In vitro enzyme mediated synthesis of metal sulfide nanoparticles: control of particle size of CdS, Ni7S6, PbS, Co3S4 nanoparticles using synthetic peptides - Ansary, Abu Ayoobul; Khan, Muhammed I.; Gaikwad, Sushama M. (Science of Advanced Materials, 2012)
We report the use of enzyme sulfite reductase for the in vitro synthesis of technologically important metal sulfide quantum dots viz. Co3S4, PbS and Ni7S6. Also we report the use of synthetic peptides to control the particle size of the above metal sulfide quantum dots in addition to CdS, synthesized using enzyme. Sulfite reductase when incubated with aqueous CdCl2, or Co(NO3)(3) or NiCl2 or Pb(NO3)(2), and Na2SO3 in the presence of the appropriate capping peptide resulted in the synthesis of particle size controlled CdS, Co3S4, Ni7S6, or PbS quantum dots respectively. These, enzyme mediated synthesized and size controlled metal sulfide quantum dots, were characterized using Absorbance and photoluminescence spectrometry, X-ray diffraction, X-ray photoelectron spectroscopy and High resolution-transmission electron microscopy.
Keywords: Capping Peptide; Enzyme; Metal Sulfide Nanoparticles; quantum dots; Size Control; Sulfite Reductase

Interrupted PET coupled TBET process for the design of a specific receptor for Hg2+ and its intracellular detection in MCF7 cells - Saha, Sukdeb; Mahato, Prasenjit; Baidya, Mithu; Ghosh, Sudip K.; Das, Amitava (Chemical Communications, 2012)
A new coumarin–rhodamine conjugate constitutes a unique example of the interrupted PET coupled TBET response for developing an imaging reagent for determining the intracellular distribution of Hg2+ in MCF7 cells exposed to [Hg2+] as low as 2 ppb.

Kernel morphometric traits in hexaploid wheat (Triticum aestivum L.) are modulated by intricate QTL x QTL and genotype x environment interactions - Prashant, Ramya; Kadoo, Narendra Y.; Desale, Charushila; Kore, Prajakta; Dhaliwal, Harcharan Singh; Chhuneja, Parveen; Gupta, Vidya (Journal of Cereal Science, 2012)
Wheat kernel size and shape influence its flour yield and market price. A hexaploid wheat population of 185 recombinant inbred lines was evaluated for five kernel morphometric traits namely, 1000-kernel weight, kernel length, width, length width ratio and factor form density in two diverse agro-climatic regions in India in five to eight year location combinations. Additive main effects and multiplicative interaction analysis revealed significant contributions from genotype (G) and genotype x environment (G x E) effects for these traits. Quantitative trait locus (QTL) analysis by composite interval mapping (CIM) was performed using a linkage map of 251 SSR markers and 59 QTLs distributed on 16 chromosomes were identified. The majority of the QTLs were located on the D genome (44.07%) and the homeologous chromosomes of Group 2 (38.98%). Stable QTLs detected in three or more year location combinations were identified for four traits. Multi-trait CIM showed 10 chromosomal regions harboring putative pleiotropic loci. Complexity in the genetic effects was further revealed by QTL analysis based on mixed-linear model that indicated 19 QTLs with significant individual effects (main-effect QTLs) and 14 QTL x QTL interactions. Five of these - nineteen main-effect QTLs and one of the fourteen QTL x QTL interactions showed environmental influence. (c) 2012 Elsevier Ltd. All rights reserved.
Keywords: Epistatic QTLs; Genotype x environment interactions; Kernel size and shape; Stable QTLs

Kinetic modeling and optimization of operating parameters for transvinylation of lauric acid - Kamble, Sanjay P.; Manjarekar, Onkar; Mawale, Ravi; Kulkarni, Bhaskar D.; Chowdary, Naresh; Gupte, Milind Y.; Barve, Prashant P. (International Journal of Chemical Kinetics, 2012)
The transition metal complex catalyzed transvinylation of carboxylic acid with vinyl acetate monomer is of significant interest to industry. The palladium complex catalyzed transvinylation of lauric acid using vinyl acetate monomer is a reversible reaction. In present article, design of experiments (DOE) statistics is used to study effects of various operating parameters on transvinylation of lauric acid. The kinetic parameters forward and backward rate constants and the thermodynamic parameters such as equilibrium constant and energy of activation of the transvinylation of lauric acid were estimated using the Dynochem model. The optimum operating parameters for the transvinylation of lauric acid were then predicted using the Dynochem model and verified by performing the actual experiments to validate the model. It was found that the experimental results match with the predicted one. (c) 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 624634, 2012

Laser synthesized super-hydrophobic conducting carbon with broccoli-type morphology as a counter-electrode for dye sensitized solar cells - Gokhale, Rohan; Agarkar, Shruti A.; Debgupta, Joyashish; Shinde, Deodatta; Lefez, Benoit; Banerjee, Abhik; Jog, Jyoti Prakash; More, Mahendra A.; Hannoyer, Beatrice; Ogale, Satishchandra B. (Nanoscale, 2012)
A laser photochemical process is introduced to realize superhydrophobic conducting carbon coatings with broccoli-type hierarchical morphology for use as a metal-free counter electrode in a dye sensitized solar cell. The process involves pulsed excimer laser irradiation of a thin layer of liquid haloaromatic organic solvent o-dichlorobenzene (DCB). The coating reflects a carbon nanoparticle-self assembled and process-controlled morphology that yields solar to electric power conversion efficiency of 5.1% as opposed to 6.2% obtained with the conventional Pt-based electrode.

Lipase-mediated hydrolysis of flax seed oil for selective enrichment of alpha-linolenic acid - Rupani, Banin; Kodam, Kisan M.; Gadre, Ramchandra V.; Najafpour, Ghasem D. (European Journal of Lipid Science and Technology, 2012)
Polyunsaturated fatty acids (PUFA) are important ingredients of human diet because of their prominent role in the function of human brain, eye and kidney. alpha-Linolenic acid (ALA), a C18, n-3 PUFA is a precursor of long chain PUFA in humans. Commercial lipases of Candida rugosa, Pseudomonas cepacea, Pseudomonas fluorescens, and Rhizomucor miehei were used for hydrolysis of flax seed oil. Reversed phase high performance liquid chromatography followed by gas chromatography showed that the purified oil contained 12 triacylglycerols (TAGs) with differences in fatty acid compositions. Flax seed oil TAGs contained alpha-linolenic acid (50%) as a major fatty acid while palmitic, oleic, linoleic made up rest of the portion. Among the four commercial lipases C. rugosa has preference for ALA, and that ALA was enriched in free fatty acids. C. rugosa lipase mediated hydrolysis of the TAGs resulted in a fatty acid mixture that was enriched in alpha-linolenic to about 72% yield that could be further enriched to 80% yield by selective removal of saturated fatty acids by urea complexation. Such purified ALA can be used for preparation of ALA-enriched glycerides. Practical applications: This methodology allows purifying ALA from fatty acid mixture obtained from flax seed oil by urea complexation.
Keywords: a-Linolenic acid; Flax seed oil; Lipases; PUFA; Urea complexation

Low plasma albumin levels are associated with increased plasma protein glycation and HbA1c in diabetes - Bhonsle, Hemangi S.; Korwar, Arvind M.; Kote, Sachin S.; Golegaonkar, Sandeep B.; Chougale, Ashok D.; Shaik, Mahemud L.; Dhande, Nitin L.; Giri, Ashok P.; Shelgikar, Kishore M.; Boppana, Ramanamurthy; Kulkarni, Mahesh J. (Journal of Proteome Research, 2012)
Albumin is one of the most abundant plasma proteins and is heavily glycated in diabetes. In this study, we have addressed whether variation in the albumin levels influence glycation of plasma proteins and HbA1c. The study was performed in three systems: (1) streptozotocin (STZ)-induced diabetic mice plasma, (2) diabetic clinical plasma, and (3) in vitro glycated plasma. Diabetic mice and clinical plasma samples were categorized as diabetic high albumin plasma (DHAP) and diabetic low albumin plasma (DLAP) on the basis of their albumin levels. For the in vitro experiment, two albumin levels, high albumin plasma (HAP) and low albumin plasma (LAP), were created by differential depletion of plasma albumin. Protein glycation was studied by using a combination of two-dimensional electrophoresis (2DE), Western blotting, and LC-MSE. In both mice and clinical experiments, an increased plasma protein glycation was observed in DLAP than in DHAP. Additionally, plasma albumin levels were negatively correlated with HbA1c. The in vitro experiment with differential depletion of albumin mechanistically showed that the low albumin levels are associated with increased plasma protein glycation and that albumin competes for glycation with other plasma proteins.
Keywords: advanced glycation end products (AGEs); Albumin; glucose; post translational modification

Magnetic properties of nanocrystalline CoFe2O4 synthesized by thermal plasma in large scale - Nawale, A. B.; Kanhe, Nilesh S.; Patil, K. R.; Reddy, V. R.; Gupta, A.; Kale, B. B.; Bhoraskar, S. V.; Mathe, Vikas L.; Das, A. K. (Materials Chemistry and Physics, 2012)
The paper reports the large scale synthesis of nanoparticles of CoFe2O4 using thermal plasma reactor by gas phase condensation method. The yield of formation was found to be around 15 g h(-1). The magnetic properties of CoFe2O4, synthesized at different reactor powers, were investigated in view of studying the effect of operating parameters of plasma reactor on the structural reorganization leading to the different cation distribution. The values of saturation magnetization, coercivity and remanent magnetization were found to be influenced by input power in thermal plasma. Although the increase in saturation magnetization was marginal (61 emu g(-1) to 70 emu g(-1)) with increasing plasma power; a significant increase in the coercivity (552 Oe to 849 Oe) and remanent magnetization (16 emu g(-1) to 26 emu g(-1)) were also noticed. The Mossbauer spectra showed mixed spinel structure and canted spin order for the as synthesized nanoparticles. The detailed analysis of cation distribution using the Mossbauer spectroscopy and X-ray photoelectron spectroscopy leads to the conclusion that the sample synthesized at an optimized power shows the different site selective states. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Magnetic materials; magnetic properties; Mossbauer spectroscopy; Nanostructures

Mapping of tms8 gene for temperature-sensitive genic male sterility (TGMS) in rice (Oryza sativa L.) - Hussain, Appibhai J.; Ali, Jauhar; Siddiq, Ebrahimali A.; Gupta, Vidya S.; Reddy, Umesh K.; Ranjekar, Prabhakar K. (Plant Breeding, 2012)
Genetic analysis of F-2 and backcross populations of an induced temperature-sensitive genic male sterility (TGMS) mutant source F 61 with normal pollen parents revealed that TGMS trait was controlled by a single recessive gene. Molecular tagging of TGMS trait was attempted using polymorphic randomly amplified polymorphic DNA (RAPD) and simple sequence repeats (SSR) markers through bulked segregant analysis. The RAPD primers UBC 345830, UBC 313927, microsatellites RM224 and RM21 produced putative markers, which differentiate parents and bulks from sterile parent and sterile bulks. The RAPD analysis of individual F-2 plants with the primer UBC345(830) showed perfect marker-phenotype cosegregation. The 830-bp RAPD fragment, which segregated with TGMS locus at a distance of 1.33 cM, was eluted and cloned, and sequence information was used for designing sequence-characterized amplified region (SCAR) primer, which cosegregated with TGMS locus at a distance of 0.8 cM. TGMS locus was mapped onto chromosome 11 using RM21 and RM224, flanking it at a distance of 4.3 and 3.0 cM, respectively. The DNA markers tightly linked to TGMS gene (tms8) in F 61 can be cost effectively used for marker-assisted selection of TGMS trait.
Keywords: Bulked segregant analysis; randomly amplified polymorphic DNA; rice; sequence-characterized amplified region; SSR; temperature-sensitive genic male sterility

Mathematical model identifies conditions for 'unexpected' increase in target protein levels due to miRNA regulation - Gokhale, S.; Gadgil, Chetan J. (Mol. BioSyst., 2012)

MCM-41 supported phosphotungstic acid for the hydroxyalkylation of phenol to phenolphthalein - Jha, Ajay; Garade, Ajit C.; Mirajkar, Subhash P.; Rode, Chandrashekhar V. (Industrial & Engineering Chemistry Research, 2012)
A novel application of phosphotungstic acid, H3PW12O40 (PWA) supported on MCM-41 molecular sieve as a solid acid catalyst has been demonstrated for the synthesis of phenolphthalein by hydroxyalkylation of phenol and phthalic anhydride. PWA/MCM-41 (20%) showed the highest activity as compared to that of parent PWA and MCM-41 individually, due to the excellent dispersion of PWA on MCM-41 leading to the redistribution of Bronsted and Lewis acid sites on MCM-41. The effect of PWA loading on phthalic anhydride conversion and phenolphthalein selectivity was also studied. All these prepared catalysts were characterized by XRD, N-2 adsorption-desorption isotherm, pyridine-FTIR, and NH3-TPD. The effect of various reaction parameters, namely, mole ratios, catalyst concentration, temperature, reaction time, and percentage of PWA present in the catalysts on conversion and selectivity of products has been also investigated. The utility of 20% PWA/MCM-41 catalyst was established by its efficient activity for hydroxyalkylation of phenol and p-cresol with formaldehyde to the corresponding dihydroxydiarylmethane products.

MgCl2 center dot 4((CH3)(2)CHCH2OH): a new molecular adduct for the preparation of TiClx/MgCl2 catalyst for olefin polymerization - Thushara, K. S.; Gnanakumar, Edwin S.; Mathew, Renny; Ajithkumar, Thalasseril G.; Rajamohanan, P. R.; Bhaduri, Sumit; Gopinath, Chinnakonda S. (Dalton Transactions, 2012)
A new molecular adduct of MgCl2 with isobutanol, namely MgCl2 center dot 4((CH3)(2)CHCH2OH) (MgiBOH), has been prepared as a precursor to the supporting material for an olefin polymerization catalyst. The MgiBOH adduct and final titanated Ziegler-Natta catalysts have been thoroughly characterized by powder XRD, thermal analysis, Raman spectroscopy and solid-state NMR for structural and spectroscopy aspects. A peak observed at 712 cm(-1) in the Raman spectra of MgiBOH indicates the characteristic Mg-O-6 breathing mode and the formation of the adduct. The diffraction feature at 2 theta = 7.8 degrees (d = 11.223 angstrom) in the XRD confirms the adduct formation and the layered structure. The aim of the present article is to study how the insertion of a bulky isobutanol moiety affects the structural and electronic properties of the MgCl2 isobutanol molecular adduct. Indeed, the focus of the present study is to explore how the presence of isobutanol, in the initial molecular adduct, influences the final Z-N catalyst properties and its activity.

MgCl2 center dot 6C(6)H(11)OH: a high mileage porous support for ziegler-natta catalyst - Gnanakumar, Edwin S.; Thushara, K. S.; Gowda, Ravikumar R.; Raman, Sumesh K.; Ajithkumar, Thalasseril G.; Rajamohanan, P. R.; Chakraborty, Debashis; Gopinath, Chinnakonda S. (Journal of Physical Chemistry C, 2012)
A new and single phase molecular adduct of MgCl2 with six cyclohexanol molecules MgCl2 center dot 6C(6)H(11)OH (MgCyOH) has been synthesized. Structural insight to this adduct was obtained by a variety of physicochemical methods. C-13 CPMAS spectrum and single pulse MAS spectra with high power proton decoupling recorded at different relaxation time showed the presence of two different sets of magnetically unequal cylcohexanol molecules present around Mg2+. A Raman feature of MgCyOH at 712 cm(-1) confirms that cylcohexanol molecules are present around Mg2+ in an octahedral environment. MgCyOH has been used as support material to prepare Ziegler-Natta (Z-N) active catalyst. Textural property of above Z-N catalyst exhibits high surface area (236 m(2)/g) with high porosity. Above active catalyst has been screened for ethylene polymerization. Depending on the cocatalyst employed (Me3Al, Et3Al, and iso-Bu3Al) and ethylene pressure, polyethylene yield varies an order of magnitude, from 378 to 3570 g/g catalyst, indicating a possible creation of different active sites and different interaction between cocatalyst and catalyst.

Microsatellite mapping identifies TTKST-effective stem rust resistance gene in wheat cultivars VL404 and Janz - Bansal, Urmil K.; Rebecca S. Zwart; Bhavani, Sridhar; Wanyera, Ruth; Gupta, Vidya; Bariana, Harbans S. (Molecular Breeding, 2012)
Wheat cultivar VL404 carries seedling resistance to Puccinia graminis f. sp. tritici pathotype TTKST. Monogenic segregation for seedling resistance was observed in a VL404/WL711 recombinant inbred line population and the resistance locus was temporarily designated SrVL. Bulked segregant analysis using Diversity Arrays Technology markers located SrVL on chromosome 2BL. Detailed simple sequence repeat mapping placed SrVL between gwm120 and wmc175, both at genetic distances of 3.3 cM. Based on adult plant responses of Janz and VL404 in India and Kenya, we expected these cultivars to carry the same gene against TTKST. A subset of Diamondbird/Janz doubled haploid (DH) population showed monogenic segregation, when tested against TTKST and the locus was temporarily named SrJNZ. SrVL-linked markers gwm120 and wmc175 flanked SrJNZ at a similar genetic distance, thereby confirming our hypothesis. Chromosome 2BL carries Sr9, Sr16 and Sr28. Sr9 is a multi-allelic locus and all known alleles of Sr9 and Sr16 are ineffective against TTKSK and its derivatives. A recombination value of 16.7 cM between Sr9g-linked stripe rust resistance gene Yr7 and SrJNZ in Diamondbird/Janz DH population suggested that SrJNZ is not an allele at the Sr9 locus. Based on comparison of published genetic distances between Lr13, Sr9, Sr28 and Sr16 with that observed in this study, we concluded SrVL and SrJNZ to be Sr28. This gene was contributed by a common parent Gabo, which also exhibited resistance against TTKST. Sr28-linked markers gwm120 and wmc175 confirmed the presence of this gene in a high proportion of Australian cultivars that showed stem rust resistance in Kenya. These markers can be used for marker-assisted pyramiding of Sr28 with other stem rust resistance genes.
Keywords: Disease resistance; Markers; Stem rust; Ug99; Wheat

MOF derived porous carbon-Fe3O4 nanocomposite as a high performance, recyclable environmental superadsorbent - Banerjee, Abhik; Gokhale, Rohan; Bhatnagar, Sumit; Jog, Jyoti Prakash; Bhardwaj, Monika; Lefez, Benoit; Hannoyer, Beatrice; Ogale, Satishchandra B. (Journal of Materials Chemistry, 2012)
A high surface area carbon composite with Fe3O4 nanoparticles is synthesized by pyrolysis of an iron containing Metal Organic Framework (MOF). The composite can be prepared by annealing the MOF at different temperatures (500 degrees C and 600 degrees C), each case exhibiting unique properties in terms of the hydrophobic behaviour and surface area, resulting in specific applicability domains. We highlight the exceptional behaviour of this material as a magnetically separable and recyclable superadsorbent for removal and recovery of environmental pollutants (oil/hydrocarbon and dye/phenol).

Molecular oxygen-assisted oxidative dehydrogenation of ethylbenzene to styrene with nanocrystalline Ti1-xVxO2 - Sivaranjani, Kumarsrinivasan; Verma, Akrati; Gopinath, Chinnakonda S. (Green Chemistry, 2012)
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.

Multifaceted folding in a foldamer featuring highly cooperative folds - Ramesh, Veera V. E.; Priya, Gowri; Kotmale, Amol S.; Gonnade, Rajesh G.; Rajamohanan, Pattuparambil R.; Sanjayan, Gangadhar J. (Chemical Communications, 2012)
Herein, we report on the folding pattern observed in a synthetic peptide featuring two highly mutually dependent, yet strikingly dissimilar, closed networks of hydrogen-bonded rings that work in a cumulative fashion to stabilize the entire folded architecture of the peptide. Structural studies unequivocally suggest that disruption of any one of these mutually-dependent hydrogen-bonded networks is deleterious to the stability of the fully folded conformation of the peptide.

Multiple topologies from glycopolypeptide-dendron conjugate self-assembly: nanorods, micelles, and organogels - Pati, Debasis; Kalva, Nagendra; Das, Soumen; Kumaraswamy, Guruswamy; Sen Gupta, Sayam; Ambade, Ashootosh V. (Journal of the American Chemical Society, 2012)
Glycopolypeptides (GPs) were synthesized by ring-opening polymerization of glycosylated N-carboxyanhydride monomer and attached to hydrophobic dendrons at one chain end by ``click'' reaction to obtain amphiphilic anisotropic macromolecules. We show that by varying polypeptide chain length and dendron generation, an organogel was obtained in dimethylsulfoxide, while nanorods and micellar aggregates were observed in aqueous solutions. Assemblies in water were characterized by electron microscopy and dye encapsulation. Secondary structure of the GP chain was shown to affect the morphology, whereas the chain length of the poly(ethylene glycol) linker between the GP and dendron did not alter rod-like assemblies. Bioactive surface chemistry of these assemblies displaying carbohydrate groups was demonstrated by interaction of mannose-functionalized nanorods with ConA.

MYB8 Controls inducible phenolamide levels by activating three novel hydroxycinnamoyl-coenzyme a:polyamine transferases in nicotiana attenuata - Onkokesung, Nawaporn; Gaquerel, Emmanuel; Kotkar, Hemlata; Kaur, Harleen; Baldwin, Ian T.; Galis, Ivan (Plant Physiology, 2012)
A large number of plants accumulate N-acylated polyamines (phenolamides [PAs]) in response to biotic and/or abiotic stress conditions. In the native tobacco (Nicotiana attenuata), the accumulation of two major PAs, caffeoylputrescine and dicaffeoylspermidine (DCS), after herbivore attack is known to be controlled by a key transcription factor, MYB8. Using a broadly targeted metabolomics approach, we show that a much larger spectrum of PAs composed of hydroxycinnamic acids and two polyamines, putrescine and spermidine, is regulated by this transcription factor. We cloned several novel MYB8-regulated genes, annotated as putative acyltransferases, and analyzed their function. One of the novel acyltransferases (AT1) is shown to encode a hydroxycinnamoyl-coenzyme A: putrescine acyltransferase responsible for caffeoylputrescine biosynthesis in tobacco. Another gene (acyltransferase DH29), specific for spermidine conjugation, mediates the initial acylation step in DCS formation. Although this enzyme was not able to perform the second acylation toward DCS biosynthesis, another acyltransferase gene, CV86, proposed to act on monoacylated spermidines, was isolated and partially characterized. The activation of MYB8 in response to herbivore attack and associated signals required the activity of LIPOXYGENASE3, a gene involved in jasmonic acid (JA) biosynthesis in N. attenuata. These new results allow us to reconstruct a complete branch in JA signaling that defends N. attenuata plants against herbivores: JA via MYB8's transcriptional control of AT1 and DH29 genes controls the entire branch of PA biosynthesis, which allows N. attenuata to mount a chemically diverse (and likely efficient) defense shield against herbivores.

