implementation.Methods We analyzed 238 P. falciparum clinical samples from 6 Indian states by sequencing 15 parasite genes associated with reduced drug effectiveness. The method involved nanopore sequencing of target gene amplicons derived from dried blood spots using a highly-sensitive PfMDR15 surveillance panel.Results India{\textquoteright}s historical policy of artesunate-sulfadoxine-pyrimethamine in central India and artemether-lumefantrine in the Northeast has shaped contrasting resistance profiles. In the Northeast, chloroquine resistance persisted at high frequency (Pfcrt K76T and CVIET haplotype; Pfaat1 S258L), alongside quintuple and sextuple Pfdhfr-Pfdhps haplotypes conferring complete sulfadoxine-pyrimethamine resistance. Central India showed variable chloroquine resistance (parasites largely retained wild-type Pfcrt) and emerging lumefantrine tolerance (Pfmdr1 Y184F, Pfaat1 S258L). Interestingly, Delhi (Central India) parasites resembled profiles from the distant Northeast, which borders South East Asia. The detection of Pfaat1 S258L, previously reported only from Africa and associated with reduced lumefantrine susceptibility, suggests convergent evolution under ACT partner-drug pressure. No WHO-validated Pfk13 artemisinin resistance mutations were detected, supporting continued efficacy of ACT.Conclusions India{\textquoteright}s resistance landscape is fragmented, with signals of expanding lumefantrine tolerance and importation or evolution of globally relevant mutations. These findings highlight the importance of integrating molecular genomic surveillance into malaria control policy to monitor and protect ACT effectiveness and advance malaria elimination. Monitoring of drug resistance associated mutations in P. falciparum parasites is critical for effective drug treatment. We have demonstrated the use of a scalable genomic surveillance protocol for tracking drug resistance linked mutations in parasite genes from clinical isolates in India. The study suggests extensive regional diversity in antimalarial resistance profiles and provides the first hint of possible emergence of lumefantrine tolerance in India.

}, keywords = {drug resistance, malaria, Oxford nanopore, P. falciparum, pfMDR15}, issn = {2328-8957}, doi = {10.1093/ofid/ofag106}, author = {Khilari, Ajinkya and Sharma, Shweta and Bajpai, Manali and Viswan, K. Anju and Chaturvedi, Rini and Mirdha, Bijay R. and Rahi, Manju and Sharma, Amit and Shanmugam, Dhanasekaran} } @article {50091, title = {Unveiling the reactivity of N-heterocyclic methylene hydrazines}, journal = {Dalton Transactions}, volume = {55}, year = {2026}, month = {APR}, pages = {5432-5436}, type = {Article}, abstract = {

We present the first reactivity profile of N-heterocyclic methylene hydrazines, revealing distinct competition between steric and electronic control. Reactions with HCl are electronically driven, resulting in protonation at the proximal nitrogen, while the bulky Lewis acid B(C6F5)3 coordinates to the sterically accessible distal nitrogen. Additionally, we demonstrate that these scaffolds undergo spontaneous, base-free HCN elimination with tetracyanoethylene (TCNE) to form highly conjugated molecules with significantly reduced HOMO-LUMO gaps.

}, issn = {1477-9226}, doi = {10.1039/d6dt00611f}, author = {Balayan, Kajal and Biswas, Arindam and Sharma, Himanshu and Tiwari, Prabhakar and Vanka, Kumar and Gonnade, Rajesh G. and Rath, Arup K. and Sen, Sakya S.} } @article {49795, title = {Vanillin-based recyclable thermosets and their glass fiber reinforced composites}, journal = {Macromolecular Chemistry and Physics}, volume = {227}, year = {2026}, month = {JAN}, type = {Article}, abstract = {

The accumulation of end-of-life plastic materials and composite reinforcement waste materials has brought much attention to developing sustainable alternatives and their re-processability. Incorporating covalent adaptable networks (CANs) into the crosslinked network bridges the concept of reversibility into the otherwise conventional non-reversible networks. This study investigates the structure-property relation in two reversible hardener systems derived from vanillin using Schiff base chemistry. The {\textquoteleft}{\textquoteleft}CAN{\textquoteright}{\textquoteright} systems were synthesized by condensation of vanillin with two amines, 4,4{\textquoteright}-oxydianiline and tris(2-aminoethyl)amine, respectively, to form Va_ODA and Va_TAEA. The epoxy thermosets exhibited glass transition temperatures (T-g) of 125 degrees C and 115 degrees C, respectively, for Va_ODA and Va_TAEA, which is superior to most reversible vanillin-based systems reported. The vitrimer-thermosets exhibited promising mechanical and thermal properties, and reshaping abilities as a function of applied temperatures, indicating the dynamic nature of linkages. Chemical degradability was demonstrated by heating to 80 degrees C for 12 h in aqueous acidic medium or excess amine. The fabricated glass fiber composites exhibited good mechanical properties with tensile strength of 361 MPa and degradability in acetic acid/water mixture with a fiber recovery of \>98 \%. The recovered glass fiber exhibited almost similar tensile strength as the virgin glass fiber, demonstrating its potential reusability. The epoxy vitrimers underwent mechanical reprocessing through hot-pressing, as well as chemical reprocessing via 3D printing and by regeneration of imine bonds to form an epoxy resin.

}, keywords = {3D printing, covalent adaptable network, re-processability, Schiff base, Vanillin}, issn = {1022-1352}, doi = {10.1002/macp.202500420}, author = {Veetil, Ashwani Puthiya and Ravikumar, Aniruddha and Rajput, Tejas and Singh, Aman Kumar and Thakur, Tamanna and Krishna, Abhijith and Pol, Harshawardhan and Shanmuganathan, Kadhiravan and Asha, S. K.} } @article {50070, title = {What drives property prediction for solid-state hydrogen storage? data or smart features?}, journal = {International Journal of Hydrogen Energy}, volume = {226}, year = {2026}, month = {APR }, pages = {154499}, type = {Article}, abstract = {

Metal hydrides play a pivotal role in a wide range of applications, including hydrogen storage, compression, heat management, and catalysis, making them a central focus of interdisciplinary research spanning chemistry, materials science, and engineering. The performance of the metal hydride-based systems is strongly governed by the thermodynamics of metal-hydrogen interactions. Among key thermodynamic properties, the equilibrium plateau pressure (P-eq) is particularly critical, as it defines operating conditions for hydrogen absorption and desorption. Traditionally, determining P-eq requires extensive experimental measurements, which limits the pace of materials discovery. On the other hand, predicting it through ML-based models is constrained by the availability of limited data. In this work, we demonstrate that smart features can be a way to overcome this limitation. EquiP, an ML model trained to predict ln(P-eq) as a function of temperature, generates Van{\textquoteright}t Hoff plots (P-eq vs. 1/T), enabling rapid determination of enthalpy and entropy of hydride formation. We demonstrate that incorporating structural descriptors derived from X-ray diffraction (XRD) data improves the performance of the model, particularly with sparse training datasets. A model trained using only compositional descriptors yields a validation mean absolute error (MAE) of 0.21 bar, whereas incorporating XRD features reduces the MAE substantially to 0.07 bar. This work demonstrates that with limited data, intelligent feature design grounded in domain knowledge is the key to improving predictions of complex material properties.

}, keywords = {Experimental data, Feature engineering, Hydrogen storage, machine learning, Metal hydrides, Property prediction}, issn = {0360-3199}, doi = {10.1016/j.ijhydene.2026.154499}, author = {Verma, Ashwini and Joshi, Kavita} }