Nanowires of silver-polyaniline nanocomposite synthesized via in situ polymerization and its novel functionality as an antibacterial agent - Tamboli, Mohaseen S.; Kulkarni, Milind V.; Patil, Rajendra H.; Gade, Wasudeo N.; Navale, Shalaka C.; Kale, Bharat B. (Colloids and Surfaces B-Biointerfaces, 2012)
Silver-polyaniline (Ag-PANI) nanocomposite was synthesized by in situ polymerization method using ammonium persulfate CAPS) as an oxidizing agent in the presence of dodecylbenzene sulfonic acid (DBSA) and silver nitrate (AgNO3). The as synthesized Ag-PANI nanocomposite was characterized by using different analytical techniques such as UV-visible (UV-vis) and Fourier transform Infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), thermo gravimetric analysis (TGA). X-ray diffraction (XRD), and transmission electron microscopy (TEM). UV-visible spectra of the synthesized nanocomposite showed a sharp peak at similar to 420 nm corresponding to the surface plasmon resonance (SPR) of the silver nanoparticles (AgNPs) embedded in the polymer matrix which is overlapped by the polaronic peak of polyaniline appearing at that wavelength. Nanowires of Ag-PANI nanocomposite with diameter 50-70 nm were observed in FE-SEM and TEM. TGA has indicated an enhanced thermal stability of nanocomposite as compared to that of pure polymer. The Ag-PANI nanocomposite has shown an antibacterial activity against model organisms, a gram positive Bacillus subtilis NCIM 6633 in Mueller-Hinton (MH) medium, which is hitherto unattempted. The Ag-PANI nanocomposite with monodispersed AgNPs is considered to have potential applications in sensors, catalysis, batteries and electronic devices. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: antibacterial activity; Conducting poly(aniline); In situ polymerization; Nanocomposite

New chemodosimetric reagents as ratiometric probes for cysteine and homocysteine and possible detection in living cells and in blood plasma - Das, Priyadip; Mandal, Amal Kumar; Chandar, Nellore Bhanu; Baidya, Mithu; Bhatt, Harshad B.; Ganguly, Bishwajit; Ghosh, Sudip K.; Das, Amitava (Chemistry a European Journal, 2012)
In this work, we have rationally designed and synthesized two new reagents (L1 and L2), each bearing a pendant aldehyde functionality. This aldehyde group can take part in cyclization reactions with β- or γ-amino thiols to yield the corresponding thiazolidine and thiazinane derivatives, respectively. The intramolecular charge-transfer (ICT) bands of these thiazolidine and thiazinane derivatives are distinctly different from those of the molecular probes (L1 and L2). Such changes could serve as a potential platform for using L1 and L2 as new colorimetric/fluorogenic as well as ratiometric sensors for cysteine (Cys) and homocysteine (Hcy) under physiological conditions. Both reagents proved to be specific towards Cys and Hcy even in the presence of various amino acids, glucose, and DNA. Importantly, these two chemodosimetric reagents could be used for the quantitative detection of Cys present in blood plasma by using a pre-column HPLC technique. Such examples are not common in contemporary literature. MTT assay studies have revealed that these probes have low cytotoxicity. Confocal laser scanning micrographs of cells demonstrated that these probes could penetrate cell membranes and could be used to detect intracellular Cys/Hcy present within living cells. Thus, the results presented in this article not only demonstrate the efficiency and specificity of two ratiometric chemodosimeter molecules for the quantitative detection of Cys and Hcy, but also provide a strategy for developing reagents for analysis of these vital amino acids in biological samples.
Keywords: charge transfer; chemodosimetric detection; cysteine/ homocysteine sensors; fluorescent probes; imaging agents; ratiometric probes

New synthetic route for 1,2-diketo compounds using unexpected C-C bond cleavage by PCC - Bhosale, Shrikar M.; Momin, Aadil A.; Gawade, Rupesh L.; Puranik, Vedavati G.; Kusurkar, Radhika S. (Tetrahedron Letters, 2012)
An efficient method has been established for the preparation of 1,2-diketones by unexpected C-C bond cleavage in 4-keto-2-hydroxy esters using pyridiniumchlorochromate (PCC). (c) 2012 Elsevier Ltd. All rights reserved.
Keywords: 1; 2-Diketones; C-C bond cleavage; PCC

Non-isothermal kinetics of free-redical polymerization of 2-phenyl ethyl acrylate, paper presented at ?third international multicomponent polymer conference? impc 2012 - Ghorpade, Ravindra V.; Rajdeo, K. S.; Ponrathnam S.; Chavan N. N. (Third International Multicomponent Polymer Conference IMPC 2012, Kottayam, India., 2012)

Novel anti-inflammatory activity of epoxyazadiradione against macrophage migration inhibitory factor inhibition of tautomerase and proinflammatory activities of macrophage migration inhibitory factor - Alam, Athar; Haldar, Saikat; Thulasiram, Hirekodathakallu V.; Kumar, Rahul; Goyal, Manish; Iqbal, Mohd Shameel; Pal, Chinmay; Dey, Sumanta; Bindu, Samik; Sarkar, Souvik; Pal, Uttam; Maiti, Nakul C.; et al. (Journal of Biological Chemistry, 2012)
Macrophage migration inhibitory factor (MIF) is responsible for proinflammatory reactions in various infectious and noninfectious diseases. We have investigated the mechanism of anti-inflammatory activity of epoxyazadiradione, a limonoid purified from neem (Azadirachta indica) fruits, against MIF. Epoxyazadiradione inhibited the tautomerase activity of MIF of both human (huMIF) and malaria parasites (Plasmodium falciparum (PfMIF) and Plasmodium yoelii (PyMIF)) non-competitively in a reversible fashion (K-i, 2.11-5.23 mu M). Epoxyazadiradione also significantly inhibited MIF (huMIF, PyMIF, and PfMIF)-mediated proinflammatory activities in RAW 264.7 cells. It prevented MIF-induced macrophage chemotactic migration, NF-kappa B translocation to the nucleus, up-regulation of inducible nitric-oxide synthase, and nitric oxide production in RAW 264.7 cells. Epoxyazadiradione not only exhibited anti-inflammatory activity in vitro but also in vivo. We tested the anti-inflammatory activity of epoxyazadiradione in vivo after co-administering LPS and MIF in mice to mimic the disease state of sepsis or bacterial infection. Epoxyazadiradione prevented the release of proinflammatory cytokines such as IL-1 alpha, IL-1 beta, IL-6, and TNF-alpha when LPS and PyMIF were co-administered to BALB/c mice. The molecular basis of interaction of epoxyazadiradione with MIFs was explored with the help of computational chemistry tools and a biological knowledge base. Docking simulation indicated that the binding was highly specific and allosteric in nature. The well known MIF inhibitor (S, R)-3-(4-hydroxyphenyl)-4,5-dihydro-5-isoxazole acetic acid methyl ester (ISO-1) inhibited huMIF but not MIF of parasitic origin. In contrast, epoxyazadiradione inhibited both huMIF and plasmodial MIF, thus bearing an immense therapeutic potential against proinflammatory reactions induced by MIF of both malaria parasites and human.

Novel mechanism involved in temporal regulation of skin pigmentation homeostasis - Ganju, Parul; Natarajan, V. T.; Singh, A.; Vijayan, V.; Dani, Prachi P.; Kar, H. K.; Natarajan, K.; Gadgil, Chetan J.; Rani, R.; Gokhale, R. S. (Journal of Investigative Dermatology, 2012)

Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof - Milstein, David; Balaraman, Ekambaram; Gunanathan, Chidambaram; Gnanaprakasam, Boopathy; Zhang, Jing (EP2629889A2, US9045381, US20130281664, WO2012052996A2, WO2012052996A3, 2012)
The present invention relates to novel Ruthenium complexes and related borohydride complexes, and their use for (1) hydrogenation of amides (including polyamides) to alcohols and amines; (2) preparing amides from alcohols with amines (including preparing polyamides (e.g., polypeptides) by reacting dialcohols and diamines or by polymerization of amino alcohols); (3) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones), cyclic di-esters (di-lactones) or polyesters); (4) hydrogenation of organic carbonates (including polycarbonates) to alcohols and of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (5) dehydrogenative coupling of alcohols to esters; (6) hydrogenation of secondary alcohols to ketones; (7) amidation of esters (synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water to form carboxylic acids; and (10) dehydrogenation of beta-amino alcohols to form pyrazines. The present invention further relates to novel uses of certain pyridine Ruthenium complexes.

Novel solid cloisite tin catalyzed polymerization of L-lactide - Selukar, Balaji Sidram; Pandey, Asutosh Kumar; Nande, Smita Sunil; Bansode, Avinash Santram; Garnaik, Baijayantimala (Journal of Chemistry and Chemical Engineering, 2012)
A novel cloisite modified solid catalyst was prepared in a single step from commercially available starting materials for the first time. The ring opening polymerization of L-lactide and D-lactide using this cloisite modified solid catalyst resulted in homopolymers of 75,000 and PDI = 1.6 and the maximum molecular weight (Mw) i.e. 180,000 with PDI = 1.9 were obtained. The catalytic activity of cloisite modified solid catalyst was compared with the conventional stannous octoate catalyst and found superior to stannous octoate in all respect such as conversion, molecular weight and molecular weight distribution etc.. Moreover, the maximum molecular weight i.e. 180,000was obtained at 220 o C, whereas, transesterification reaction predominate in presence of stannous octoate. The linear structure was confirmed by quantitative 13C NMR Spectroscopy. Blend films were obtained by casting mixed solutions of poly (D-lactide) and poly (L lactide) at various compositions, and stereocomplex was formed at 50/50 composition with molecular weight of 75,000.

One pot glucose detection by [Fe-III(biuret-amide)] immobilized on mesoporous silica nanoparticles: an efficient HRP mimic - Malvi, Bharmana; Panda, Chakadola; Dhar, Basab B.; Sen Gupta, Sayam (Chemical Communications, 2012)
An [Fe-III(biuret-amide)] complex has been immobilized onto mesoporous silica nanoparticles via Cu(I) catalyzed azide-alkyne click chemistry. This hybrid material functions as an efficient peroxidase mimic and was successfully used for the quantitative determination of hydrogen peroxide and glucose via a one-pot colorimetric assay.

One-pot sol-gel preparation for efficient cobalt-molybdenum-titania hydrotreating catalysts - Nguyen, D. L.; Gillot, S.; Souza, D. O.; Blanchard, P.; Lamonier, Carole; Berrier, E.; Kotbagi, T. V.; Dongare, Mohan K.; Shubhangi B. Umbarkar; Cristol, S.; Payen, E.; Lancelot, Christine (Chemcatchem, 2012)
Titania-based hydrodesulfurization catalysts were prepared by using a one-pot solgel method with the titanium peroxo complex as titanium precursor and molybdenum and cobalt precursors dissolved in the aqueous hydrogen peroxide solution used during synthesis. Catalysts with MoO3 loadings varying from 5 to 40 wt?% and a Co/Mo atomic ratio of 0.5 were prepared. Solids with molybdenum loadings below 20 wt?% MoO3 demonstrated poor hydrodesulfurization activity for the model compound thiophene. This was attributed to the presence of a large amount of embedded cobalt and molybdenum species in the titania matrix. A significant increase in the catalytic activity was observed for solids containing 20 and 25 wt?% of MoO3 on which active species appeared to be accessible on the titania surface. Furthermore, the highest conversion obtained on these solgel solids was superior to the highest conversion obtained on reference catalysts prepared through the impregnation of ammonium heptamolybdate and cobalt nitrate on commercial titania.
Keywords: cobalt; heterogeneous catalysis; Molybdenum; sol-gel process; titanium

Organocatalytic stereoselective synthesis of passifloricin A - Kumar, Pradeep; Pandey, Menaka; Gupta, Priti; Dhavale, Dilip D. (Organic & Biomolecular Chemistry, 2012)
The enantioselective synthesis of passifloricin A has been achieved in high diastereomeric excess. The 1,3-polyol moiety was constructed by iterative proline-catalyzed sequential alpha-aminoxylation and Horner-Wadsworth-Emmons (HWE) olefination of aldehydes while the synthesis of lactone moiety was achieved by ring-closing metathesis (RCM).

Photocatalytic degradation of phosphamidon using Ag-doped ZnO nanorods - Korake, Prakash V.; Sridharkrishna, R.; Hankare, P. P.; Garadkar, K. M. (Toxicological and Environmental Chemistry, 2012)
The photocatalytic degradation of the organo-phosphorous pesticide phosphamidon at low concentration in aqueous solution on Ag-doped ZnO nanorods was investigated. Nanosized Ag-doped ZnO rods were synthesized by using a microwave assisted aqueous method. High molecular weight polyvinyl alcohol was used as a stabilizing agent. Composition and structure were investigated using energy-dispersive X-ray spectroscopy (EDAX) and X-ray diffraction (XRD). The XRD pattern reveals that ZnO nanorods are of hexagonal wurtzite structure. The average crystallite size calculated from Scherrer's relation was found to be 30 nm. The effects of catalyst loading, pH value, and initial concentration of phosphamidon on the photocatalytic degradation efficiency using Ag-doped ZnO nanorods as a photocatalyst have been discussed. The results revealed that Ag-doped ZnO nanorods with a diameter of 30 nm showed highest photocatalytic activity at a surface density of 1 g dm(-3). The catalyst doped with 0.2 mol% Ag is effective for the degradation of phosphamidon with visible light. This opens a new possibility to decompose pesticides that are present in wastewater.
Keywords: Ag-doped zinc oxide; phosphamidon; Photocatalysis; Photodegradation

Photopolymerization kinetics of 2-phenylethyl (meth) acrylates studied by photo DSC - Ghorpade, Ravindra V.; Bhosle, Sonali Madhavrao; Ponrathnam, S.; Rajan, C. R.; Chavan, Nayaku; Harikrishna, Reghunathan (Journal of Polymer Research, 2012)
The present work deals with the photopolymerization of 2-phenylethyl (meth)acrylates and estimation of their kinetic parameters. Formulations were made by independently homogenizing the monomers with photoinitiators of two different classes. Two different compositions of photoinitiators were used to study the effect of concentration of photoinitiator on cure kinetics. These compositions obtained were tested for photo curing performance using differential photocalorimetry (DPC) or photo DSC under polychromatic radiation. The heat flow against time was recorded for all formulations under isothermal conditions and the rates of polymerization as well as the percentage conversions were estimated. It was observed that due to a longer timescale for reaction diffusion, the methacrylate formulations showed a higher conversion than acrylate formulations. Other parameters such as induction time, maximum rate and conversion attained as well as the time to attain peak maximum were noted. The photopolymerization and kinetic estimations of the formulations including evaluation of kinetic models are discussed.
Keywords: Bimolecular termination model; Photo DSC; Photopolymerization; Variable autocatalytic model

Photosensitization of nanoparticulate TiO2 using a Re(I)-polypyridyl complex: studies on interfacial electron transfer in the ultrafast time domain - Kar, Prasenjit; Banerjee, Tanmay; Verma, Sandeep; Sen, Anik; Das, Amitava; Ganguly, Bishwajit; Ghosh, Hirendra N. (Physical Chemistry Chemical Physics, 2012)
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.

Phyllocladane diterpenes from anisomeles heyneana - Kulkarni, Roshan R.; Shurpali, Ketaki; Gawade, Rupesh L.; Sarkar, Dhiman; Puranik, Vedavati G.; Joshi, Swati P. (Journal of Asian Natural Products Research, 2012)
New phyllocladane diterpene, phyllocladan-16 alpha,17-dihydroxy-19-oic acid (1), together with known phyllocladane diterpene, phyllocladan-16 alpha,19-diol (2), cembrane diterpene ovatodiolide (3), sitosteryl-3-O-beta-D-glucoside (4), and verbascoside (5), were isolated from aerial parts of Anisomeles heyneana. The structure of compound 1 was elucidated by 1D and 2D NMR analyses which included HSQC, HMBC, and nuclear overhauser effect spectroscopy (NOESY) experiments as well as X-ray crystallography. This is the first report of phyllocladane diterpenes from genus Anisomeles. Compounds 1, 3, 4, and 5 were evaluated for inhibition of Mycobacterium tuberculosis and 3 was found to exhibit anti-mycobacterial activity with IC90 6.53 mu g/ml. Compounds 1, 3, and 5, at 100 mu g/ml, were also evaluated for inhibition of Thp-1 cell lines, and compounds 1 and 3 showed 59.02% and 96.4% inhibitions, respectively.
Keywords: Anisomeles heyneana; Lamiaceae; Mycobacterium tuberculosis; phyllocladane diterpenes

Phylogenomic analysis of UDP glycosyltransferase 1 multigene family in Linum usitatissimum identified genes with varied expression patterns - Barvkar, Vitthal T.; Pardeshi, Varsha C.; Kale, Sandip M.; Kadoo, Narendra Y.; Gupta, Vidya S. (BMC Genomics, 2012)
Background: The glycosylation process, catalyzed by ubiquitous glycosyltransferase (GT) family enzymes, is a prevalent modification of plant secondary metabolites that regulates various functions such as hormone homeostasis, detoxification of xenobiotics and biosynthesis and storage of secondary metabolites. Flax (Linum usitatissimum L.) is a commercially grown oilseed crop, important because of its essential fatty acids and health promoting lignans. Identification and characterization of UDP glycosyltransferase (UGT) genes from flax could provide valuable basic information about this important gene family and help to explain the seed specific glycosylated metabolite accumulation and other processes in plants. Plant genome sequencing projects are useful to discover complexity within this gene family and also pave way for the development of functional genomics approaches. Results: Taking advantage of the newly assembled draft genome sequence of flax, we identified 137 UDP glycosyltransferase (UGT) genes from flax using a conserved signature motif. Phylogenetic analysis of these protein sequences clustered them into 14 major groups (A-N). Expression patterns of these genes were investigated using publicly available expressed sequence tag (EST), microarray data and reverse transcription quantitative real time PCR (RT-qPCR). Seventy-three per cent of these genes (100 out of 137) showed expression evidence in 15 tissues examined and indicated varied expression profiles. The RT-qPCR results of 10 selected genes were also coherent with the digital expression analysis. Interestingly, five duplicated UGT genes were identified, which showed differential expression in various tissues. Of the seven intron loss/gain positions detected, two intron positions were conserved among most of the UGTs, although a clear relationship about the evolution of these genes could not be established. Comparison of the flax UGTs with orthologs from four other sequenced dicot genomes indicated that seven UGTs were flax diverged. Conclusions: Flax has a large number of UGT genes including few flax diverged ones. Phylogenetic analysis and expression profiles of these genes identified tissue and condition specific repertoire of UGT genes from this crop. This study would facilitate precise selection of candidate genes and their further characterization of substrate specificities and in planta functions.

Polymorphs, salts, and cocrystals: what's in a name? - Aitipamula, Srinivasulu; Banerjee, Rahul; Bansal, Arvind K.; Biradha, Kumar; Cheney, Miranda L.; Choudhury, Angshuman Roy; Desiraju, Gautam R.; Dikundwar, Amol G.; Dubey, Ritesh; Duggirala, Nagakiran; Ghogale, Preetam P.; Ghosh, Soumyajit; et al. (Crystal Growth & Design, 2012)
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 ``API-excipient'' 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.

Polymorphs, salts and cocrystals: what's in a name? (vol 12, pg 2147, 2012) - Aitipamula, Srinivasulu; Banerjee, Rahul; Bansal, Arvind K.; Biradha, Kumar; Cheney, Miranda L.; Choudhury, Angshuman Roy; Desiraju, Gautam R.; Dikundwar, Amol G.; Dubey, Ritesh; Duggirala, Nagakiran; Ghogale, Preetam P.; Ghosh, Soumyajit; et al. (Crystal Growth & Design, 2012)

Porous ZnO nanorod for targeted delivery of doxorubicin: in vitro and in vivo response for therapeutic applications - Mitra, Shouvik; Subia, B.; Patra, Prasun; Chandra, Sourov; Debnath, Nitai; Das, Sumistha; Banerjee, Rahul; Kundu, Subhas C.; Pramanik, Panchanan; Goswami, Arunava (Journal of Materials Chemistry, 2012)
Cancer cell specific targeted delivery (TDD) by porous nanocarrier is on a high role. Here in a simple route for the synthesis of porous ZnO nanorods (ZnO) has been demonstrated. ZnO expressed very high surface area of 305.14 m(2) g(-1) (S-BET) and uniformly distributed pores of 5 nm. In continuation ZnO has been fabricated with 3-aminophosphonic acid followed by folic acid to yield folate conjugated porous ZnO nanorod (ZnO-FA). High surface area, uniformly distributed pores on its surface make the nanocarrier suitable for high drug loading (88%) of the anticancer drug doxorubicin (DOX). A pH triggered drug release was observed with minimum release in pathophysical conditions. In vitro efficacy of DOX loaded ZnO-FA (ZnO-FA-DOX) has been evaluated against breast cancer cells MDA-MB-231, which is not possible alone by DOX or ZnO-FA. Targeted scaffold with pendant -NH2 group has been covalently bonded with fluorescent dye (RITC) for cellular uptake and imaging studies in MDA-MB-231 cells; the possible pathway for cancer regression has also been evaluated. Even in vivo acute and intravenous toxicological evaluation on murine model system complemented biocompatibility of ZnO-FA in TDD. All together we have collaged a template free synthesis of porous ZnO nanorod, successful targeting on to cancer cells, high drug loading, pH triggered drug release, in vitro efficacy of ZnO-FA-DOX against MDA-MB-231 cells and in vivo compatibility as well. We envisioned the future prospect of porous ZnO nanostructures in TDD.

Preparation and characterization of calcium silicate for CO2 sorption - Kale, Kishor B.; Raskar, Reshma Y.; Rane, Vilash H.; Gaikwad, Abaji G. (Adsorption Science & Technology, 2012)
An attempt has been made to develop different samples of calcium silicate and to screen these samples for CO2 sorption and alkalinity in order to achieve maximum CO2 sorption. The CO2 sorption capacity of these samples was examined at different temperatures. Various methods such as solid-solid fusion, sol-gel, molten salt and templates (CTAB, cetyltrimethylammonium bromide or Aliquat 336, tricaprylmethylammonium chloride) were used to prepare the calcium silicate samples. The solid mass of calcium silicate samples were obtained by calcining the solid product obtained in an atmosphere of air or helium at 900 degrees C for 3 hours. The calcium silicate samples were characterized for surface area, alkalinity, scanning electron microscopic images and X-ray diffraction patterns. The temperature profile of CO2 sorption by calcium silicate was studied in the temperature range of 40-850 degrees C. Our results showed that the alkalinity and surface area of calcium silicate were in the range from 2.35 to 20 mmol g(-1) and 1.4 to 10 m(2) g(-1), respectively. The sorption of CO2 at 500 degrees C over calcium silicate for the different Ca/Si mol ratio (range: 1-6) was found to be in the range from 3.12 to 29.96 wt%. Addition of a promoter such as sodium, potassium, caesium and lanthanum was found to enhance the sorption of CO2 by calcium silicate. Several samples of different mol ratios of Ca/Si prepared by different methods were tested for the sorption of CO2 at 500 degrees C.

Preparation of cross-linked enzyme aggregates of L-aminoacylase via co-aggregation with polyethyleneimine - Vaidya, Bhalchandra K.; Kuwar, Suyog S.; Golegaonkar, Sandeep B.; Nene, Sanjay N. (Journal of Molecular Catalysis B-Enzymatic, 2012)
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

Preparation of pure methyl esters from corresponding alkali metal salts of carboxylic acids using carbon dioxide and methanol - Barve, Prashant P.; Kamble, Sanjay P.; Joshi, Jyeshtharaj B.; Gupte, Milind Y.; Kulkarni, Bhaskar D. (Industrial & Engineering Chemistry Research, 2012)
In the present article, for the first time, we report the synthesis of alkyl esters by direct esterification of alkali metal salts of carboxylic acids using carbon dioxide and alcohol. Methyl acetate, methyl benzoate, methyl salicylate, and methyl lactate have been synthesized by esterification of sodium acetate, sodium benzoate, sodium salicylate, and calcium lactate, respectively. The esterification reaction was carried out in a batch as well as in a semicontinuous mode of operation. A detailed study on the esterification of calcium lactate using methanol and carbon dioxide was carried out to record the effects of various operating parameters (like CO2 pressure, reaction temperature, moisture content in the calcium lactate, and initial concentrations of calcium lactate) on the esterification reaction. This synthesis route produces highly pure methyl lactate by direct esterification of calcium lactate with calcium carbonate as byproduct. The byproduct calcium carbonate was characterized for its crystallinity, surface area, and pore volume. The process route has the advantage that the synthesized byproduct can be recycled into the fermenter to make corresponding alkali metal lactate or the finely precipitated calcium carbonate can be used for various other applications. Thus, the recovery and recycle of alkali metal is possible providing a pollution free process for synthesis of pure methyl lactate.

Production, purification, and characterization of a beta-glucosidase of penicillium funiculosum NCL1 - Ramani, Gurusamy; Meera, Balasubramanian; Vanitha, Chinnathambi; Rao, Mala; Gunasekaran, Paramasamy (Applied Biochemistry and Biotechnology, 2012)
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

Proteome profiling of flax (linum usitatissimum) seed: characterization of functional metabolic pathways operating during seed development - Barvkar, Vitthal T.; Pardeshi, Varsha C.; Kale, Sandip M.; Kadoo, Narendra Y.; Giri, Ashok P.; Gupta, Vidya S. (Journal of Proteome Research, 2012)
Flax (Linum usitatissimum L.) seeds are an important source of food and feed due to the presence of various health promoting compounds, making it a nutritionally and economically important plant. An in-depth analysis of the proteome of developing flax seed is expected to provide significant information with respect to the regulation and accumulation of such storage compounds. Therefore, a proteomic analysis of seven seed developmental stages (4, 8, 12, 16, 22, 30, and 48 days after anthesis) in a flax variety, NL-97 was carried out using a combination of ID-SDS-PAGE and LC-MSE methods. A total 1716 proteins were identified and their functional annotation revealed that a majority of them were involved in primary metabolism, protein destination, storage and energy. Three carbon assimilatory pathways appeared to operate in flax seeds. Reverse transcription quantitative PCR of selected 19 genes was carried out to understand their roles during seed development. Besides storage proteins, methionine synthase, RuBisCO and S-adenosylmethionine synthetase were highly expressed transcripts, highlighting their importance in flax seed development. Further, the identified proteins were mapped onto developmental seed specific expressed sequence tag (EST) libraries of flax to obtain transcriptional evidence and 81% of them had detectable expression at the mRNA level. This study provides new insights into the complex seed developmental processes operating in flax.
Keywords: alpha-linolenic acid; carbon flux; Digital expression analysis; flax seed development; MSE; secoisolariciresinol diglucoside

Proteomic analysis of glycated proteins from streptozotocin-induced diabetic rat kidney - Chougale, Ashok D.; Bhat, Shweta P.; Bhujbal, Swapnil V.; Zambare, Mandar R.; Puntambekar, Shraddha; Somani, Rahul S.; Boppana, Ramanamurthy; Giri, Ashok P.; Kulkarni, Mahesh J. (Molecular Biotechnology, 2012)
Glycation of proteins leading to formation of advanced glycation end products (AGEs) has been considered as one of the important causes of diabetic nephropathy. Therefore, in this study, glycated proteins were detected by anti-AGE antibodies from kidney of streptozotocin-induced diabetic rat showing nephropathic symptoms, by using two dimensional electrophoresis and western blot analysis. These glycated proteins were identified and characterized by using combination of peptide mass finger printing and tandem mass spectrometric approaches. Glycated proteins identified included proteins from metabolic pathways, oxidative stress, cell signaling, and transport. Several of the proteins modified by glycation were involved in glucose metabolism. The extent of glycation was higher in diabetes compared to control, in the glycated proteins that were common to both control and diabetic kidney. Two dimensional electrophoresis proteins profiling of glycated proteins suggest that four of the glycated proteins were significantly up regulated in diabetes.
Keywords: AGE; Diabetes; Glucose toxicity; Nephropathy; Post-translation modification

Purification and characterization of YxeI, a penicillin acylase from Bacillus subtilis - Rathinaswamy, Priya; Gaikwad, Sushama M.; Suresh, C. G.; Prabhune, Asmita; Brannigan, James A.; Dodson, Guy G.; Pundle, Archana V. (International Journal of Biological Macromolecules, 2012)
The paper reports the purification and characterization of the first penicillin acylase from Bacillus subtilis. YxeI, the protein annotated as hypothetical, coded by the gene yxeI in the open reading frame between iol and hut operons in B. subtilis was cloned and expressed in Eshcherichia coli, purified and characterized. The purified protein showed measurable penicillin acylase activity with penicillin V. The enzyme was a homotetramer of 148 kDa. The apparent Km of the enzyme for penicillin V and the synthetic substrate 2-nitro-5-(phenoxyacetamido)-benzoic acid was 40 mM and 0.63 mM, respectively, and the association constants were 8.93 x 10(2) M-1 and 2.51 x 10(5) M-1, respectively. It was inhibited by cephalosporins and conjugated bile salts, substrates of the closely related bile acid hydrolases. It had good sequence homology with other penicillin V acylases and conjugated bile acid hydrolases, members of the Ntn hydrolase family. The N-terminal nucleophile was a cysteine which is revealed by a simple removal of N-formyl-methionine. The activity of the protein was affected by high temperature, acidic pH and the presence of the denaturant guanidine hydrochloride. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Bacillus subtilis; Conjugated bile acid hydrolases; Ntn hydrolase; Penicillin acylase

Quantum dot bio-conjugate: as a western blot probe for highly sensitive detection of cellular proteins - Kale, Sonia; Kale, Anup; Gholap, Haribhau; Rana, Abhimanyu; Desai, Rama; Banpurkar, Arun G.; Ogale, Satishchandra; Shastry, Padma (Journal of Nanoparticle Research, 2012)
In the present study, we report a quantum dot (QD)-tailored western blot analysis for a sensitive, rapid and flexible detection of the nuclear and cytoplasmic proteins. Highly luminescent CdTe and (CdTe) ZnS QDs are synthesized by aqueous method. High resolution transmission electron microscopy, Raman spectroscopy, fourier transform infrared spectroscopy, fluorescence spectroscopy and X-ray diffraction are used to characterize the properties of the quantum dots. The QDs are functionalized with antibodies of prostate apoptosis response-4 (Par-4), poly(ADP-ribose) polymerases and beta actin to specifically bind with the proteins localized in the nucleus and cytoplasm of the cells, respectively. The QD-conjugated antibodies are used to overcome the limitations of conventional western blot technique. The sensitivity and rapidity of protein detection in QD-based approach is very high, with detection limits up to 10 pg of protein. In addition, these labels provide the capability of enhanced identification and localization of marker proteins in intact cells by confocal laser scanning microscopy.
Keywords: Detection; Imaging; nanomedicine; quantum dot; Rapid; sensors; Western blot

Radical mediated deoxygenation of inositol benzylidene acetals: conformational analysis, DFT calculations, and mechanism - Gurale, Bharat P.; Vanka, Kumar; Shashidhar, Mysore S. (Carbohydrate Research, 2012)
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

Rapid microwave synthesis of fluorescent hydrophobic carbon dots - Mitra, Shouvik; Chandra, Sourov; Kundu, Tanay; Banerjee, Rahul; Pramanik, Panchanan; Goswami, Arunava (RSC Advances, 2012)
Fluorescent hydrophobic carbon dots (HCDs) have been fabricated from a poloxamer by a simple microwave assisted process within a few minutes for the first time. Small and distinct spherical HCDs emitted bright blue and green fluorescent light depending upon the excitation wavelength and were dispersed easily in a wide variety of organic solvents. HCDs exhibited excellent water resistant behavior with a contact angle of similar to 122 degrees enforcing good hydrophobic character which will be quite useful in potential surface applications.

Ratiometric detection of Cr3+ and Hg2+ by a naphthalimide-rhodamine based fluorescent probe - Mahato, Prasenjit; Saha, Sukdeb; Suresh, E.; Liddo, Rosa Di; Parnigotto, Pier Paolo; Conconi, Maria Teresa; Kesharwani, Manoj K.; Ganguly, Bishwajit; Das, Amitava (Inorganic Chemistry, 2012)
Newly synthesized rhodamine derivatives, L1 and L2, are found to bind specifically to Hg2+ or Cr3+ in presence of large excess of other competing ions with associated changes in their optical and fluorescence spectral behavior. These spectral changes are significant enough in the visible region of the spectrum and thus, allow the visual detection. For L1, the detection limit is even lower than the permissible [Cr3+] or [Hg2+] in drinking water as per standard U.S. EPA norms; while the receptor, L2 could be used as a ratiometric sensor for detection of Cr3+ and Hg2+ based on the resonance energy transfer (RET) process involving the donor naphthalimide and the acceptor Cr3+/Hg2+-bound xanthene fragment. Studies reveal that these two reagents could be used for recognition and sensing of Hg2+/Cr3+. Further, confocal laser microscopic studies confirmed that the reagent L2 could also be used as an imaging probe for detection of uptake of these ions in A431 cells.

Recognition of Hg 2+ and Cr 3+ in physiological conditions by a rhodamine derivative and its application as a reagent for cell-imaging studies - Saha, Sukdeb; Mahato, Prasenjit; Reddy, Upendar G.; Suresh, E.; Chakrabarty, Arindam; Baidya, Mithu; Ghosh, Sudip K.; Das, Amitava (Inorganic Chemistry, 2012)
A new rhodamine-based receptor, derivatized with an additional fluorophore (quinoline), was synthesized for selective recognition of Hg2+ and Cr3+ in an acetonitrile/HEPES buffer medium of pH 7.3. This reagent could be used as a dual probe and allowed detection of these two ions by monitoring changes in absorption and the fluorescence spectral pattern. In both instances, the extent of the changes was significant enough to allow visual detection. More importantly, the receptor molecule could be used as an imaging reagent for detection of Hg2+ and Cr3+ uptake in live human cancer cells (MCF7) using laser confocal microscopic studies. Unlike Hg(ClO4)2 or Hg(NO3)2 salts, HgCl2 or HgI2 failed to induce any visually detectable change in color or fluorescence upon interaction with L1 under identical experimental conditions. Presumably, the higher covalent nature of HgII in HgCl2 or HgI2 accounts for its lower acidity and its inability to open up the spirolactam ring of the reagent L1. The issue has been addressed on the basis of the single-crystal X-ray structures of L1·HgX2 (X– = Cl– or I–) and results from other spectral studies.

Recognition of Hg2+ion through restricted imine isomerization: crystallographic evidence and imaging in live cells - Mandal, Amal Kumar; Suresh, Moorthy; Das, Priyadip; Suresh, E.; Baidya, Mithu; Ghosh, Sudip K.; Das, Amitava (Organic Letters, 2012)
A newly synthesized imine-based receptor (L) showed remarkable specificity toward the Hg2+ ion in aqueous media over other metal ions. Coordination of L to Hg2+ induces a turn-on fluorescence response. This was explained based on the restricted imine isomerization along with PET on coordination to Hg2+. X-ray structural evidence tends to favor a C–C bond rotation rather than C═N isomerization for adopting a favorable conformation in L for coordination to Hg2+. This reagent could be used for imaging the accumulation of Hg2+ ions in HeLa cells.

Regio- and stereoselective synthesis of new substituted tetrahydrocarbazoles and carbazoles using diels-alder reactions - Hingane, Dattatray G.; Goswami, Shailesh K.; Puranik, Vedavati G.; Kusurkar, Radhika S. (Synthetic Communications, 2012)
Diels-Alder reactions of 3-vinylindoles were carried out with methyl acrylate and N-phenylmaleimide as dienophiles under microwave conditions to furnish unreported tetrahydrocarbazoles regio- and stereoselectively in good yields. Further dehydrogenation resulted in new substituted carbazoles.
Keywords: Carbazoles; regio- and stereoselective Diels-Alder reactions; tetrahydrocarbazoles

Regulation of BACE1 by miR-29a/b in a cellular model of spinocerebellar ataxia 17 - Roshan, Reema; Ghosh, Tanay; Gadgil, Mugdha; Pillai, Beena (RNA Biology, 2012)
Polyglutamine diseases are a class of neurodegenerative disorders characterized by expansion of polyglutamine repeats, protein aggregation and neuronal cell death in specific regions of the brain. The expansion of a polyglutamine repeat in the TATA binding protein (TBP) causes a neurodegenerative disease, Spinocerebellar Ataxia 17 (SC A17). This disease is characterized by intranuclear protein aggregates and selective loss of cerebellar neurons, including Purkinje cells. MicroRNAs are small, endogenous, regulatory non-coding RNA molecules that bind to mRNAs with partial complementarity and interfere in their expression. Here, we used a cellular model of SC A17 where we expressed TBP with 16 (normal) or 59 (pathogenic) polyglutamines and found differential expression of several microRNAs. Specifically, we found two microRNAs, miR-29a/b, were downregulated. With miR-29a/b downregulation, we found an increased expression of targets of miR-29a/b-beta-site amyloid precursor protein cleaving enzyme 1 (BACE 1), p53 upregulated modulator of apoptosis (PUMA) and BAK, increased cytochrome c release and apoptosis. Restoration of miR-29a/b in the pathogenic polyglutamine background reduced the BACE 1 expression. While, antagomiRs against miR-29a/b resulted in an increase in BACE 1 levels and neuronal apoptosis. In spite of the elevation of BACE 1 in Alzhemiers disease, its role in neuronal cell death has not been established. Here, we show that increased BACE 1 expression is not sufficient to cause apoptosis. However restoring level of BACE 1 to normal in polyglutamine cells partially reduced neuronal apoptosis. We show a role for the miR-29a/b-BACE 1 regulatory interaction in SC A17, suggesting that this microRNA could be part of a common molecular mechanism leading to neuronal cell death in multiple neurodegenerative disorders. The identification of a common mechanism of microRNA mediated neurodegeneration not only improves our understanding of the process, but also provides promising and novel therapeutic targets.
Keywords: BACE1; miR-29a/b; neurodegeneration; SCA17; TBP

Ruthenium pincer-catalyzed cross-dehydrogenative coupling of primary alcohols with secondary alcohols under neutral conditions - Srimani, Dipankar; Balaraman, Ekambaram; Gnanaprakasam, Boopathy; Ben-David, Yehoshoa; Milstein, David (Advanced Synthesis & Catalysis, 2012)
Cross-dehydrogenative coupling of primary alcohols with secondary alcohols to obtain mixed esters with the liberation of molecular hydrogen is achieved in high yield and good selectivity under neutral conditions, using a bipyridyl-based PNN ruthenium(II) pincer catalyst.

Ruthenium-catalyzed C6-propenylation reactions of substituted pyridine derivatives: directed and direct C-H activation - Goriya, Yogesh; Ramana, Chepuri V. (Chemistry-A European Journal, 2012)
Keywords: alkenylation; C?H activation; nitrogen heterocycles; pyridine derivatives; ruthenium

Scandium-decorated MOF-5 as potential candidates for room-temperature hydrogen storage: a solution for the clustering problem in MOFs - Dixit, Mudit; Maark, Tuhina Adit; Ghatak, Kamalika; Ahuja, Rajiv; Pal, Sourav (Journal of Physical Chemistry C, 2012)
Transition-metal-based systems show promising binding energy for hydrogen storage but suffer from clustering problem. The effect of light transition metal (M = Sc, Ti) decoration, boron substitution on the hydrogen storage properties of MOF-5, and clustering problem of metals has been investigated using ab initio density, functional theory. Our results of solid-tate calculations reveal that whereas Ti clusters strongly Sc atoms do not suffer from this problem when decorating MOF-5. Boron substitution on metal-decorated MOF-5 enhances the interaction energy of both the metals with MOF-5. Sc-decorated MOF-5 shows a hydrogen storage capacity of 5.81 wt % with calculated binding energies of 20-40 kJ/mol, which ensures the room-teniperature applicability of this hydrogen storage material.

Sequential energy and electron transfer in polynuclear complex sensitized TiO2 nanoparticles - Verma, Sandeep; Kar, Prasenjit; Banerjee, Tanmay; Das, Amitava; Ghosh, Hirendra N. (Journal of Physical Chemistry Letters, 2012)
Polynuclear–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–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.

Simple method for incorporating dynamic effects of intronic miRNA mediated regulation - Gokhale, Sucheta A.; Hariharan, Manoj; Brahmachari, Samir K.; Gadgil, Chetan J. (Molecular Biosystems, 2012)
The importance of microRNA (miRNA) in modulating gene expression at the post-transcriptional level is well known. Such regulation has been shown to influence the dynamics of several regulatory networks including the cell cycle. In this study we incorporated regulatory effects of intronic miRNA into an existing mathematical model of the cell cycle through the use of an existing `proxy' protein - the host protein. It was observed that the incorporation of intronic miRNA mediated regulation improved the performance of the model resulting in a closer match to experimental results. To test the universality of this approach we compared the effects of intronic miRNA mediated regulation and host protein mediated regulation. Further, we compared miRNA mediated and protein mediated positive and negative feedback regulations of the target protein. We found that the target protein profiles were predominantly similar. These observations show the applicability of our method for incorporating intronic miRNA mediated dynamic effects in models for regulation of gene expression.

Simple one pot synthesis of nano gold-mesoporous silica and its oxidation catalysis - Sekhar, A. C. Sunil; Sivaranjani, Kumarsrinivasan; Gopinath, Chinnakonda S.; Vinod, C. P. (Catalysis Today, 2012)
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

Solvent induced crystallization of 1,2,3,4(6),5-penta-O-acetyl-6(4)-O-[(1S)-10-camphor sulfonyl]-myo-inositol diastereomers associated via weak trifurcated C-H center dot center dot center dot O interactions - Manoj, Kochunnoonny; Gonnade, Rajesh G.; Shashidhar, Mysore S.; Bhadbhade, Mohan M. (CrystEngComm, 2012)
The title compound produced three different types of solvent inclusion crystals having a conserved dimeric association via trifurcated C-H center dot center dot center dot O interactions between the diastereomers. These `dimeric' units are organized differently to produce three crystal types containing guest molecules. In type I and II, unit translated dimers created voids for guest inclusion, whereas in type III the guest sites were produced by helical association of dimers. Inclusion of dichloromethane gave two different types of crystals; however, we were unable to obtain unsolvated crystals of the title compound.

Stereoselective construction of 5,11-methanomorphanthridine and 5,10b-phenanthridine structural frameworks: total syntheses of (+/-)-pancracine, (+/-)-brunsvigine, (+/-)-maritidine, and (+/-)-crinine - Pandey, Ganesh; Gadre, Smita R. (Pure and Applied Chemistry, 2012)
The core structure of the complex pentacyclic 5,11-methanomorphanthridine skeleton and the vicinal quaternary and tertiary stereocenters of the 5,10b-phenanthridine skeleton are constructed stereospecifically in one step employing intramolecular 1,3-dipolar cyclo addition of a nonstabilized azomethine ylide (AMY) generated by the sequential double desilylation of appropriate bis-trimethylsilylmethyl amines using Ag(I)F as a single-electron oxidant. The strategy is successfully applied for the total synthesis of biologically active alkaloids such as (+/-)-pancracine, (+/-)-brunsvigine, (+/-)-maritidine, and (+/-)-crinine.
Keywords: alkaloid synthesis; cycloadditions; organic synthesis; stereocontrolled synthesis

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 - Shivakumar, Kota; Vidyasagar, Adiyala; Naidu, Andra; Gonnade, Rajesh G.; Sureshan, Kana M. (Crystengcomm, 2012)
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.

Stress inducible proteinase inhibitor diversity in capsicum annuum - Mishra, Manasi; Mahajan, Neha S.; Tamhane, Vaijayanti A.; Kulkarni, Mahesh J.; Baldwin, Ian T.; Gupta, Vidya S.; Giri, Ashok P. (BMC Plant Biology, 2012)
Background: Wound-inducible Pin-II Proteinase inhibitors (PIs) are one of the important plant serine PIs which have been studied extensively for their structural and functional diversity and relevance in plant defense against insect pests. To explore the functional specialization of an array of Capsicum annuum (L.) proteinase inhibitor (CanPIs) genes, we studied their expression, processing and tissue-specific distribution under steady-state and induced conditions. Inductions were performed by subjecting C. annuum leaves to various treatments, namely aphid infestation or mechanical wounding followed by treatment with either oral secretion (OS) of Helicoverpa armigera or water. Results: The elicitation treatments regulated the accumulation of CanPIs corresponding to 4-, 3-, and 2-inhibitory repeat domains (IRDs). Fourty seven different CanPI genes composed of 28 unique IRDs were identified in total along with those reported earlier. The CanPI gene pool either from uninduced or induced leaves was dominated by 3-IRD PIs and trypsin inhibitory domains. Also a major contribution by 4-IRD CanPI genes possessing trypsin and chymotrypsin inhibitor domains was specifically revealed in wounded leaves treated with OS. Wounding displayed the highest number of unique CanPIs while wounding with OS treatment resulted in the high accumulation of specifically CanPI-4, -7 and -10. Characterization of the PI protein activity through two dimensional gel electrophoresis revealed tissue and induction specific patterns. Consistent with transcript abundance, wound plus OS or water treated C. annuum leaves exhibited significantly higher PI activity and isoform diversity contributed by 3- and 4-IRD CanPIs. CanPI accumulation and activity was weakly elicited by aphid infestation yet resulted in the higher expression of CanPI-26, -41 and -43. Conclusions: Plants can differentially perceive various kinds of insect attacks and respond appropriately through activating plant defenses including regulation of PIs at transcriptional and post-translational levels. Based on the differentially elicited CanPI accumulation patterns, it is intriguing to speculate that generating sequence diversity in the form of multi-IRD PIs is a part of elaborative plant defense strategy to obtain a diverse pool of functional units to confine insect attack.
Keywords: CanPI; Herbivory; Oral secretions; Pin-II type proteinase inhibitors; Plant-insect interaction

Structural and surface morphological properties of chemically deposited Mo0.5W0.5S2 thin film - Patil, A. A.; Hankare, P. P.; Gaikwad, A. B.; Garadkar, K. M. (Journal of Materials Science-Materials in Electronics, 2012)
Preparation of layered type semiconductor Mo0.5W0.5S2- thin films has been successfully done by using chemical bath deposition method. Objective of the studies are related to structural, optical, morphological and electrical properties of the thin films. The preparation method is based on the reaction between tartarate complex of Mo and W with thiourea in an aqueous alkaline medium at 363 K. X-Ray diffraction reveals a polycrystalline film composed of both MoS2 and WS2 phases. The optical study shows that the band gap of the film is 1.6 eV. Electrical conductivity is high which is in the order of 10(-3)-10(-2) (Omega cm)(-1).

Structural determination and chemical esterification of the sophorolipids produced by Candida bombicola grown on glucose and alpha-linolenic acid - Gupta, Reetika; Prabhune, Asmita (Biotechnology Letters, 2012)
The extracellular surface-active glycolipids produced by the yeast, Candida bombicola when grown on glucose and alpha-linolenic acid, were analyzed by HPLC with electro-spray ionization (ESI-MS) and collision-induced dissociation mass spectrometry. The analysis confirmed that the sophorolipid (SL) mixture contained three different forms of C18:3 SL molecules: free acid, lactone and a diacetylated lactone, which has not been reported previously. Also a minor amount of diacetylated lactone form of C18:1 SL was detected. Further, the SL mixture was subjected to chemical esterification reaction with sodium methoxide. The reaction product was analyzed with ESI-MS and confirmed to be the single homogenous esterified product containing C18:3 moieties in its fatty acid chain.
Keywords: Candida bombicola; Collision-induced dissociation mass spectrometry; Electrospray ionization mass spectrometry; HPLC; Linolenic acid; Sophorolipid methyl ester

Synthesis and self-assembly of glycopolypeptides - Pati, Debasis; Sen Gupta, Sayam (Abstracts of Papers of the American Chemical Society, 2012)

Synthesis and structural characterization of homochiral homo-oligomers of cis-gamma-methoxy-substituted cis- and trans-furanoid-beta-amino acids - Giri, Awadut G.; Jogdand, Ganesh F.; Rajamohanan, Pattuparampil R.; Pandey, Sunil K.; Ramana, Chepuri V. (European Journal of Organic Chemistry, 2012)
Herein we describe the synthesis of cis-/trans-3-aminotetrahydrofuran-2-carboxylic acids (cis-/trans-FAA) having a ?-methoxy group cis to the amine. The homo-oligomers of these two diastereomeric FAAs have been prepared. Preliminary investigation of their solution secondary structures revealed that they are the same as the homo-oligomers of the parent cis-/trans-FAA with the methoxy group only being a spectator substituent.
Keywords: Amino acids; helical structures; Oxygen heterocycles; Peptides

Synthesis of functional hybrid silica scaffolds with controllable hierarchical porosity by dynamic templating - Ganai, Anal Kumar; Kumari, Sushma; Sharma, Kamendra P.; Panda, Chakadola; Kumaraswamy, Guruswamy; Sen Gupta, Sayam (Chemical Communications, 2012)
We report a facile one-pot synthesis of hierarchically porous scaffolds, with independent control over nanoparticle mesoporosity and scaffold macroporosity. Our technique combines the chemistry of mesoporous silica nanoparticles with the control afforded by dynamic templating of surfactant mesophases. These materials are readily functionalizable and allow controllable spatial variation in macroporosity.

Synthesis of glycidol from glycerol and dimethyl carbonate using ionic liquid as a catalyst - Gade, Swapna M.; Munshi, Mudassir K.; Chherawalla, Batul M.; Rane, Vilas H.; Kelkar, Ashutosh A. (Catalysis Communications, 2012)
Transesterification of dimethyl carbonate with glycerol has been investigated using various ionic liquids as catalysts. Synthesis of glycidol with high selectivity (78%) has been achieved using tetramethylammonium hydroxide ([TMA][OH]) as a catalyst at 80 degrees C. Effect of various reaction conditions on the activity and selectivity was investigated and catalyst concentration had a significant influence on conversion as well as selectivity to glycidol. Activity as well as selectivity of the catalyst decreased significantly with increase in moisture content. Recycle experiment indicated slight drop in glycerol conversion and selectivity to glycidol because of dilution of reaction mixture and also the presence of products from the initial experiment. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Glycerol carbonate; Glycidol; Ionic liquid; Transesterification of glycerol

Synthesis of isomeric corniculatolides - Raut, Gajanan N.; Chakraborty, Kasturi; Verma, Priyanka; Gokhale, Rajesh S.; Reddy, D. Srinivasa (Tetrahedron Letters, 2012)
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

Synthesis of linear polylactic acid –based urethanes using tin modified closite -30b catalyst - Selukar, Balaji S.; Parwe, Sharad P.; Mohite, Kavita K.; Garnaik, Baijayantimala (Advance Material Letters, 2012)

Synthesis of polyamides from diols and diamines with liberation of H2 - Gnanaprakasam, Boopathy; Balaraman, Ekambaram; Gunanathan, Chidambaram; Milstein, David (Journal of Polymer Science Part A: Polymer Chemistry, 2012)
The amidation reaction based on catalytic coupling of alcohols with amines previously reported by us, using the pincer complexes 1 and 2 as catalysts, was applied to the generation of polyamides from nonactivated diols and diamines. A range of polymers was prepared, with Mn up to 26.9 kDa. Unlike the traditional syntheses of polyamides based on carboxylic acid derivatives, which require the use of toxic reagents and generate stoichiometric amounts of waste, this process generates only molecular hydrogen as byproduct. Both aromatic and aliphatic diols and diamines were used. Gel permeation chromatography measurements of the dimethylformamide-soluble polymers and thermal studies of the polyamides were performed. Matrix assisted laser desorption/ionization time-of-flight (MALDI-TOF) spectra are also reported. Thermogravimetric analyses studies indicate that the aromatic polyamides (with the exception of the pyridine-based polyamide) are more thermally stable than the aliphatic ones. This general, environmentally benign method for the synthesis of polyamides is homogeneously catalyzed under neutral conditions by dearomatized ruthenium-pincer complexes 1 and 2 and proceeds in 1,4-dioxane under an inert atmosphere. Conditions for polyamidation in the absence of solvent are also reported, using the pincer complex 2 as catalyst. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Synthesis of silk fibroin-glycopolypeptide conjugates and their recognition with lectin - Das, Soumen; Pati, Debasis; Tiwari, Neha; Nisal, Anuya; Sen Gupta, Sayam (Biomacromolecules, 2012)
Silk fibroin (SF), the natural fibrous protein created by the Bombyx mori silk worm, is being increasingly excellent mechanical strength, high oxygen/water permeability, excellent mechanical strength; high oxygen/water:permeability, and biocompatibility: :It is also well known that surface. modification of SF, With Organic ligands such as the extracellular protein :binding. Arg-Gly-Asp, (RGD) peptides:,: help adhesion and,proliferation. of cells better-a key; requirement for it to function as extracellular. matrices; In this, Work, We have conjugated synthetic glycopolypeptides (GPs) that were synthesized by controlled ring opening polymerization of alpha-manno-lys N-carboxyanhydrides (NCAs) onto SF by using Cu catalyzed click reaction to synthesize 1 a new hybrid :Material (SF GP), Which We believe will have :both the mechanical properties of native SF and the molecular recognition property of the carbohydrates in the GP. By controlling the :amount of GP grafted onto SF, we have made three SF GP conjugates that differ in their ability to assemble into films. SF GP conjugates having a very high content of GP formed completely water soluble brush like polymer that displayed very high affinity toward the lectin concanavalin-A (Con-A) Films cast from SF-GP conjugates using lower amounts of grafted GP were more stable in water, and the stability can be modulated by varying the amount of G grafted. The water insoluble film SF-GP(25) was also found to bind to fluorescently labeled Con A, as was seen by confocal microscopy Such SF-GP hybrid films may be useful as mimics of extracellular matrices for tissue engineering:

Synthesis of the aminocyclitol units of (-)-hygromycin a and methoxyhygromycin from myo-inositol - Gurale, Bharat P.; Shashidhar, Mysore S.; Gonnade, Rajesh G. (Journal of Organic Chemistry, 2012)
Concise and efficient syntheses of the aminocyclitol cores of hygromycin A (HMA) and methoxyhygromycin (MHM) have been achieved starting from readily available myo-inositol. Reductive cleavage of myo-inositol orthoformate to the corresponding 1,3-acetal, stereospecific introduction of the amino group via the azide, and resolution of a racemic cyclitol derivative as its diastereomeric mandelate esters are the key steps in the synthesis. Synthesis of the aminocyclitol core of hygromycin A involved chromatography in half of the total number of steps, and the aminocyclitol core of methoxyhygromycin involved only one chromatography.

Thermal, mechanical, and rheological characterization of polypropylene/layered double hydroxide nanocomposites - Lonkar, Sunil P.; Therias, Sandrine; Leroux, Fabrice; Gardette, Jean Luc; Singh, Raj Pal (Polymer Engineering and Science, 2012)
Polypropylene (PP)/organomodified layered double hydroxide (LDH) nanocomposites were prepared in order to examine the influence of LDH content on thermal, mechanical, and rheological properties. The nanostructure examinations by X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the exfoliated/intercalated dispersion of LDH. Incorporation of the LDH resulted in a noteworthy improvement in the thermal stability of PP. It was shown that the addition of LDH contributed to the reinforcement effect by increasing the elastic modulus. The mechanical performance, as evaluated by stressstrain curves, reveal that PP/LDH hybrid materials showed significant contribution toward increment in elastic modulus, tensile strength but at the expense of impact strength. The rheological response showed a strong influence of LDH particles on the flow behavior of the PP/LDH melt which resulted in enhancement of storage, loss of moduli, and complex viscosity of nanocomposites. Therefore, the nanocomposites have higher moduli but better processibility compared with pure PP. Overall, the results indicated that the LDH particles in nanometer size might act as potential reinforcing agent for polypropylene. POLYM. ENG. SCI., 52:20062014, 2012. (c) 2012 Society of Plastics Engineers

TiO2-Au plasmonic nanocomposite for enhanced dye-sensitized solar cell (DSSC) performance - Muduli, Subas; Game, Onkar S.; Dhas, Vivek V.; Vijayamohanan, K.; Bogle, Kashinath A.; Valanoor, N.; Ogale, Satishchandra B. (Solar Energy, 2012)
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

Topochemical click reaction: spontaneous self-stitching of a monosaccharide to linear oligomers through lattice-controlled azide-alkyne cycloaddition - Pathigoolla, Atchutarao; Gonnade, Rajesh G.; Sureshan, Kana M. (Angewandte Chemie-International Edition, 2012)
Keywords: Click chemistry; green chemistry; polymerization; pseudosugars; topochemistry

Toward a quantitative correlation between microstructure and DSSC efficiency: a case study of TiO2-xNx nanoparticles in a disordered mesoporous framework - Sivaranjani, Kumarsrinivasan; Agarkar, Shruti A.; Ogale, Satishchandra B.; Gopinath, Chinnakonda S. (Journal of Physical Chemistry C, 2012)
The efficiency (eta) of a dye-sensitized solar cell (DSSC) depends on various parameters, the critical factors being a fast charge carrier transport and a slow rate of electron-hole recombination. The present article describes a simple combustion synthesis method to prepare TiO2-xNx with following four important features that directly influences eta: (1) a disordered mesoporous structural framework with high surface area to give high dye-loading and a small diffusion length for charge carriers allowing rapid movement to the surface; (2) electrically interconnected nanocrystalline TiO2-xNx particles with good necking and predominant (101) anatase facets to minimize electron-hole recombination; (3) low charge storage capacity in the titania framework; and (4) surface unsaturation assisting all the above factors. The pseudo-three-dimensional nature of mesoporous TiO2-xNx with the above features demonstrates the importance of textural features, and porosity allows faster diffusion of charge carriers to surface and their utilization to generate power. A quantitative correlation between interconnected nanoparticles over larger distances in a mesoporous framework and eta is demonstrated. This study also demonstrates an inexpensive and rapid method of producing the photoanode material with high eta in about 10 min.

Toward understanding the redox properties of model chromophores from the greenfluorescent protein family: an interplay between conjugation, resonance stabilization, and solvent effects - Ghosh, Debashree; Acharya, Atanu; Tiwari, Subodh C.; Krylov, Anna I. (Journal of Physical Chemistry B, 2012)
The redox properties of model chromophores from the green fluorescent protein family are characterized computationally using density functional theory with a long-range corrected functional, the equation-of-motion coupled-cluster method, and implicit solvation models. The analysis of electron-donating abilities of the chromophores reveals an intricate interplay between the size of the chromophore, conjugation, resonance stabilization, presence of heteroatoms, and solvent effects. Our best estimates of the gas-phase vertical/adiabatic detachment energies of the deprotonated (i.e., anionic) model red, green, and blue chromophores are 3.27/3.15, 2.79/2.67, and 2.75/2.35 eV, respectively. Vertical/adiabatic ionization energies of the respective protonated (i.e., neutral) species are 7.64/7.35, 7.38/7.15, and 7.70/7.32 eV, respectively. The standard reduction potentials (E-red(0)) of the anionic (Chr(center dot)/Chr(-)) and neutral (Chr(+center dot)/Chr) model chromophores in acetonitrile are 0.34/1.40 V (red), 0.22/1.24 V (green), and -0.12/1.02 V (blue), suggesting, counterintuitively, that the red chromophore is more difficult to oxidize than the green and blue ones (in both neutral and deprotonated forms). The respective redox potentials in water follow a similar trend but are more positive than the acetonitrile values.

Transformation of (+/-)-lavandulol and (+/-)-tetrahydrolavandulol by a fungal strain Rhizopus oryzae - Daramwar, Pankaj P.; Rincy, Raju; Niloferjahan, Siddiqui; Krithika, Ramakrishnan; Gulati, Arvind; Yadav, Amit; Sharma, Rakesh; Thulasiram, Hirekodathakallu V. (Bioresource Technology, 2012)
Biotransformation of an irregular monoterpene alcohol, (+/-)-lavandulol [(+/-)-5-methyl-2-(1-methylethenyl)-4-hexen-1-ol] (I) and its tetrahydro derivative, (+/-)-tetrahydrolavandulol [(+/-)-2-isopropyl-5-methylhexan-1-ol] (II) were studied using a soil isolated fungal strain Rhizopus oryzae. Five metabolites, 2-((3,3-dimethyloxiran-2-yl)methyl)-3-methylbut-3-en-1-ol (Ia), 2-methyl-5-(prop-1-en-2-yl)hex-2ene-1,6-diol (Ib), 2-methyl-5-(prop-1-en-2-yl)hexane-1,6-diol (Ic), 2-(3-methylbut-2-enyl)-3-methylenebutane-1,4-diol (Id), 5-methyl-2-(2-methyloxiran-2-yl)hex-4-en-1-01 (Ie) have been isolated from the fermentation medium and characterized with lavandulol as a substrate. When tetrahydrolavandulol used as a substrate, two metabolites 2-isopropyl-5-methylhexane-1,5-diol (IIa) and 2-isopentyl-3-methylbutane-1,3-diol (lib) have been isolated from the fermentation medium. Biotransformation studies with R. oryzae clearly indicate that the organism initiates the transformation either by hydroxylation at allylic methyl groups or epoxidation of double bond. GC and GCMS analyses indicated that both (R)and (S)-enantiomers of I and II have been transformed into corresponding hydroxylated or epoxy derivatives, when racemic I and II were used as substrates. (C) 2011 Elsevier Ltd. All rights reserved.
Keywords: Biotransformation; Fungus; Lavandulol; Rhizopus oryzae; Tetrahydrolavandulol

Trehalose as an indicator of desiccation stress in Drosophila melanogaster larvae: a potential marker of anhydrobiosis - Thorat, Leena J.; Gaikwad, Sushama M.; Nath, Bimalendu B. (Biochemical and Biophysical Research Communications, 2012)
In the current scenario of global climate change, desiccation is considered as one of the major environmental stressors for the biota exposed to altered levels of ambient temperature and humidity. Drosophila melanogaster, a cosmopolitan terrestrial insect has been chosen as a humidity-sensitive bioindicator model for the present study since its habitat undergoes frequent stochastic and/or seasonally aggravated dehydration regimes. We report here for the first time the occurrence of anhydrobiosis in D. melanogaster larvae by subjecting them to desiccation stress under laboratory conditions. Larvae desiccated for ten hours at <5% relative humidity could enter anhydrobiosis and could revive upon rehydration followed by resumption of active metabolism. As revealed by FIR and HPLC analyzes, our findings strongly indicated the synthesis and accumulation of trehalose in the desiccating larvae. Biochemical measurements pointed out the desiccation-responsive trehalose metabolic pathway that was found to be coordinated in concert with the enzymes trehalose 6-phosphate synthase and trehalase. Further, an inhibitor-based experimental approach using deoxynojirimycin, a specific trehalase inhibitor, demonstrated the pivotal role of trehalose in larval anhydrobiosis of D. melanogaster. We therefore propose trehalose as a potential marker for the assessment of anhydrobiosis in Drosophila. The present findings thus add to the growing list of novel biochemical markers in specific bioindicator organisms for fulfilling the urgent need of environmental biomonitoring of climate change. (C) 2012 Elsevier Inc. All rights reserved.
Keywords: Anhydrobiosis; biomarker; Deoxynojirimycin; Desiccation; Drosophila melanogaster; trehalose

Trehalose as an indicator of desiccation stress in Drosophila melanogaster larvae: a potential marker of anhydrobiosis (vol 419, pg 638, 2012) - Thorat, Leena J.; Gaikwad, Sushama M.; Nath, Bimalendu B. (Biochemical and Biophysical Research Communications, 2012)

Trends towards zero discharge of distillery effluents - Gokarn, A. N.; Pande, Anita R.; Mayadevi, S. (Trends towards zero discharge of distillery effluents, 2012)
In the present paper we have described briefly a customer friendly process for the treatment of distillery effluent to obtain colourless water.In order to bring about improvement of cost factor, our developmental efforts towards cheaper and efficient adsorbents have been elucidated. Further improvement of its cost factor could be achieved by enhancing the colour removal ability of the adsorbent (activecharcoal) with small quantities of oxidizing agents (in ppm level). Recent developments towards obtaining valueadded products from spent wash using various methodologies and techniques have been reviewed with a view to encourage technocrats and entrepreneurs to take lead in this challenging and economically attractive endeavor

Tuning spectral properties of phenothiazine based donor-pi-acceptor dyes for efficient dye-sensitized solar cells - Marszalek, Magdalena; Nagane, Satyawan; Ichake, Amol; Humphry-Baker, Robin; Paul, Vincent; Zakeeruddin, Shaik M.; Graetzel, Michael (Journal of Materials Chemistry, 2012)
Two novel metal-free organic donor-pi-acceptor dyes were synthesized using electron-rich 10-butyl-(2-methylthio)-10H-phenothiazine as a donor and cyanoacrylic acid as an acceptor. The spectral response of the dye was tuned by introducing a vinylene thiophene pi-bridge. Obtained optical and electrochemical properties of the dyes seemed to be promising in terms of employing them as light harvesters in dye-sensitized solar cells (DSCs). The efficiencies of the devices under standard AM 1.5G (100 mW cm(-2)) conditions reached 7.3% with volatile electrolyte. The differences in the photovoltaic parameters of these DSCs were explained by comparing the results of electrochemical impedance spectroscopy (EIS) measurements and transient photovoltage and photocurrent decay experiments.

Ultrasound assisted one pot synthesis of imidazole derivatives using diethyl bromophosphate as an oxidant - Nagargoje, Deepak; Mandhane, Priyanka; Shingote, Savita; Badadhe, Pravin; Gill, Charansingh H. (Ultrasonics Sonochemistry, 2012)
A one pot, three-component condensation of benzoin/benzyl, an aldehyde, and ammonium acetate using diethyl bromophosphate as a mild oxidant is achieved to form trisubstituted imidazole compounds. Under ultrasound irradiation, a smooth condensation occurs to get the 2, 4, 5-triaryl-1H-imidazole compounds in good to excellent yields. The study explores the scope and limitation of diethyl bromophosphate as an oxidant and suggests advantages, viz., simplicity of operation, reduction in time, and an increase in product yields. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Diethyl bromophosphate (DEP); Imidazole; One pot synthesis; Ultrasound

Understanding the growth of micro and nano-crystalline AlN by thermal plasma process - Kanhe, Nilesh S.; Nawale, Ashok B.; Gawade, Rupesh L.; Puranik, Vedavati G.; Bhoraskar, S. V.; Das, Asoka K.; Mathe, Vikas L. (Journal of Crystal Growth, 2012)
We report the studies related to the growth of crystalline AlN in a DC thermal plasma reactor, operated by a transferred arc plasma torch. The reactor is capable of producing the nanoparticles of Al and AlN depending on the composition of the reacting gas. Al and AlN micro crystals are formed at the anode placed on the graphite and nano crystalline Al and AlN gets deposited on the inner surface of the plasma reactor. X-ray diffraction, Raman spectroscopy analysis, single crystal X-ray diffraction and TGA-DTA techniques are used to infer the purity of post process crystals as a hexagonal AlN. The average particle size using SEM was found to be around 30 mu m. The morphology of nanoparticles of Al and AlN, nucleated by gas phase condensation in a homogeneous medium were studied by transmission electron microscopy analysis. The particle ranged in size between 15 and 80 nm in diameter. The possible growth mechanism of crystalline AlN at the anode has been explained on the basis of non-equilibrium processes in the core of the plasma and steep temperature gradient near its periphery. The gas phase species of AlN and various constituent were computed using Murphy code based on minimization of free energy. The process provides 50% yield of microcrystalline AlN and remaining of Al at anode and that of nanocrystalline h-AlN and c-Al collected from the walls of the chamber is about 33% and 67%, respectively. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Crystal morphology; Growth from high temperature solutions; Nitride; Semiconducting aluminum compound

Unusual conformational similarity of two peptide folds featuring sulfonamide and carboxamide on the backbone - Vijayadas, Kuruppanthara N.; Davis, Hilda C.; Kotmale, Amol S.; Gawade, Rupesh L.; Puranik, Vedavati G.; Rajamohanan, Pattuparambil R.; Sanjayan, Gangadhar J. (Chemical Communications, 2012)
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.

Use of ruthenium complexes for formation and/or hydrogenation of amides and related carboxylic acid derivatives - Milstein, David; Gunanathan, Chidambaram; Ben-David, Yehoshoa; Balaraman, Ekambaram; Gnanaprakasam, Boopathy; Zhang, Jing (US20120253042, US20160152663, 2012)
A process for preparing amides by reacting a primary amine and a primary alcohol in the presence of a Ruthenium complex to generate the amide and molecular hydrogen. Primary amines are directly acylated by equimolar amounts of alcohols to produce amides and molecular hydrogen (the only byproduct) in high yields and high turnover numbers. Also disclosed are processes for hydrogenation of amides to alcohols and amines; hydrogenation of organic carbonates to alcohols; hydrogenation of carbamates or urea derivatives to alcohols and amines; amidation of esters; acylation of alcohols using esters; coupling of alcohols with water and a base to form carboxylic acids; dehydrogenation of beta-amino alcohols to form pyrazines and cyclic dipeptides; and dehydrogenation of secondary alcohols to ketones. These reactions are catalyzed by a Ruthenium complex which is based on a dearomatized PNN-type ligand of formula A1 or precursors thereof of formulae A2 or A3.

Visible-light-induced photosplitting of water over gamma `-Fe4N and gamma `-Fe4N/alpha-Fe2O3 nanocatalysts - Dhanasekaran, P.; Salunke, Hemant G.; Gupta, Narendra M. (Journal of Physical Chemistry C, 2012)
The application of gamma'-Fe4N, a noble-metal-free, low-cost catalyst, in the photosplitting of neat water into stoichiometric amounts of H-2 and O-2 under visible-light irradiation is reported for the first time. The catalyst showed optical absorption and photoluminescence emission bands in the entire visible region. The photocatalytic water-splitting activity was wavelength-dependent, the quantum efficiency for H-2 evolution being ca. 1.7 and 0.7% at excitation wavelengths of 450 and 500 nm, respectively. Addition of electron donor/acceptor sacrificial reagents considerably affected the yield and stoichiometry of H-2 and O-2. At the same time, the product yield increased in a composition-dependent manner for (gamma'-Fe4N)(x) + (alpha-Fe2O3)(1-x) nanocomposites. This activity augmentation is ascribed to the better dispersion of the active component gamma'-Fe4N and also to the availability of more active surface sites at Fe4N/Fe2O3 contacts. Moreover, the proximity of the valence band potential of the component photosystems promotes the preferential transfer/entrapment of photoexcited hole carriers. We envisage that the defect/impurity-induced interband-gap energy states may play a vital role in these charge-transfer processes, leading thereby to more effective e(-)-h(+) separation and the enhanced rate of the water-splitting reaction. First-principles electronic structure analysis suggests that the extraordinary photocatalytic and optical properties of intermetallic gamma'-Fe4N may arise from the particle-size-dependent changes in electronic structure.

VUV Photoionization and Ab initio determination of the ionization energy of a gas-phasesugar (deoxyribose) - Ghosh, Debashree; Golan, Amir; Takahashi, Lynelle K.; Krylov, Anna I.; Ahmed, Musahid (Journal of Physical, 2012)
The ionization energy of gas-phase deoxyribose was determined using tunable vacuum ultraviolet synchrotron radiation coupled to an effusive thermal source. Adiabatic and vertical ionization energies of the ground and first four excited states of alpha-pyranose, the structure that dominates in the gas phase, were calculated using high-level electronic structure methods. An appearance energy of 9.1(+/- 0.05) eV was recorded, which agrees reasonably well with a theoretical value of 8.8 eV for the adiabatic ionization energy. A clear picture of the dissociative photoionization dynamics of deoxyribose emerges from the fragmentation pattern recorded using mass spectrometry and from ab initio molecular dynamics calculations. The experimental threshold 9.4 (+/- 0.05) eV for neutral water elimination upon ionization is captured well in the calculations, and qualitative insights are provided by molecular orbital analysis and molecular dynamics snapshots along the reaction coordinate.

Alpha-trimethylsilylmethylamine radical cation in the synthesis of cyclic amines and beyond - Pandey, Ganesh; Dey, Debasis; Gadre, Smita R. (Chimia, 2013)
The evolution of chemistry associated with the photoinduced electron transfer (PET)-generated alpha-trimethylsilylmethylamine radical cation cyclization to a tethered olefin to synthesize byclic amine structural frame works is presented in chronological order. The importance of this interesting chemistry is demonstrated by the synthesis of several novel glycosidase inhibitors.
Keywords: 1-N-Iminosugars; alpha-Amine radical; alpha-Trimethylsilyl methylamine radical cation; Glycosidase inhibitors; Photoinduced electron transfer (PET)

Alterations in the helicoverpa armigera midgut digestive physiology after ingestion of pigeon pea inducible leucine aminopeptidase - Lomate, Purushottam R.; Jadhav, Bhakti R.; Giri, Ashok P.; Hivrale, Vandana K. (Plos One, 2013)
Jasmonate inducible plant leucine aminopeptidase (LAP) is proposed to serve as direct defense in the insect midgut. However, exact functions of inducible plant LAPs in the insect midgut remain to be estimated. In the present investigation, we report the direct defensive role of pigeon pea inducible LAP in the midgut of Helicoverpa armigera (Lepidoptera: Noctuidae) and responses of midgut soluble aminopeptidases and serine proteinases upon LAP ingestion. Larval growth and survival was significantly reduced on the diets supplemented with pigeon pea LAP. Aminopeptidase activities in larvae remain unaltered in presence or absence of inducible LAP in the diet. On the contrary, serine proteinase activities were significantly decreased in the larvae reared on pigeon pea LAP containing diet as compared to larvae fed on diet without LAP. Our data suggest that pigeon pea inducible LAP is responsible for the degradation of midgut serine proteinases upon ingestion. Reduction in the aminopeptidase activity with LpNA in the H. armigera larvae was compensated with an induction of aminopeptidase activity with ApNA. Our findings could be helpful to further dissect the roles of plant inducible LAPs in the direct plant defense against herbivory.

Aminosilicate sol-gel stabilized N-doped TiO2-Au nanocomposite materials and their potential environmental remediation applications - Pandikumar, Alagarsamy; Sivaranjani, Kumarsrinivasan; Gopinath, Chinnakonda S.; Ramaraj, Ramasamy (RSC Advances, 2013)
A facile chemical reduction method to synthesize amine functionalized silicate sol-gel-supported gold-deposited nitrogen-doped Degussa-TiO2 nanocomposite materials (APS/(N-P25-Au)(NCM)) is reported and the materials are characterized by DRS, PL, XRD, TEM, Raman, XPS and BET surface area analysis. The application of the synthesized APS/(N-P25-Au)(N)CM towards environmental remediation processes are investigated by studying the catalytic oxidation of carbon monoxide (CO) and photocatalytic reduction of toxic mercuric (Hg(II)) ions. The catalytic and photocatalytic activity of the prepared catalysts are found to be in the order of APS/(N-P25-Au)(NCM) >> APS/(P25-Au)(NCM) > N-P25 > P25. The enhanced catalytic and photocatalytic activities of the APS/(N-P25-Au)(NCM) can be attributed to the synergistic effect of Au-nps and N-doped P25. The catalytic activities of the APS/(N-P25-Au)(NCM) are very promising in the field of green technology for the environmental cleaning applications.

Ant-pro reverse-turn motif. structural features and conformational characteristics - Thorat, Vijaykumar H.; Ingole, Tukaram S.; Vijayadas, Kuruppanthara N.; Nair, Roshna V.; Kale, Sangram S.; Ramesh, Veera V. E.; Davis, Hilda C.; Prabhakaran, Panchami; Gonnade, Rajesh G.; Gawade, Rupesh L.; Puranik, Vedavati G.; Rajamohanan, Pattuparambil R.; et al. (European Journal of Organic Chemistry, 2013)
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

Applications of lithium zirconium silicate at high temperature for the carbon dioxide sorption and conversion to syn-gas - Raskar, Reshma; Rane, Vilas; Gaikwad, Abaji G. (Water Air and Soil Pollution, 2013)
The applications of different samples of lithium zirconium silicate contributing to CO2 sorption and conversion of CO2 to syn-gas at high temperatures were investigated. Several samples of lithium zirconium silicate prepared by solid-solid fusion method were calcined in air or nitrogen atmosphere at 900 degrees C for 3 h. The lithium zirconium silicate samples were characterized by acidity/alkalinity, surface area, XRD pattern, SEM images, and CO2 sorption. The alkalinity and surface area of the samples of lithium zirconium silicate were found to be in the range of 15.1 to 20.0 mmol g(-1) and 0.05 to 2.13 m(2) g(-1), respectively. The temperature profile of CO2 sorption by samples of lithium zirconium silicate was given for the range 100 to 700 degrees C. The CO2 sorption was found to be in the range of 12.81 to 18.04 wt.% at 550 degrees C for samples of lithium zirconium silicate with different Li/Zr/Si mole ratios from 1 to 6. The crystalline phases in the samples of the lithium zirconium silicate, Li6Si2O7, ZrSiO4, Li2SiO3, Li2ZrO3, Li4ZrO4, and Li4SiO4 could contribute to CO2 capture. The conversion of CO2 by methane to syn-gas over the lithium silicate samples and PdO (5 wt.%)/Al2O3 at 500 degrees C with the gas hourly space velocities 6,000, 12,000, and 36,000 mL h(-1) g(-1) of methane and 6,000 mL h(-1) g(-1) of CO2 was explored. However, the higher conversion of CO2 to syn-gas was observed at the low gas hourly space velocity of 6,000 mL h(-1) g(-1) of methane.
Keywords: Applications of lithium zirconium silicate; CO2 sorption; Solid-solid fusion method; Syn-gas; Temperature profile

Arsenomics of exiguobacterium sp PS (NCIM 5463) - Sacheti, Poonam; Bhonsle, Hemangi S.; Patil, Rajendra; Kulkarni, Mahesh J.; Srikanth, Rapole; Gade, Wasudeo N. (RSC Advances, 2013)
In the present study, arsenate [As(V)] tolerant organisms were isolated from a metal contaminated site, and identified by 16S rDNA sequencing as Exiguobacterium sp. Arsenomics (omics of arsenic response) in Exiguobacterium sp. PS via two-dimensional gel electrophoresis (2-DGE) coupled with identification of proteins using MALDI-TOF MS, MALDI-TOF MS/MS and LC/MSE are studied vide this paper. Out of 2460 Coomassie stained proteins, 270 were differentially expressed (p < 0.05). Considering the resolution and abundance level, 45 spots (proteins) were subjected to MALDI-TOF MS/MS, MALDI-TOF/TOF and LC/MSE. Out of these, 33 were identified and categorized into several functional categories (including both known and novel/putative stress responsive proteins) viz., carbohydrate and energy metabolism, stress response, motility, amino acid, and purine and protein synthesis. The identifications of unique proteins, phosphate ABC transporter ATPase subunit and pyridine nucleotide disulfide oxidoreductase, are the significant findings of the present study which may be used as markers of As(V) stress in Exiguobacterium sp. PS. The absence of As(V) reductase activity and non-amplification of the arsC gene of the ars operon suggests that the classical mechanism of As(V) resistance may not be operating in Exiguobacterium sp. PS. Lastly, considering the fact that proteomic studies under As(V) stress were performed only in Gram negative organisms, this study is the first comprehensive endeavour to explore the mechanism of As(V) response in Gram positive organisms, Exiguobacterium sp. PS at the proteomic level.

Asymmetric N-heterocyclic carbene (NHC)-catalyzed annulation of modified enals with enolizable aldehydes - Yetra, Santhivardhana Reddy; Kaicharla, Trinadh; Kunte, Sunita S.; Gonnade, Rajesh G.; Biju, Akkattu T. (Organic Letters, 2013)
N-Heterocyclic carbene (NHC)-catalyzed highly enantioselective lactonization of modified enals with enolizable aldehydes, proceeding via the alpha,beta-unsaturated acylazolium intermediates, is reported. The reaction results in the asymmetric synthesis of synthetically important 4,5-disubstituted dihydropyranones.

Azide-functionalized lanthanide-based metal-organic frameworks showing selective CO2 gas adsorption and postsynthetic cavity expansion - Ganguly, Sumi; Pachfule, Pradip; Bala, Sukhen; Goswami, Arijit; Bhattacharya, Sudeshna; Mondal, Raju (Inorganic Chemistry, 2013)
We report herein selective CO2 gas adsorption by two azide-functionalized lanthanide-based metal-organic frameworks (MOFs). This work also demonstrates that azide-functionalized MOFs can be used for postsynthetic cavity expansion, further corroborated by enhanced gas-sorption data.

Basic structural motif and major biophysical properties of Amyloid-beta are encoded in the fragment 18-35 - Chandrakesan, Muralidharan; Sarkar, Bidyut; Mithu, Venus Singh; Rajiv M. Abhyankar; Bhowmik, Debanjan; Nag, Suman; Sahoo, Bankanidhi; Shah, Riddhi; Gurav, Sushma; Banerjee, Raja; Dandekar, Sucheta; Jose, Jaya C.; et al. (Chemical Physics, 2013)
Aggregation and misfolding of the amyloid beta (A beta) peptide is thought to initiate Alzheimer's disease (AD). Here we study the role played by its central segment (A beta(18-35)) in determining these properties. A beta(18-35) has a solubility of 18 mu M. The soluble fraction consists mainly of small oligomers, which have mixed beta-sheet and random coil structures. The monomer is mostly a random coil with some residual compactness. Aggregated A beta(18-35) forms fibrils of width 3.0 +/- 0.7 nm, which is consistent with a hairpin shape. Each of these properties has a close similarity to A beta(40). Remarkably, solid state NMR indicates that the fibrils also retain the secondary structure and tertiary contacts of A beta(40). This is the shortest fragment of A beta reported so far which preserves its fibrillar architecture, including the hairpin turn, as well as its solution phase conformational properties. Residues 18-35 should therefore be a key target of AD therapeutics. (C) 2013 Published by Elsevier B. V.
Keywords: Alzheimer's disease; Fluorescence correlation spectroscopy; Protein aggregation; Solid-state NMR

Biocatalyst mediated production of 6 beta,11 alpha-dihydroxy derivatives of 4-ene-3-one steroids - Kolet, Swati P.; Niloferjahan, Siddiqui; Haldar, Saikat; Gonnade, Rajesh G.; Thulasiram, Hirekodathakallu V. (Steroids, 2013)
Biotransformation of steroids with 4-ene-3-one functionality such as progesterone (I), testosterone (II), 17 alpha-methyltestosterone (III), 4-androstene-3,17-dione (IV) and 19-nortestosterone (V) were studied by using a fungal system belonging to the genera of Mucor (M881). The fungal system efficiently and quantitatively converted these steroids in regio- and stereo-selective manner into corresponding 6 beta,11 alpha-dihydroxy compounds. Time course experiments suggested that the transformation was initiated by hydroxylation at 6 beta- or 11 alpha-(10 beta-hydroxy in case of V) to form monohydroxy derivatives which upon prolonged incubation were converted into corresponding 613,11oc-dihydroxy derivatives. The fermentation studies carried out using 5 L table-top fermentor with substrates (I and II) clearly indicates that 6 beta,11 alpha-dihydroxy derivatives of steroids with 4-ene-3-one functionality can be produced in large scale by using M881. (C) 2013 Elsevier Ltd.
Keywords: 4-Ene-3-one steroids; Biotransformation; Mucor sp.

Biodegradation of phenol by the yeast candida tropicalis: an investigation by NMR spectroscopy - Phalgune, U. D.; Rajamohanan, P. R.; Gaikwad, B. G.; Varma, R. J.; George, S. (Applied Biochemistry and Biotechnology, 2013)
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

Biomass to biodegradable polymer (PLA) - Singhvi, Mamata; Gokhale, Digambar V. (RSC Advances, 2013)
Lignocellulosic biomass is renewable and cheap, and it has the potential to displace fossil fuels for the production of fuels and chemicals. Biomass derived lactic acid is an important compound that can be used as a chemical platform for the production of a variety of important chemicals on a large scale. The quality of the monomers of lactic acid and lactide, as well as the chemical changes induced during polymerization and processing, are crucial parameters for controlling the properties of the resulting polylactic acid (PLA) products. In this review, we outline the process of exploiting biomass for the production of polylactic acid, a biodegradable polymer which is well-known as a sustainable bioplastic material.

Biosynthesis of antinutritional alkaloids in solanaceous crops is mediated by clustered genes - Itkin, M.; Heinig, U.; Tzfadia, O.; Bhide, Amey J.; Shinde, B.; Cardenas, Pablo D.; Bocobza, S. E.; Unger, T.; Malitsky, Sergey; Finkers, R.; Tikunov, Y.; Bovy, A.; et al. (Science, 2013)
Steroidal glycoalkaloids (SGAs) such as alpha-solanine found in solanaceous food plants-as, for example, potato-are antinutritional factors for humans. Comparative coexpression analysis between tomato and potato coupled with chemical profiling revealed an array of 10 genes that partake in SGA biosynthesis. We discovered that six of them exist as a cluster on chromosome 7, whereas an additional two are adjacent in a duplicated genomic region on chromosome 12. Following systematic functional analysis, we suggest a revised SGA biosynthetic pathway starting from cholesterol up to the tetrasaccharide moiety linked to the tomato SGA aglycone. Silencing GLYCOALKALOID METABOLISM 4 prevented accumulation of SGAs in potato tubers and tomato fruit. This may provide a means for removal of unsafe, antinutritional substances present in these widely used food crops.

CAP/EOM-CCSD method for the study of potential curves of resonant states - Ghosh, Aryya; Karne, Anagha S.; Pal, Sourav; Vaval, Nayana (Physical Chemistry Chemical Physics, 2013)
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.

Carboxamide versus sulfonamide in peptide backbone folding: a case study with a hetero foldamer - Ramesh, Veera V. E.; Kale, Sangram S.; Kotmale, Amol S.; Gawade, Rupesh L.; Puranik, Vedavati G.; Rajamohanan, P. R.; Sanjayan, Gangadhar J. (Organic Letters, 2013)
Strikingly dissimilar hydrogen-bonding patterns have been observed for two sets of closely similar hetero foldamers containing carboxamide and sulfonamides at regular intervals. Although both foldamers maintain conformational ordering, the hydrogen-bonding pattern and backbone helical handedness differ diametrically.

Catalytic dehydration of lactic acid to acrylic acid using calcium hydroxyapatite catalysts - Ghantani, Vidhya C.; Lomate, Samadhan T.; Dongare, Mohan K.; Shubhangi B. Umbarkar (Green Chemistry, 2013)
A series of calcium hydroxyapatite (HAP) catalysts were synthesised with a Ca/P ratio ranging from 1.3 to 1.89 by a co-precipitation method that involved changing the pH of the calcium and phosphorous precursors. The physicochemical characterization by XRD, SEM, BET surface area and CO2 and NH3-TPD techniques confirmed the hydroxyapatite formation. These HAP catalysts were used for the vapour phase dehydration of lactic acid to acrylic acid. The HAP catalyst with a Ca/P ratio of 1.3 was found to be the most efficient catalyst among the synthesised series, which gave 100% conversion of lactic acid and 60% selectivity towards acrylic acid at 375 degrees C when a 50% (w/w) aqueous solution of lactic acid was used. The higher selectivity towards acrylic acid has been correlated to the increased acidity and reduced basicity of the HAP catalyst with a Ca/P ratio of 1.3 compared to the other HAP catalysts. The catalyst was found to be very stable and no deactivation was observed even after 300 h of reaction time. In situ FTIR studies were performed for understanding the mechanistic aspects and showed the formation of calcium lactate as an intermediate species during the dehydration of lactic acid to acrylic acid.

Catalytic signal amplification using [Fe-III(biuret-amide)]-mesoporous silica nanoparticles: visual cyanide detection - Panda, Chakadola; Dhar, Basab B.; Malvi, Bharmana; Bhattacharjee, Yudhajit; Sen Gupta, Sayam (Chemical Communications, 2013)
Catalytic signal amplification was used for the colorimetric detection of CN- in aqueous media by using the enzyme catalase in tandem with mesoporous silica nanoparticle based synthetic HRP enzyme mimic Fe-MSNs. Signal amplification up to a maximum of eight fold was observed for the reporter ``oxidized TMB'' with respect to the added CN- ion.

C-C Bond formation catalyzed by natural gelatin and collagen proteins - Kuehbeck, Dennis; Dhar, Basab Bijayi; Schoen, Eva-Maria; Cativiela, Carlos; Gotor-Fernandez, Vicente; Diaz, David Diaz (Beilstein Journal of Organic Chemistry, 2013)
The activity of gelatin and collagen proteins towards C-C bond formation via Henry (nitroaldol) reaction between aldehydes and nitroalkanes is demonstrated for the first time. Among other variables, protein source, physical state and chemical modification influence product yield and kinetics, affording the nitroaldol products in both aqueous and organic media under mild conditions. Significantly, the scale-up of the process between 4-nitrobenzaldehyde and nitromethane is successfully achieved at 1 g scale and in good yield. A comparative kinetic study with other biocatalysts shows an increase of the first-order rate constant in the order chitosan < gelatin < bovine serum albumin (BSA) < collagen. The results of this study indicate that simple edible gelatin can promote C-C bond forming reactions under physiological conditions, which may have important implications from a metabolic perspective.
Keywords: biocatalysis; carbon-carbon bond formation; gelatin; Henry reaction; protein

Characterization of a chemostable serine alkaline protease from Periplaneta americana - Sanatan, Prashant T.; Lomate, Purushottam R.; Giri, Ashok P.; Hivrale, Vandana K. (BMC Biochemistry, 2013)
Background: Proteases are important enzymes involved in numerous essential physiological processes and hold a strong potential for industrial applications. The proteolytic activity of insects' gut is endowed by many isoforms with diverse properties and specificities. Thus, insect proteases can act as a tool in industrial processes. Results: In the present study, purification and properties of a serine alkaline protease from Periplaneta americana and its potential application as an additive in various bio-formulations are reported. The enzyme was purified near to homogeneity by using acetone precipitation and Sephadex G-100 gel filtration chromatography. Enzyme activity was increased up to 4.2 fold after gel filtration chromatography. The purified enzyme appeared as single protein-band with a molecular mass of similar to 27.8 kDa in SDS-PAGE. The optimum pH and temperature for the proteolytic activity for purified protein were found around pH 8.0 and 60 degrees C respectively. Complete inhibition of the purified enzyme by phenylmethylsulfonyl fluoride confirmed that the protease was of serine-type. The purified enzyme revealed high stability and compatibility towards detergents, oxidizing, reducing, and bleaching agents. In addition, enzyme also showed stability towards organic solvents and commercial detergents. Conclusion: Several important properties of a serine protease from P. Americana were revealed. Moreover, insects can serve as excellent and alternative source of industrially important proteases with unique properties, which can be utilized as additives in detergents, stain removers and other bio-formulations. Properties of the P. americana protease accounted in the present investigation can be exploited further in various industrial processes. As an industrial prospective, identification of enzymes with varying essential properties from different insect species might be good approach and bioresource.
Keywords: Chemostability; Industrial catalyst; Insect proteases; Periplaneta americana; Serine alkaline protease

Characterization of three novel isoprenyl diphosphate synthases from the terpenoid rich mango fruit - Kulkarni, Ram; Pandit, Sagar; Chidley, Hemangi G.; Nagel, Raimund; Schmidt, Axel; Gershenzon, Jonathan; Pujari, Keshav; Giri, Ashok P.; Gupta, Vidya (Plant Physiology and Biochemistry, 2013)
Mango (cv. Alphonso) is popular due to its highly attractive, terpenoid-rich flavor. Although Alphonso is clonally propagated, its fruit-flavor composition varies when plants are grown in different geo-climatic zones. Isoprenyl diphosphate synthases catalyze important branch-point reactions in terpenoid biosynthesis, providing precursors for common terpenoids such as volatile terpenes, sterols and carotenoids. Two geranyl diphosphate synthases and a farnesyl diphosphate synthase were isolated from Alphonso fruits, cloned for recombinant expression and found to produce the respective products. Although, one of the geranyl diphosphate synthases showed high sequence similarity to the geranylgeranyl diphosphate synthases, it did not exhibit geranylgeranyl diphosphate synthesizing activity. When modeled, this geranyl diphosphate synthase and farnesyl diphosphate synthase structures were found to be homologous with the reference structures, having all the catalytic side chains appropriately oriented. The optimum temperature for both the geranyl diphosphate synthases was 40 degrees C and that for farnesyl diphosphate synthase was 25 degrees C. This finding correlated well with the dominance of monoterpenes in comparison to sesquiterpenes in the fruits of Alphonso mango in which the mesocarp temperature is higher during ripening than development. The absence of activity of these enzymes with the divalent metal ion other than Mg2+ indicated their adaptation to the Mg2+ rich mesocarp. The typical expression pattern of these genes through the ripening stages of fruits from different cultivation localities depicting the highest transcript levels of these genes in the stage preceding the maximum terpene accumulation indicated the involvement of these genes in the biosynthesis of volatile terpenes. (C) 2013 Elsevier Masson SAS. All rights reserved.
Keywords: Alphonso; Flavor variation; Fruit; Isoprenyl diphosphate synthase; Mangifera indica; Terpene volatiles

Chemically conjugated sophorolipids on CdTe QDs: a biocompatible photoluminescence nanocomposite for theranostic applications - Singh, Pooja; Joshi, Kasturi; Guin, Debanjan; Prabhune, Asmita (RSC Advances, 2013)
Functional nontoxic cadmium telluride (CdTe) quantum dots (QDs) have been synthesized using a natural functional glycolipid belonging to the family of sophorolipids (SL) as a surface-modifying agent. These SLs with open acidic form are highly suitable for QDs stabilization, are readily obtained by a fermentation process of the yeast Candida bombicola (polymorph Starmerella bombicola) in large amounts. In this work chemically stable, water soluble, and photoluminescent CdTe QDs were successfully conjugated to sophorolipids via a cross-linking reaction. The formation of SLs conjugated CdTe QDs was confirmed using different analytical techniques X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscopy (TEM), Electron Diffraction (ED), Atomic Force Microscopy (AFM), Dynamic Light Scattering (DLS), and Photoluminescence (PL). It was shown that after being conjugated with SL the SL-CdTe QDs becomes biocompatible, still maintaining its water solubility and photoluminescence properties. The final SL coated photoluminescent CdTe QDs represent interesting biocompatible materials potentially useful for biomedical applications.

CN? specific turn-on phosphorescent probe with probable application for enzymatic assay and as an imaging reagent - Reddy, Upendar G.; Das, Priyadip; Saha, Sukdeb; Baidya, Mithu; Ghosh, Sudip K.; Das, Amitava (Chemical Communications, 2013)
A new “turn-on” luminescence probe for imaging the uptake of 0.2 ppm inorganic CN− in live HeLa cells as well as for probing the CN− generation through an enzymatic process in a virtual aqueous medium at appropriate pH.

Combinatorial approach of statistical optimization and mutagenesis for improved production of acidic phytase by Aspergillus niger NCIM 563 under submerged fermentation condition - Bhavsar, Kavita P.; Gujar, P.; Shah, P.; Kumar, V. Ravi; Khire, Jayant Malhar (Applied Microbiology and Biotechnology, 2013)
Combination of statistical optimization and mutagenesis to isolate hypersecretory strains is studied to maximize phytase production from Aspergillus niger NCIM 563 under submerged fermentation. The overall results obtained show a remarkable 5.98-fold improvement in phytase production rates when compared to that using basal medium. Optimization of culture conditions from parent strain is studied first by the Plackett-Burman technique to evaluate the effects of 11 variables for phytase production. The results showed that glucose, MgSO4, KCl, incubation period, and MnSO4 are the most significant variables affecting enzyme production. Further optimization in these variables, using a central composite design technique, resulted in 3.74-fold increase in the yield of phytase production to 254,500 U/l when compared with the activity observed with basal media (68,000 U/l) in shake flask. Our experiments show that the phytase from A. niger NCIM 563 exhibits desirable activity in simulated gastric fluid conditions with low pH and also improved thermostability when compared to commercial phytase. The improved yield demonstrates the potential applicability of phytase enzyme as a source of phytase supplement for phosphorus nutrition and environmental protection in animal feed industry. Physical and chemical mutagenesis experiments were carried out in parallel to isolate hypersecretory mutants that could possibly further enhance the enzyme production. Using optimized media conditions of the parent strain, our results show that mutant strain A. niger NCIM 1359 increased the phytase activity by another 1.6-fold to 407,200 U/l.
Keywords: Animal feed; Aspergillus niger; Mutagenesis; Phytase; Statistical optimization

Comparison of methods for identifying periodically varying genes - Vijayan, V.; Deshpande, P.; Gadgil, Chetan J.; Gadgil, Mugdha (International Journal of Bioinformatics Research and Applications, 2013)

Complementation of intramolecular interactions for structural-functional stability of plant serine proteinase inhibitors - Joshi, Rakesh S.; Mishra, Manasi; Suresh, C. G.; Gupta, Vidya S.; Giri, Ashok P. (Biochimica Et Biophysica Acta-General Subjects, 2013)
Background: Plant protease inhibitors (PIs) constitute a diverse group of proteins capable of inhibiting proteases. Among Pls, serine Pls (SPIs) display stability and conformational restrictions of the reactive site loop by virtue of their compact size, and by the presence of disulfide bonds, hydrogen bonds, and other weak interactions. Scope of review: The significance of various intramolecular interactions contributing to protein folding mechanism and their role in overall stability and activity of SPIs is discussed here. Furthermore, we have reviewed the effect of variation or manipulation of these interactions on the activity/stability of SPIs. Major conclusions: The selective gain or loss of disulfide bond(s) in SPIs can be associated with their functional differentiation, which is likely to be compensated by non-covalent interactions (hydrogen bonding or electrostatic interactions). Thus, these intramolecular interactions are collectively responsible for the functional activity of SPIs, through the maintenance of scaffold framework, conformational rigidity and shape complementarities of reactive site loop. General significance: Structural insight of these interactions will provide an in-depth understanding of kinetic and thermodynamic parameters involved in the folding and stability mechanisms of SPIs. These features can be explored for engineering canonical SPIs for optimizing their overall stability and functionality for various applications. (C) 2013 Elsevier B.V. All rights reserved.
Keywords: Disulfide bond; hydrogen bonding; Intramolecular weak interaction; Protease; Reactive site loop; Serine proteinase inhibitor

Comprehensive study on mutual interplay of multiple V-shaped ligands on the helical nature of a series of coordination polymers and their properties - Goswami, Arijit; Bala, Sukhen; Pachfule, Pradip; Mondal, Raju (Crystal Growth & Design, 2013)
{V-shaped ligands are commonly used for helical coordination polymer synthesis. However, employment of multiple V-shaped ligands does not always lead to a helical network. The mutual interplay of two V-shaped ligands, which is neither easily predictable nor well documented, plays a major role directing the self-assembly of the resultant network. We report here the construction of a series of novel coordination polymers {[Ni(OBA)(H2MDP)(H2O)]center dot(DMF)(3)}(n) (1),{[Ni(FBA)(H2MDP)]center dot(H2O)(3)center dot(DMF)\

Copolymerization of aleuritic acid with l-lactic acid and study the aggregation behavior in different solvents - Pandey, Asutosh K.; Garnaik, Baijayantimala (International Journal of Research in Pharmacy and Chemistry, 2013)
In this present work, we highlight the copolymerization of L-lactic acid (L-LA with protected aleuritic acid in presence of Lewis acid catalyst using dehyropolycondensation method. The resulted copolymers are pliable, soft, waxy or even viscous liquid copolymers influenced by the aleuritic acid content. The purpose of this study is to investigate the physical properties. In addition, deprotected copolymers focus micelle-like aggregates in various organic solvents and mixed organic solvent at various proportions.

Correlation of hydrogen-bonding propensity and anticancer profile of tetrazole-tethered combretastatin analogues - Jedhe, Ganesh S.; Paul, Debasish; Gonnade, Rajesh G.; Santra, Manas K.; Hamel, Ernest; Tam Luong Nguyen; Sanjayan, Gangadhar J. (Bioorganic & Medicinal Chemistry Letters, 2013)
A series of 1,5-disubstituted tetrazole-tethered combretastatin analogues with extended hydrogen-bond donors at the ortho-positions of the aryl A and B rings were developed and evaluated for their antitubulin and antiproliferative activity. We wanted to test whether intramolecular hydrogen-bonding used as a conformational locking element in these analogues would improve their activity. The correlation of crystal structures with the antitubulin and antiproliferative profiles of the modified analogues suggested that hydrogen-bond-mediated conformational control of the A ring is deleterious to the bioactivity. In contrast, although there was no clear evidence that intramolecular hydrogen bonding to the B ring enhanced activity, we found that increased substitution on the B ring had a positive effect on antitubulin and antiproliferative activity. Among the various analogues synthesized, compounds 5d and 5e, having hydrogen-bonding donor groups at the ortho and meta-positions on the 4-methoxy phenyl B ring, are strong inhibitors of tubulin polymerization and antiproliferative agents having IC50 value in micromolar concentrations. (C) 2013 Elsevier Ltd. All rights reserved.
Keywords: Colchicine; Combretastatin; Crystal; Tetrazole; Tubulin

Crystal structure and fluorescence analysis of alkaline thermostable xylanase from bacillus sp (NCL 87-6-10) - Satyanarayana, L.; Gaikwad, Sushama M.; Balkrishnan, H.; Suresh, C. G. (Protein and Peptide Letters, 2013)
Structural information deduced from the new crystal form of xylanase from Bacillus sp (NCL 87-6-10) (ATBXYL-C) helped us to identify the active site and interpret the stability of the enzyme. The analysis of the tetragonal crystal structure of ATBXYL-C with a bound and cleaved xylotriose revealed the two glutamic acid residues in the structure that could act as nucleophile (Glu94) and base (Glu184) in the enzyme activity and also the tryptophan residues interacting with the substrate. The cleavage of xylotriose in the crystal showed xylobiose to be the major product. Intrinsic fluorescence of the enzyme showed the presence of tryptophans in partially exposed to the solvent at the active site and surface tryptophans in electropositive environment. The titration experiments with xylobiose and xylotriose revealed slightly enhanced preference for longer chain X3 compared with X2. The crystal structure also account for some of the factors, such as increased number of ionic interactions and additional interactions at the N-terminus, which contributed to increased alkalophilicity and thermostability of the enzyme.
Keywords: active site residues; Alkaline thermophile Bacillus xylanase (ATBXYL-C); fluorescence studies; three-dimensional structure

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 - Roy, Kanak; Vinod, C. P.; Gopinath, Chinnakonda S. (Journal of Physical Chemistry C, 2013)
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.

Designing a thiol specific fluorescent probe for possible use as a reagent for intracellular detection and estimation in blood serum: kinetic analysis to probe the role of intramolecular hydrogen bonding - Das, Priyadip; Mandal, Amal Kumar; Reddy, Upendar G.; Baidya, Mithu; Ghosh, Sudip K.; Das, Amitava (Organic & Biomolecular Chemistry, 2013)
A new and simple chemodosimetric probe L-1 is utilized for the selective detection of biothiols in the presence of other relevant amino acids under physiological conditions (pH = 7.4). This eventually led to a turn-off luminescence response due to an effective photoinduced electron transfer based signaling mechanism. A comparison of the results of the fluorescence kinetic analysis and H-1 NMR studies of the reaction between thiol and L-1 or the analogous compound L-2 revealed the role of intramolecular hydrogen bonding in activating the imine functionality towards nucleophilic addition. Such an example is not common in contemporary literature. Conventional MTT assay studies revealed that this probe (L-1) has low cytotoxicity. Results of the cell imaging studies revealed that this probe was cell membrane permeable and could detect the intracellular distribution of biothiols within living HeLa cells. Furthermore, our studies with human blood plasma demonstrated the possibility of using this reagent for the quantitative optical detection of total biothiols in biological fluid. Such an example for the detection of biothiols in real biological samples is rare in the contemporary literature. These results clearly demonstrate the possibility of using this reagent in medicinal biology and diagnostic applications.

Detection and knockdown of MicroRNA-34a using thioacetamido nucleic acid - Soni, Kartik; Gupta, Shivani; Gokhale, Sachin S.; Dey, Rakesh; Gunjal, Anita D.; Kumar, Vaijayanti A.; Pillai, Beena (Nucleic Acid Therapeutics, 2013)
Thioacetamido nucleic acids (TANA) contain a backbone modification of dinucleotides consisting of a 5-atom amide linker N3'-COCH2-S-CH2 at thymidine or thymidine-cytidine dimer blocks. Here, the chemical synthesis of the TANA linked 5-methyl-cytidine-cytidine ((Me)cc) dimer block and its incorporation into the DNA sequence, complementary to human microRNA 34 (miR-34) is described. Further, for the first time, we demonstrate the biological applications of TANA modified oligonucleotides in detection and intracellular knockdown of a cancer related microRNA in comparison with DNA containing locked nucleic acid (LNA) and 2'-O-methyl modifications. The human microRNA miR-34 is a pro-apoptotic microRNA under the transcriptional control of protein 53 (p53). It gets expressed in response to DNA damage and regulates several cell cycle and apoptosis related targets. Here, we show that the TANA modified antisense oligonucleotide binds specifically to miR-34a, allowing its detection using primer extension. We also show that, using the TANA modified antisense oligonucleotide against miR-34a, intracellular levels of miR-34 can be reduced, and consequently, the expression of its target oncogene V-myc myelocytomatosis viral related oncogene, neuroblastoma derived (MYCN) is enhanced. Further, we assessed the toxicity and serum stability of the oligonucleotide to conclude that it is suitable for detection and modulation of the vital biomarker and tumor suppressor microRNA.

Development and validation of a sensitive bioanalytical method for the determination of sumatriptan in rat plasma by UPLC-MS - Kumbhar, Amruta B.; Galgatte, Upendra C.; Warkad, Shrikant D.; Santhakumari, B. (International Journal of Pharmacy and Pharmaceutical Sciences, 2013)

Development of a multifunctional catalyst for a ``relay'' reaction - Ganai, Anal Kumar; Shinde, Pravin; Dhar, Basab B.; Sen Gupta, Sayam; Bhagavatula L. V. Prasad (RSC Advances, 2013)
In the area of catalysis, nanoparticles and enzymes are two of the most important systems. By amalgamating the two, we present here proof of the concept that it is possible to prepare a multifunctional catalyst that can carry out a ``relay'' reaction. The catalyst consists of a surface bound enzyme on a metal(core)-silica(shell) nanoparticle architecture. Here the enzyme catalyzes the 1st reaction and the metal nanoparticles act as a catalyst for the 2nd reaction of the product from the 1st reaction. In particular, we have studied the catalytic activity of glucosidase grafted Au@mSiO(2) on 4-nitrophenyl-beta-glucopyranoside, where glucosidase will catalyse the 1st step to generate 4-nitrophenol, which acts as a substrate for the next reduction step which is catalysed by the Au nanoparticles present inside the mesoporous silica shell.

Differential protease activity augments polyphagy in helicoverpa armigera - Chikate, Yojana R.; Tamhane, V. A.; Joshi, Rakesh S.; Gupta, Vidya S.; Giri, Ashok P. (Insect Molecular Biology, 2013)
Helicoverpa armigera (Lepidoptera: Noctuidae) and other polyphagous agricultural pests are extending their plant host range and emerging as serious agents in restraining crop productivity. Dynamic regulation, coupled with a diversity of digestive and detoxifying enzymes, play a crucial role in the adaptation of polyphagous insects. To investigate the functional intricacy of serine proteases in the development and polyphagy of H.armigera, we profiled the expression of eight trypsin-like and four chymotrypsin-like phylogenetically diverse mRNAs from different life stages of H.armigera reared on nutritionally distinct host plants. These analyses revealed diet- and stage-specific protease expression patterns. The trypsins expressed showed structural variations, which might result in differential substrate specificity and interaction with inhibitors. Protease profiles in the presence of inhibitors and their mass spectrometric analyses revealed insight into their differential activity. These findings emphasize the differential expression of serine proteases and their consequences for digestive physiology in promoting polyphagy in H.armigera.
Keywords: adaptation; chymotrypsin; Helicoverpa armigera; polyphagy; Trypsin

Disordered mesoporous V/TiO2 system for ambient oxidation of sulfides to sulfoxides - Negi, Sanjay Singh; Sivaranjani, Kumarsrinivasan; Singh, Anand Pal; Gopinath, Chinnakonda S. (Applied Catalysis A-General, 2013)
High sulfide conversion and predominant sulfoxide yield has been observed with 0.1% vanadium doped disordered mesoporous Ti1-xVxO2 material at ambient and sub ambient temperatures using environmentally green H2O2 oxidant. Ti1-xVxO2 materials were prepared by one-pot solution combustion method in less than 15 min and thoroughly characterized by X-ray diffraction, HRTEM, Raman spectra and other physicochemical techniques. Different sulfides, such as, phenylsulfide, methyl-p-tolylsulfide, ethylsulfide, thioanisole, were converted into the corresponding sulfoxide. Isolated V5+ incorporated in the TiO2 lattice is likely to be the active species for the sulfide oxidation reaction. Catalyst recycling studies indicates the robustness of the catalyst. (c) 2012 Elsevier B.V. All rights reserved.
Keywords: Ambient oxidation; Combustion synthesis; heterogeneous catalysis; Hydrogen peroxide; Mesoporous TiO2; Sulfoxidation; Sulfoxide

Effect of phytase from aspergillus niger on plant growth and mineral assimilation in wheat (Triticum aestivum Linn.) and its potential for use as a soil amendment - Gujar, Pradnya D.; Bhavsar, Kavita P.; Khire, Jayant Malhar (Journal of the Science of Food and Agriculture, 2013)
Background Extensive use of non-replenishable phosphate reserves as phosphate supplements in agriculture and animal feed poses a threat for environmental pollution and necessitated a search for alternative phosphate sources. Unlocking the phytate phosphorus using microbial phytase can provide an ecofriendly solution in agriculture. The aim of the present work was to evaluate the effect of phytase from Aspergillus niger NCIM 563 in degradation of phytate phosphorus to benefit plant nutrition and soil amendment in comparison with chemical fertilizers. Results An enzyme dose of 12 IU was sufficient to hydrolyze phytate and increase assimilation of phosphorus by about 74%. Phytase supplementation leads to increase in shoot:total length ratio by about 200%, indicating its growth-promoting effect. Consistency in phytase-induced growth was reflected at pot and tray levels, wherein shoot:total length ratio was observed to be 2.01 and 2.12 respectively. Mineral assimilation due to phytase was more efficient as compared to chemical fertilizers, thus overcoming the constraints of practicability and economics in the agriculture industry. Phytase was efficient in reducing the phytic acid content of soil by about 30% while simultaneously increasing the phytate phosphate availability by 1.18-fold. Conclusion Phytase from A. niger showed improvement in phytate phosphorus and mineral availability. Besides a plant growth-promoting effect, reduction in use of chemical fertilizers and soil improvement could be achieved simultaneously for maintaining the sustainability of agriculture. (c) 2012 Society of Chemical Industry
Keywords: mineral assimilation; Phytase; phytate degradation; plant growth promotion; soil amendment

Effective fragment potential method in Q-CHEM: a guide for users and developers - Ghosh, Debashree; Kosenkov, Dmytro; Vanovschi, Vitalii; Flick, Joanna; Kaliman, Ilya; Shao, Yihan; Gilbert, Andrew T. B.; Krylov, Anna I.; Slipchenko, Lyudmila V. (Journal of Computational Chemistry, 2013)
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'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'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

Electron rich porous extended framework as a heterogeneous catalyst for Diels-Alder reactions - Gole, Bappaditya; Bar, Arun Kumar; Mallick, Arijit; Banerjee, Rahul; Mukherjee, Partha Sarathi (Chemical Communications, 2013)
An electron rich porous metal-organic framework (MOF) has been synthesized, which acts as an effective heterogeneous catalyst for Diels-Alder reactions through encapsulation of the reactants in confined nano-channels of the framework.

Enhanced electrochromic coloration in Ag nanoparticle decorated WO3 thin films - Kharade, Rohini R.; Mali, Sawanta S.; Patil, Satish P.; Patil, Kashinath R.; Gang, Myong G.; Patil, Pramod S.; Kim, Jin H.; Bhosale, Popatrao N. (Electrochimica Acta, 2013)
WO3/Ag composite thin films were prepared by microwave assisted sol-gel synthesis (MW-SGS) of WO3 followed by vacuum evaporation of Ag nanoparticles and their enhanced electrochromic coloration was investigated. The composition and morphology of WO3 thin films with different thickness of Ag layer obtained by vacuum evaporation were investigated. Distinct plasmon absorption bands of Ag nanoparticle thin films were obtained. The optical band gap energy of WO3/Ag films decreased with increasing the Ag layer thickness. The surface of these films has been examined using X-ray photoelectron spectroscopy (XPS) to gain information about the chemical states of species present at surfaces. Experimental results indicated that the conductivity of the films increased after surface modification by Ag layer. To investigate the origin of enhanced electrochromic absorption in optical properties, working electrode consisting of WO3/Ag thin film was used and observed the optical properties during electrochemical reaction. It was found that composite electrode shows enhancement in electrochromic properties in terms of optical modulation (Delta OD) and coloration efficiency (eta). (C) 2013 Elsevier Ltd. All rights reserved.
Keywords: Ag2WO4; CIE coordinates; Electrochromism; SPR; WO3/Ag composite thin films

Environmentally benign enhanced H-2 production from abundant copious waste H2S using size tuneable cubic bismuth (Bi-0) quantum dots-GeO2 glass photocatalyst under solar light - Apte, Sanjay K.; Garaje, Sunil N.; Naik, Sonali D.; Waichal, Rupali P.; Kale, Bharat B. (Green Chemistry, 2013)
Hydrogen sulfide is a copious gas produced in refineries (15-20%) as well as billions of tons produced as a by-product in alkali industries. Selectively, only 5% has been utilised for the Claus process to produce liquid sulfur and it is also well known for its uneconomical and environmental problems. Here, we have demonstrated a significant green approach for conversion of poisonous H2S into H-2 by stable cubic bismuth (Bi-0) quantum dot-glass nanosystems using solar light as the energy source. Previously, metal oxides and sulfides have been demonstrated as solar light photocatalysts. However, a unique bismuth quantum dot-glass nanosystem has been designed where cubic phase bismuth quantum dots of size 1-2 nm are grown in the germanate glass matrix successfully. The presence of bismuth (Bi-0) was confirmed by XRD, Raman, TEM and X-ray photoelectron spectroscopy (XPS). The glass nanosystem shows quantum confinement with variation of the band gap from 2.95-1.51 eV. Considering the broad absorption from visible to near IR, we used this glass nanosystem as a solar light active photocatalyst and hydrogen production with respect to the quantum confinement of bismuth (Bi-0) quantum dots has been demonstrated for the first time. The photocatalytic activity for hydrogen production using glass nano-systems having bismuth quantum dot sizes of 1-2 nm and 3-6 nm was measured under solar light and prima fascia observations revealed that the glass nanosystems with very small quantum dots (1-2 nm) showed enhanced hydrogen evolution (11 541 mu mol h(-1) g(-1)) from H2S. The hydrogen evolution obtained is much higher than for previously reported visible light active nanostructured sulfide/oxide or embedded glass nanosystems. The glass nanosystems were also used for water splitting and show evolution of hydrogen without any co-catalyst. It is noteworthy that the quantum dot-glass photocatalyst is highly stable and catalyst regeneration is quite easy and fast. Hence, the QD-bismuth-glass nanocomposites have significant advantages over normal nanosized powder catalysts. Such unique glass nanosystems will also have great potential in photonics and optoelectronic applications.

Ester vs. amide on folding: a case study with a 2-residue synthetic peptide - Vijayadas, Kuruppanthara N.; Nair, Roshna V.; Gawade, Rupesh L.; Kotmale, Amol S.; Prabhakaran, Panchami; Gonnade, Rajesh G.; Puranik, Vedavati G.; Rajamohanan, Pattuparambil R.; Sanjayan, Gangadhar J. (Organic & Biomolecular Chemistry, 2013)
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 ``fray apart''. 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.

Evaluation of viability of halogen•••O2N interactions: insight form crystal packing in a series of isomeric halo and nitro substituted triaryl compounds with modular positioning of halogen and NO2 groups - Ramana, Chepuri V.; Goriya, Yogesh; Durugkar, Kulbhushan A.; Chatterjee, Soumitra; Krishnaswamy, Shobhana; Gonnade, Rajesh G. (CrystEngComm, 2013)
A series of isomeric triaryl compounds with a modular positioning of the halogen and NO2 groups have been synthesized by the azide–alkyne “click reaction” and have been characterized by single crystal X-ray structure analysis. This isomeric series has provided an opportunity for understanding the efficiency of the bifurcated halogen⋯NO2 synthon in the organization of the molecules in the crystalline lattice. The changes in molecular conformation, crystal packing and supramolecular aggregation due to the change in the relative positioning of the complementary groups, halogen atom and the NO2 group on ring A and ring C respectively, have been discussed. All the isomers synthesized are crystalline and establish the triazole as a reliable linker for crystal engineering oriented molecular synthesis. The 2-NO2 derivatives display in general, a helical architecture and 3-NO2 derivatives exhibit a centrosymmetric dimeric assembly via the complementary C–H⋯O interactions leading to either a helical or a 2-dimensional sheet pattern. The molecular organization in 4-NO2 derivatives revealed in general a 2D sheet pattern.

Exclusion from hexagonal mesophase surfactant domains drives end-to-end enchainment of rod-like particles - Sharma, Kamendra P.; Ganai, Anal Kumar; Sen, Debasis; Bhagavatula L. V. Prasad; Kumaraswamy, Guruswamy (Journal of Physical Chemistry B, 2013)
Anisotropic rod-like particles assemble end-to-end when the surfactant/water matrix in which they are dispersed is cooled from the isotropic to the lyotropic hexagonal phase. We demonstrate the formation of such end-to-end assemblies for gold nanorods, which are tens of nanometers in size, as well as for micrometer-sized ellipsoidal polystyrene particles. In both cases, the particles are well-dispersed in the low-viscosity surfactant/water phase above the isotropic-H-1 transition temperature. On cooling into the H-1 phase, mesophase domains form and the particles are expelled to the isotropic phase. As the H-1 domains grow and finally impinge, the particles are localized at the domain boundaries where they reorient and assemble end-to-end. Remarkably, we observe the formation of end-to-end assemblies of gold nanorods even for volume fractions as low as 2 x 10(-6) in the initially dispersed state. The extent of particle ``enchainment'' increases with the particle concentration and with the aspect ratio of the particles.

Extended coupled cluster through nth perturbation order for molecular response properties: a comparative study - Gupta, Jitendra; Manohar, Prashant Uday; Ghosh, Aryya; Vaval, Nayana; Pal, Sourav (Chemical Physics, 2013)
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

Ferromagnetism in metal oxide systems: interfaces, dopants, and defects - Thakare, Vishal P.; Game, Onkar S.; Ogale, Satishchandra B. (Journal of Materials Chemistry C, 2013)
Ferromagnetism in metal oxide systems has always attracted scientific attention in view of the intriguing and interesting interplay of spin, charge, orbital and lattice degrees of freedom that such systems display. This trend appears to be continuing with enhanced focus on interface systems, multiferroics, diluted magnetic semiconducting oxides (DMSOs) and nanomaterial magnetism. Newer techniques are being applied to bring out materials issues that are critical to the precise understanding of the origin of magnetism in certain cases. Interest is also beginning to grow in exploring application potential of some such systems. In this article we review the developments in this field by late 2011 and 2012.

First total synthesis of hunanamycin A - Shingare, Rahul D.; Velayudham, R.; Gawade, Jalindar R.; Reddy, D. Srinivasa (Organic Letters, 2013)
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.

Fluorescent sophorolipid molecular assembly and its magnetic nanoparticle loading: a pulsed laser process - Singh, Pradeep Kumar; Mukherji, Ruchira; Joshi-Navare, Kasturi; Banerjee, Abhik; Gokhale, Rohan; Nagane, Satyawan; Prabhune, Asmita; Ogale, Satishchandra (Green Chemistry, 2013)
We report realization of strong green fluorescence in a fully biocompatible highly spherical mesoscale molecular assembly of sophorolipid created by pulsed UV laser processing of a water-based dispersion of sophorolipid. Remarkably, the said fluorescence is totally absent in the original molecule of sophorolipid and is thus the property of the pulsed laser induced modifications in the molecule and the assembly. We have separately examined the consequences of laser irradiation for glucose and oleic acid components which form the sophorolipid. This fluorescence character appears to be driven by the oleic acid component while the assembly process is assisted by the glucose component. Importantly the laser synthesized mesostructures can be easily redispersed in an aqueous medium after being dried and can also be loaded with magnetic nanoparticles (magnetite) for inducing the hyperthermia effect.

Four 3D Cd(II)-based metal organic hybrids with different N,N `-donor spacers: syntheses, characterizations, and selective gas adsorption properties - Bhattacharya, Biswajit; Dey, Rajdip; Pachfule, Pradip; Banerjee, Rahul; Ghoshal, Debajyoti (Crystal Growth & Design, 2013)
{Four new metal organic frameworks with bivalent cadmium, disodium succinate (Na(2)suc), and four different N,N'-donor ligands, i.e., {[Cd(L1)(suc)]center dot(H2O)(3)}(n) (1), {[Cd(L2)(suc)]center dot(H2O)(2)\

Functional and disordered meso-macroporous gamma-Al2-xMxO3 +/- y (M = Cu and/or Ce) - Gnanakumar, Edwin S.; John, Jino C.; Raja, Thirumalaiswamy; Gopinath, Chinnakonda S. (Journal of Nanoscience and Nanotechnology, 2013)
Disordered meso-macro porous Cu-Ce-Al2O3 nanocomposite (gamma-Al2-xMxO3 +/- y, M = Cu and or Ce) with different compositions has been synthesized. In situ templated sol-gel method has been adopted with simple EDTA ethylenediamine tetra aceticacid and ethylenediamine molecules to prepare gamma-Al2-xMxO3 +/- y, (M = Cu and or Ce). Above meso-macro porous materials were characterized by structural, spectroscopy, microscopy and textural techniques. Detailed characterization indicates that Cu2+ ions are introduced into the ceria and alumina lattice positions. Nano composite nature of the gamma-Al2-xMxO3 +/- y has been confirmed by detailed microscopy investigations. Catalytic activity of the above nanocomposite materials have been screened for environmentally important CO oxidation reaction. 30% Ce-60% Al and 10% Cu containing material shows the best activity among other meso-nnacroporous material with (50%) 100% CO oxidation at (107 degrees C) 145 degrees C.
Keywords: Alumina; CO oxidation; heterogeneous catalysis; Meso-Macroporous Material; Nanocomposite; Sol-gel synthesis

Genome-wide identification and characterization of microRNA genes and their targets in flax (Linum usitatissimum) - Barvkar, Vitthal T.; Pardeshi, Varsha C.; Kale, Sandip M.; Qiu, Shuqing; Rollins, Meaghen; Datla, Raju; Gupta, Vidya S.; Kadoo, Narendra Y. (Planta, 2013)
MicroRNAs (miRNAs) are small (20-24 nucleotide long) endogenous regulatory RNAs that play important roles in plant growth and development. They regulate gene expression at the post-transcriptional level by translational repression or target degradation and gene silencing. In this study, we identified 116 conserved miRNAs belonging to 23 families from the flax (Linum usitatissimum L.) genome using a computational approach. The precursor miRNAs varied in length; while most of the mature miRNAs were 21 nucleotide long, intergenic and showed conserved signatures of RNA polymerase II transcripts in their upstream regions. Promoter region analysis of the flax miRNA genes indicated prevalence of MYB transcription factor binding sites. Four miRNA gene clusters containing members of three phylogenetic groups were identified. Further, 142 target genes were predicted for these miRNAs and most of these represent transcriptional regulators. The miRNA encoding genes were expressed in diverse tissues as determined by digital expression analysis as well as real-time PCR. The expression of fourteen miRNAs and nine target genes was independently validated using the quantitative reverse transcription PCR (qRT-PCR). This study suggests that a large number of conserved plant miRNAs are also found in flax and these may play important roles in growth and development of flax.
Keywords: Digital expression analysis; Gene cluster; Linseed; miRNA; MiRNA target transcript; Promoter analysis

Genome-wide identification and characterization of nucleotide binding site leucine-rich repeat genes in linseed reveal distinct patterns of gene structure - Kale, Sandip M.; Pardeshi, Varsha C.; Barvkar, Vitthal T.; Gupta, Vidya S.; Kadoo, Narendra Y. (Genome, 2013)
Plants employ different disease-resistance genes to detect pathogens and to induce defense responses. The largest class of these genes encodes proteins with nucleotide binding site (NBS) and leucine-rich repeat (LRR) domains. To identify the putative NBS-LRR encoding genes from linseed, we analyzed the recently published linseed genome sequence and identified 147 NBS-LRR genes. The NBS domain was used for phylogeny construction and these genes were classified into two well-known families, non-TIR (CNL) and TIR related (TNL), and formed eight clades in the neighbor-joining bootstrap tree. Eight different gene structures were observed among these genes. An unusual domain arrangement was observed in the TNL family members, predominantly in the TNL-5 clade members belonging to class D. About 12% of the genes observed were linseed specific. The study indicated that the linseed genes probably have an ancient origin with few progenitor genes. Quantitative expression analysis of five genes showed inducible expression. The in silico expression evidence was obtained for a few of these genes, and the expression was not correlated with the presence of any particular regulatory element or with unusual domain arrangement in those genes. This study will help in understanding the evolution of these genes, the development of disease resistant varieties, and the mechanism of disease resistance in linseed.
Keywords: Flax; in silico gene expression; motif analysis; NBS-LRR; Phylogenetic analysis; Promoter analysis

Glucose oxidase conjugated H2O2 sensitive CdTe QDs: an effective fluorescence tool for glucose sensing - Singh, Pooja; Prabhune, Asmita; Ogale, Satishchandra B.; Guin, Debanjan (Journal of Materials Chemistry B, 2013)
Water-soluble quantum dots (QDs) are extensively used for molecular sensing because of the flexibility they offer in terms of modification of the QDs surface with a variety of functional groups using thiol chemistry and monitoring by fluorescence intensity. We describe a simple assay that allows the photoluminescence (PL) detection of H2O2 and glucose in aqueous samples and demonstrate its applicability by estimating glucose in blood. To enable the glucose detection, we functionalized the 3-mercaptopropanoic acid (MPA) capped CdTe QDs with glucose oxidase (GOx), the enzyme specific to b-D-glucose, using carbodiimide chemistry. The fluorescence of the GOx-functionalized CdTe QDs was quenched on the interaction with glucose. The same photoluminescence quenching was also observed in gel form, when a GOx modified CdTe QDs loaded agarose gel was dipped in H2O2 and glucose solutions, respectively.

Glycated proteome: from reaction to intervention - Kulkarni, Mahesh J.; Korwar, Arvind M.; Mary, Sheon; Bhonsle, Hemangi S.; Giri, Ashok P. (Proteomics Clinical Applications, 2013)
Glycation, a nonenzymatic reaction between reducing sugars and proteins, is a proteome wide phenomenon, predominantly observed in diabetes due to hyperglycemia. Glycated proteome of plasma, kidney, lens, and brain are implicated in the pathogenesis of various diseases, including diabetic complications, neurodegenerative diseases, cancer, and aging. This review discusses the strategies to characterize protein glycation, its functional implications in different diseases, and intervention strategies to protect the deleterious effects of protein glycation.
Keywords: aging; Diabetes; Glycation; RAGE

High-resolution outgoing longwave radiation dataset from Kalpana-1 satellite during 2004-2012 - Mahakur, M.; Prabhu, A.; Sharma, A. K.; Rao, V. R.; Senroy, S.; Singh, Randhir; Goswami, B. N. (Current Science, 2013)
Long record of high-resolution quality-controlled outgoing longwave radiation (OLR) from geostationary platforms like Kalpana-1 has the potential not only to provide detailed information of cloud types contributing to the measure of rain, but also helps unravel convective cloud organization in the tropics from small scale to meso- and synoptic scales. A research quality product of three hourly OLR for the period May 2004 June 2012 is produced from Kalpana-1 very high resolution radiometer (VHRR) radiances over the Indian region (40 degrees S-40 degrees N, 25-125 degrees E) in a regular grid of 0.25 x 0.25 degrees. The quality and usefulness of the dataset is demonstrated here using some illustrative examples. Although these data are available for a relatively short-period, it is shown that they will be potentially more useful than the widely used OLR from NOAA satellites in representing the annual cycles, particularly over the desert and humid oceans, due to their frequent sampling and quality. The active-break periods in the Indian summer monsoon picked up by both the OLR match well. This three hourly OLR estimated from Kalpana-1 VHRR is able to describe the fine-scale structure of the diurnal variation over the region.
Keywords: Active break periods; diurnal variation; geostationary platforms; outgoing longwave radiation

Human mitochondrial NDUFS3 protein bearing leigh syndrome mutation is more prone to aggregation than its wild-type - Jaokar, Tulika M.; Patil, Deepak P.; Shouche, Yogesh S.; Gaikwad, Sushama M.; Suresh, C. G. (Biochimie, 2013)
NDUFS3 is an integral subunit of the Q module of the mitochondrial respiratory Complex-I. The combined mutation (T145I + R199W) in the subunit is reported to cause optic atrophy and Leigh syndrome accompanied by severe Complex-I deficiency. In the present study, we have cloned and overexpressed the human NDUFS3 subunit and its double mutant in a soluble form in Escherichia coli. The wild-type (w-t) and mutant proteins were purified to homogeneity through a serial two-step chromatographic purification procedure of anion exchange followed by size exclusion chromatography. The integrity and purity of the purified proteins was confirmed by Western blot analysis and MALDI-TOF/TOF. The conformational transitions of the purified subunits were studied through steady state as well as time resolved fluorescence and CD spectroscopy under various denaturing conditions. The mutant protein showed altered polarity around tryptophan residues, changed quenching parameters and also noticeably altered secondary and tertiary structure compared to the w-t protein. Mutant also exhibited a higher tendency than the w-t protein for aggregation which was examined using fluorescent (Thioflavin-T) and spectroscopic (Congo red) dye binding techniques. The pH stability of the w-t and mutant proteins varied at extreme acidic pH and the molten globule like structure of w-t at pH1 was absent in case of the mutant protein. Both the w-t and mutant proteins showed multi-step thermal and Gdn-HCI induced unfolding. Thus, the results provide insight into the alterations of NDUFS3 protein structure caused by the mutations, affecting the overall integrity of the protein and finally leading to disruption of Complex-I assembly. (C) 2013 Elsevier Masson SAS. All rights reserved.
Keywords: Aggregation Fluorescence lifetime; Complex-I; Leigh syndrome; NDUFS3

Hydrolytic conversion of a metal-organic polyhedron into a metal-organic framework - Mallick, Arijit; Garai, Bikash; Diaz, David Diaz; Banerjee, Rahul (Angewandte Chemie-International Edition, 2013)
Keywords: cage compounds; crystal engineering; hydrophobic effect; metal-organic frameworks; Self-assembly

Hydrophobic and hydrophilic balance and its effect on mesophase behaviour in hydroxyalkyl ethers of methyl glucopyranoside - Singh, Madan K.; Xu, Rui; Moebs, Sylvie; Kumar, Anil; Queneau, Yves; Cowling, Stephen J.; Goodby, John W. (Chemistry-A European Journal, 2013)
Four series of monosubstituted methyl -D-glucopyranoside hydroxyalkyl ethers were prepared and their thermotropic and lyotropic self-organising properties were investigated in terms of the hydrophobichydrophilic balance with respect to their molecular structures. The results obtained lead us to a new understanding of the forces that drive the formation of condensed soft-matter phases.
Keywords: carbohydrates; liquid crystals; mesophases; Self-assembly; soft matter

Hydroxyapatite supported palladium catalysts for suzuki-miyaura cross-coupling reaction in aqueous medium - Indra, Arindam; Gopinath, Chinnakonda S.; Bhaduri, Sumit; Lahiri, Goutam Kumar (Catalysis Science & Technology, 2013)
Supported palladium catalyst 1 has been prepared by the immobilisation of [Pd(COD)Cl-2] (COD = 1,5-cyclooctadiene) on hydroxyapatite. Catalyst 2 has been prepared by subsequent reduction of catalyst 1 with sodium borohydride in ethanol. Under similar reaction conditions, catalyst 1 with Pd2+, is found to be almost five times more active than 2. Using 1 as the catalyst and water as the solvent, reaction conditions for Suzuki-Miyaura cross-coupling reactions have been optimised under aerobic conditions. The best catalytic activities are observed in the presence of potassium carbonate as the base and tetrabutylammonium bromide as a promoter. Catalyst 1 has been tested for catalytic cross-coupling reactions with sixteen different, electronically neutral, electron rich, electron poor and sterically hindered aryl boronic acids, and several different aryl halides including aryl chlorides. More than thousand turnovers and high selectivities to the hetero-coupled products have been observed in most cases. For many substrates the turnovers with 1 are notably more than what has been reported with other supported catalysts in water. The recyclability and scale-up potential of catalyst 1 have been tested and found to be satisfactory. A negligible drop in activity is observed over ten recycles with an accumulated turnover number of similar to 30000.

Identification of molecular crystals capable of undergoing an acyl-transfer reaction based on intermolecular interactions in the crystal lattice - Tamboli, Majid I.; Krishnaswamy, Shobhana; Gonnade, Rajesh G.; Shashidhar, Mysore S. (Chemistry-A European Journal, 2013)
Investigation of the intermolecular acyl-transfer reactivity in molecular crystals of myo-inositol orthoester derivatives and its correlation with crystal structures enabled us to identify the essential parameters to support efficient acyl-transfer reactions in crystals: 1)the favorable geometry of the nucleophile (OH) and the electrophile (CO) and 2)the molecular assembly, reinforced by CH interactions, which supports a domino-type reaction in crystals. These parameters were used to identify another reactive crystal through a data-mining study of the Cambridge Structural Database. A 2:1 co-crystal of 2,3-naphthalene diol and its di-p-methylbenzoate was selected as a potentially reactive crystal and its reactivity was tested by heating the co-crystals in the presence of solid sodium carbonate. A facile intermolecular p-toluoyl group transfer was observed as predicted. The successful identification of reactive crystals opens up a new method for the detection of molecular crystals capable of exhibiting acyl-transfer reactivity.
Keywords: Acylation; domino reactions; intermolecular interactions; solid-state reactions; X-ray diffraction

Interatomic coulombic decay in (HF)n,(n=2-3) clusters using CAP/EOM-CCSD method - Ghosh, Aryya; Pal, Sourav; Vaval, Nayana (Molecular Physics, 2013)
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)

Interfacial charge recombination of Os(II)-polypyridyl-resorcinol complex on oleic acid capped TiO2 surface: what determines the dynamics? - Banerjee, Tanmay; Das, Amitava; Ghosh, Hirendra N. (New Journal of Chemistry, 2013)
Femtosecond transient absorption spectroscopic studies of an osmium(II)-polypyridyl-resorcinol complex, 1, on oleic acid capped TiO2 have been carried out and the results have been compared with our previous studies on poly(vinyl) alcohol capped TiO2. While on both these surfaces the complex exhibits a single exponential <120 fs injection, the back electron transfer reaction is slower on the oleic acid capped TiO2 surface early on while it is faster on the same surface at longer times than on poly(vinyl)alcohol capped TiO2. The probable origin of these disparate observations has been analyzed.

Kinetics and thermodynamics of glycans and glycoproteins binding to holothuria scabra lectin: a fluorescence and surface plasmon resonance spectroscopic study - Gowda, Nagaraj M.; Gaikwad, Sushama M.; Khan, Mohammad Islam (Journal of Fluorescence, 2013)
Holothuria scabra produces a monomeric lectin (HSL) of 182 kDa. HSL showed strong antibacterial activity and induced bacterial agglutination under in vitro conditions, indicating its role in animals' innate immune responses. Very few lectins have been reported from echinoderms and none of these lectins have been explored in detail for their sugar-binding kinetics. Affinity, kinetics and thermodynamic analysis of glycans and glycoproteins binding to HSL were studied by fluorescence and surface plasmon resonance spectroscopy. Lectin binds with higher affinity to O-linked than N-linked asialo glycans, and the affinities were relatively higher than that for sialated glycans and glycoproteins. T-antigen alpha-methyl glycoside was the most potent ligand having the highest affinity (Ka 8.32 x10(7) M-1). Thermodynamic and kinetic analysis indicated that the binding of galactosyl Tn-antigen and asialo glycans is accompanied by an enthalpic contribution in addition to higher association rate coupled by low activation energy for the association process. Presence of sialic acid or protein matrix inhibits binding. Higher affinity of HSL for O-glycans than N-glycans had biological implications; since HSL specifically recognizes bacteria, which have mucin or O-glycan cognate on their cell surfaces and play a major role in animal innate immunity. Since, HSL had higher affinity to T-antigen, makes it a useful tool for cancer diagnostic purpose.
Keywords: Holothuria scabra; Kinetic analysis; Lectin; Surface plasmon resonance spectroscopy; Thermodynamic properties

Lagrange multiplier approach for excited state properties through intermediate hamiltonian formulation of fock space multireference coupled-cluster theory - Gupta, Jitendra; Vaval, Nayana; Pal, Sourav (Journal of Chemical Physics, 2013)
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.

Large centimeter-sized macroporous ferritin gels as versatile nanoreactors - Kumari, Sushma; Kulkarni, Amol; Kumaraswamy, Guruswamy; Sen Gupta, Sayam (Chemistry of Materials, 2013)
Organized assemblies of bionanoparticles such as ferritin provides templates that can be exploited for nanotechnological applications. Organization of ferritin into well-defined three-dimensional assemblies is challenging and has attracted considerable attention recently. We have synthesized, for the first time, large (centimeter-sized) self-standing macroporous scaffold monoliths from ferritin bionanoparticles, using dynamic templating of surfactant H-1 domains. These scaffolds comprise three-dimensionally connected strands of ferritin, organized as a porous gel with porosity similar to 55 mu m. The iron oxide inside the ferritin scaffold can be easily replaced with catalytically active monodisperse zerovalent transition metal nanoparticles using a very simple protocol. Since the ferritin is cross-linked in the scaffold, it is significantly robust with enhanced thermal stability and better tolerance toward several organic solvents in Comparison to the native ferritin bionanoparticle. In addition, the scaffold macropores facilitate substrate and reagent transport and hence the monoliths containing active Pd or iron oxide nanoparticles inside apo-ferritin bionanoparticles were used as a recyclable heterogeneous catalyst for the oxidation of 2,3,6-trimethyl phenol to 2,3,6-trimethyl-1,4-benzoquinone (precursor for Vitamin E synthesis) and for Suzuki-Miyaura cross-coupling reaction in both aqueous and organic solvents. The protein shell around the nanoparticles protects them from agglomeration, a phenomenon that otherwise plagues nanoparticles-based catalysis. The presence of macropores allow the ferritin scaffold to act as catalytic monolith for continuous flow reactions having rapid reaction rates, while offering a low pressure drop. Finally, the Pd@apo-ferritin scaffold was immobilized inside a steel cartridge and used for the continuous flow hydrogenation of alkenes to their corresponding alkanes for 15 cycles without any loss of activity.
Keywords: catalysis; continuous flow; ferritin; gel; macroporous materials; Self-assembly

Magnetically separable single-site Ti-Fe3O4@MCM-41 catalyst for selective epoxidation of olefins - Jha, Ajay; Patil, Chetana R.; Garade, Ajit C.; Rode, Chandrashekhar V. (Industrial & Engineering Chemistry Research, 2013)
Magnetically separable Ti-Fe3O4@MCM-41 (Ti-MS) catalysts were prepared by postgrafting Ti with varying loading on mesoporous silica containing dispersed magnetite. The hexagonal structure of Ti-MS catalysts with a periodicity in the pores and a highly ordered hexagonal matrix was established by X-ray diffraction and transmission electron microscopy, while diffuse reflectance UV showed the isolated tetrahedral Ti species coordinated with O2-. From the Fourier transform infrared studies, the extent of Ti-O-Si linkage was found to increase with increase in Ti-loading from 1 to 5 wt %beyond which (10%), the intensity of Ti-O-Si band decreased due to the polymerization of the Ti on the silica surface. Silanol groups on the surface of silica interact with the precursor Ti((OPr)-Pr-i)(4) to give site isolated tetrahedral Ti-species responsible for complete selectivity to the epoxide in the epoxidation of cyclooctene. The magnetic property facilitated easy recovery of the catalyst for its successful eight recycles showing its stability under reaction conditions.

Metal cation-exchanged montmorillonite clay as catalysts for hydroxyalkylation reaction - Jha, Ajay; Garade, Ajit C.; Shirai, M.; Rode, C. V. (Applied Clay Science, 2013)
Several solid acid catalysts were prepared by exchanging metal cations such as Zn2+, Fe3+ and Al3+ with montmorillonite clay. Among these, Al-montmorillonite showed the highest acidity determined by the pyridine-IR as well as NH3-TPD methods. A systematic comparison of the performance of these catalysts along with parent montmorillonite was carried out for the hydroxyalkylation of p-cresol with formaldehyde to give 2, 2'-methylenebis (4-methyl phenol) (DAM). It was found that the activity of these catalysts was in accordance with the increase in acidity of parent montmorillonite after the exchange of cations in the order of Zn2+, Fe3+ and Al3+. The selectivity pattern was also influenced by the exchanged cations. Since Al-montmorillonite showed the highest conversion of 51% with 98% selectivity to DAM, the effects of various reaction parameters, namely, mole ratio, catalyst concentration, temperature, reaction time on conversion and selectivity pattern were also studied using the same catalyst This catalyst also showed an excellent stability as evidenced by its eight times reuse. (C) 2012 Published by Elsevier B.V.
Keywords: Cations-exchanged clay; Montmorillonite; NH3-TPD; Pyridine-IR

Metal or nonmetal cooperation with a phenyl group: route to catalysis? a computational investigation - Ghatak, Kamalika; Mane, Manoj; Vanka, Kumar (ACS Catalysis, 2013)
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

MgCl2 center dot 6CH(3)OH: a simple molecular adduct and its influence as a porous support for olefin polymerization - Gnanakumar, Edwin S.; Gowda, Ravikumar R.; Kunjir, Shrikant; Ajithkumar, Thalasseril G.; Rajamohanan, P. R.; Chakraborty, Debashis; Gopinath, Chinnakonda S. (ACS Catalysis, 2013)
A single phase molecular adduct, MgCl2 center dot 6CH(3)OH has been synthesized using MgCl2 and the simplest alcohol, methanol. Structural, spectroscopic, and morphological studies have been carried out for a better understanding of the single phase MgCl2 center dot 6CH(3)OH adduct. C-13 CPMAS solid state NMR studies show all six methanol molecules are magnetically equivalent and present in a single environment around the Mg2+ center. Raman spectral analysis of the characteristic peak at 708 cm(-1) substantiates octahedral coordination of six CH3OH molecules around Mg2+. Solid state C-13 NMR measurements, made after heat treatment at different temperatures, have been utilized to understand the variations in CH3OH stoichiometry and coordination around Mg2+ with temperature. A titanated active catalyst, TiCl4 on MgCl2 center dot 6CH(3)OH, has also been synthesized and subjected to detailed characterizations. The active catalyst shows high surface area (102 m(2)/g) and mesoporosity. The titanated catalyst has been screened for ethylene polymerization reactions using different cocatalysts (R3Al; R= -CH3, -CH2CH3, and -CH2CH(CH3)(2)). A total of 7.25 kg of polyethylene per gram of catalyst has been obtained with Me3Al cocatalyst, which is six times higher in activity compared with commercial Me3Al/TiCl4/MgCl2 center dot 6EtOH-supported orted catalystAlthough porosity influences the catalytic activity, other factors also seem to contribute to the total catalytic activity.
Keywords: heterogeneous catalysis; MgCl2; Molecular adduct; olefin polymerization; Ziegler-Natta catalyst

Molecular insights into resistance mechanisms of lepidopteran insect pests against toxicants - Dawkar, Vishal V.; Chikate, Yojana R.; Lomate, Purushottam R.; Dholakia, Bhushan B.; Gupta, Vidya S.; Giri, Ashok P. (Journal of Proteome Research, 2013)
Insect pests remain a major reason for crop loss worldwide despite extensive use of chemical insecticides. More than B 50% of all insecticides are organophosphates, followed by synthetic pyrethroids, organochlorines, carbamates, and biopesticides, and their continued use may have many environmental, agricultural, medical, and socioeconomic issues. Importantly, only a countable number of insects have acquired the status of crop pests, mostly due to monoculture of crop plants and polyphagous nature of the insects. We focus on A adaptations of Lepidopteran insects to phytochemicals and synthetic pesticides in native and modern agricultural systems. Because of heavy use of chemical insecticides, a strong selection pressure is imposed on insect populations, resulting in the emergence of resistance against candidate compound(s). Current knowledge suggests that insects generally implement a three-tier system to overcome the effect of toxic compounds at physiological, biochemical, and genetic levels. Furthermore, we have discussed whether the adaptation to phytochemicals provides an advantage to the insect while encountering synthetic insecticide molecules. Specific metabolic pathways employed by insects to convert deterrents into less toxic forms or their removal from the system are highlighted. Using the proteomics approach, insect proteins interacting with insecticides can be identified, and their modification in resistant insects can be characterized. Also, systems biology studies can offer useful cues to decipher the molecular networks participating in the metabolism of detrimental compounds.
Keywords: field crops; insect-pests; insecticide; Lepidoptera; proteomics; resistance mechanisms

Molecular interactions, proton exchange, and photoinduced processes prompted by an inclusion process and a [2]pseudorotaxane formation - Mandal, Amal Kumar; Suresh, Moorthy; Kesharwani, Manoj K.; Gangopadhyay, Monalisa; Agrawal, Manoj; Boricha, Vinod P.; Ganguly, Bishwajit; Das, Amitava (Journal of Organic Chemistry, 2013)
Appropriate design of the host and guest components allows formation of a novel [2]pseudorotaxane complex with an interrupted photoinduced electron transfer (PET)-coupled fluorescence resonance energy transfer (FRET) response. This is the first example of an inclusion complex with NO6-based azacrown ether as the host unit (H). Different guest molecules (G1, G2, G3, and G4) with varying stopper size are used for the studies. Unlike G1, G2, and G3, G4 with a relatively bulkier stopper fails to form a [2]pseudorotaxane complex. Isothermal titration microcaloiimetry measurements reveal a systematic increase in the association constant for H.G1, H.G2, and H.G3 with a change in the stopper size. Thermodynamic data suggest that the formation of H.G1/H.G2/H.G3 is exclusively driven by a large positive entropic gain (T Delta S = 19.69/26.80/21.81 kJ.mol(-1)), while the enthalpy change is slightly negative for H.G1/H.G3 (-2.61/-1.97 kJ.mol(-1)) and slightly positive for H.G2 (Delta H = 5.98 kJ.mol(-1)). For these three inclusion complexes, an interrupted PET-coupled FRET response is observed with varying efficiency, which is attributed to the subtle differences in acidity of the NH2+ unit of the guest molecules and thus the proton exchange ability between the host and respective guest. This is substantiated by the results of the computational studies.

Molecular mapping of leaf rust resistance gene Lr15 in hexaploid wheat - Dholakia, Bhushan B.; Rajwade, A. V.; Hosmani, P.; Khan, R. R.; Chavan, S.; Reddy, D. M. R.; Lagu, Meena D.; Bansal, Urmil K.; Saini, R. G.; Gupta, V. S. (Molecular Breeding, 2013)
Leaf rust is a widespread and commonly occurring rust disease of wheat. Genetic resistance is the most economical method of reducing losses due to leaf rust. Lr15 has been shown to be present on wheat chromosome 2D and is reported to be a seedling resistance gene. However, tightly linked markers associated with Lr15 have not been reported to date. To identify molecular markers linked to Lr15, an F-2 mapping population of Thatcher x Thatcher-Lr15 was generated. Available wheat simple sequence repeat markers were utilized in parental screening and polymorphic markers were used to analyze the entire population of 221 plants. Phenotypic evaluations of the F-2-derived F-3 progenies with Puccinia triticina Eriks. pathotype 162A (93R15) confirmed the monogenic inheritance of Lr15. The linkage group representing chromosome 2DS was constructed at LOD 4.0 which revealed the closest flanking markers Xgwm4562 and Xgwm102 at a distance of 3.1 and 9.3 cM, respectively. Furthermore, utilization of these flanking markers in combination has successfully identified wheat lines with or without Lr15. These markers could potentially be useful in gene pyramiding with other genes to enhance rust resistance in wheat.
Keywords: Disease resistance; Leaf rust; Marker-assisted selection; Simple sequence repeat; Wheat

Multicomponent reactions involving arynes, quinolines, and aldehydes - Bhunia, Anup; Porwal, Digvijay; Gonnade, Rajesh G.; Biju, Akkattu T. (Organic Letters, 2013)
The multicomponent reaction involving arynes, quinolines, and aldehydes leading to the diastereoselective synthesis of benzoxazino quinoline derivatives in good yields proceeding via 1,4-zwitterionic intermediates is reported. In addition, the synthetic potential of various carbonyl compounds in this reaction as well as the utility of isoquinoline as the nucleophilic trigger has been examined.

New chemodosimetric probe for the specific detection of Hg2+ in physiological condition and its utilisation for cell imaging studies - Saha, Sukdeb; Agarwalla, Hridesh; Gupta, Hariom; Baidya, Mithu; Suresh, E.; Ghosh, Sudip K.; Das, Amitava (Dalton Transactions, 2013)
A dithiane derivative of BODIPY is synthesized. This new reagent could be used for the specific and instantaneous detection of Hg2+ in physiological condition. This dithiane reagent reacts specifically with Hg2+ to regenerate the parent BODIPY-aldehyde with consequential change in visually detectable optical responses and this provides the possibility of using this reagent as a colorimetric probe or as a fluorescent biomarker/imaging reagent. Further, non-covalent interactions could be utilized for formation of an inclusion complex with biologically benign beta-cyclodextrin for enhancing its solubility in aqueous environment and this included adduct could be used as a fluorescent marker and imaging reagent for Hg2+. Uptake of Hg2+ ions in live HeLa cells, exposed to a solution having Hg2+ ion concentration as low as 2 ppb, could also be detected by confocal laser microscopic studies.

New receptor with a FRET based fluorescence response for selective recognition of fumaric and maleic acids in aqueous medium - Reddy, Upendar G.; Lo, Rabindranath; Roy, Sovan; Banerjee, Tanmay; Ganguly, Bishwajit; Das, Amitava (Chemical Communications, 2013)
Preferential binding of a new reagent to fumaric acid could be utilized for its estimation in aqueous medium and in commercial fruit juice.

Newly designed resorcinolate binding for Ru(II)- and Re(I)- polypyridyl complexes on oleic acid capped tio2 in non-aqueous solvent: prolonged charge separation and substantial thermalized 3MLCT injection - Banerjee, Tanmay; Kaniyankandy, Sreejith; Das, Amitava; Ghosh, Hirendra Nath (Journal of Physical Chemistry C, 2013)
Femtosecond pump–probe spectroscopic studies on a series of newly synthesized resorcinol-based Ru(II) and Re(I) complexes on oleic acid capped TiO2 nanoparticles have been carried out in chloroform, and the results are compared with those of the catechol analogues. The ruthenium complex shows biexponential injection; the second component arises due to injection from the thermally equilibrated 3MLCT states as a result of a weaker strength of the resorcinolate binding. Also, in comparison with catechol binding, as a result of a greater diffusion of the injected electrons into TiO2, the back electron transfer (BET) is slowed down significantly for the ruthenium complex. These are distinctive observations for any mononuclear ruthenium–polypyridyl–enediol complex reported thus far. However, the rhenium complex educes single exponential ultrafast injection (<120 fs) because of apparent injection in a high density of states and shows the most prominent results with ∼50% slowdown in the charge recombination rate as compared to the analogous catechol bound system. These results exemplify the probable development of highly capable sensitizer dyes with resorcinol as the anchoring group for the development of efficient dye-sensitized solar cells.

Novel, band-controlled metal oxide compositions for semiconductor-mediated photocatalytic splitting of water to produce H-2 - Gupta, Narendra M. (57th DAE Solid State Physics Symposium, 2013)

One pot solvent free synthesis and in vitro antitubercular screening of 3-aracylphthalides against mycobacterium tuberculosis - Limaye, Rohan A.; Kumbhar, Virendra B.; Natu, Arun D.; Paradkar, Madhusudan V.; Honmore, Varsha S.; Chauhan, Rubia R.; Gample, Suvarna P.; Sarkar, Dhiman (Bioorganic & Medicinal Chemistry Letters, 2013)
One pot synthesis of 3-Aracylphthalide was accomplished in good yield by reacting 2-carboxy benzaldehyde with various aromatic methyl ketones in presence of methane sulphonic acid. Various phthalides thus obtained were characterized with spectral techniques. These phthalides were subjected to in vitro antitubercular screening against Mycobacterium tuberculosis H37Ra (MTB) by using XRMA protocol. Among the phthalides screened, four exhibited half maximal inhibitory concentration (IC50) in the range of 0.81-1.24 mu g/ml thereby providing potential lead compounds for future drug discovery studies. (c) 2012 Elsevier Ltd. All rights reserved.
Keywords: 3-Aracylphthalide; Antitubercular activity; Methane sulphonic acid; One pot synthesis

One size does not fit all: on how markov model order dictates performance of genomic sequence analyses - Narlikar, Leelavati; Mehta, Nidhi; Galande, Sanjeev; Arjunwadkar, Mihir (Nucleic Acids Research, 2013)
The structural simplicity and ability to capture serial correlations make Markov models a popular modeling choice in several genomic analyses, such as identification of motifs, genes and regulatory elements. A critical, yet relatively unexplored, issue is the determination of the order of the Markov model. Most biological applications use a predetermined order for all data sets indiscriminately. Here, we show the vast variation in the performance of such applications with the order. To identify the `optimal' order, we investigated two model selection criteria: Akaike information criterion and Bayesian information criterion (BIC). The BIC optimal order delivers the best performance for mammalian phylogeny reconstruction and motif discovery. Importantly, this order is different from orders typically used by many tools, suggesting that a simple additional step determining this order can significantly improve results. Further, we describe a novel classification approach based on BIC optimal Markov models to predict functionality of tissue-specific promoters. Our classifier discriminates between promoters active across 12 different tissues with remarkable accuracy, yielding 3 times the precision expected by chance. Application to the metagenomics problem of identifying the taxum from a short DNA fragment yields accuracies at least as high as the more complex mainstream methodologies, while retaining conceptual and computational simplicity.

One-step method for the synthesis of aryl olefins from aryl aldehydes and aliphatic aldehydes - Borate, Hanumant B.; Gaikwad, Supriya H.; Kudale, Ananada S.; Chavan, Subhash P.; Pharande, Shrikant G.; Wagh, Vitthal D.; Sawant, Vikram S. (Tetrahedron Letters, 2013)
A conceptually new one-step reaction affording unexpected aryl olefinic product from aromatic aldehyde, aliphatic aldehyde and malononitrile in the presence of acetic acid-ammonium acetate under mild reaction conditions without using any metal catalyst is reported. This novel reaction was used to prepare a number of substituted aryl olefins including new molecules. (c) 2013 Elsevier Ltd. All rights reserved.
Keywords: Aliphatic aldehyde; Aromatic aldehyde; Aryl olefin; Dicyanoaniline; Malononitrile

Orthanilic acid-promoted reverse turn formation in peptides - Kale, Sangram S.; Priya, Gowri; Kotmale, Amol S.; Gawade, Rupesh L.; Puranik, Vedavati G.; Rajamohanan, P. R.; Sanjayan, Gangadhar J. (Chemical Communications, 2013)
Orthanilic acid (2-aminobenzenesulfonic acid, (S)Ant), an aromatic beta-amino acid, has been shown to be highly useful in inducing a folded conformation in peptides. When incorporated into peptide sequences (Xaa-(S)Ant-Yaa), this rigid aromatic beta-amino acid strongly imparts a reverse-turn conformation to the peptide backbone, featuring robust 11-membered-ring hydrogen-bonding.

Oxidoreductase from `Alphonso' mango catalyzing biosynthesis of furaneol and reduction of reactive carbonyls - Kulkarni, Ram; Chidley, Hemangi G.; Deshpande, Ashish; Schmidt, Axel; Pujari, Keshav; Giri, Ashok P.; Gershenzon, Jonathan; Gupta, Vidya (SpringerPlus, 2013)
Two furanones, furaneol (4-hydroxy-2,5-dimethyl-3(2H)-furanone) and mesifuran (2,5-dimethyl-4-methoxy-3(2H)-furanone), are important constituents of flavor of the Alphonso cultivar of mango (Mangifera indica). To get insights into the biosynthesis of these furanones, we isolated an enone oxidoreductase gene from the Alphonso mango. It has high sequence similarity to an alkenal/one oxidoreductase from cucumber (79% identity) and enone oxidoreductases from tomato (73% identity) and strawberry (72% identity). The complete open reading frame was expressed in E. coli and the (his) 6-tagged recombinant protein was purified by affinity chromatography. The purified protein assayed with NADH as a reducing agent converted D-fructose-1,6-diphosphate into furaneol, the immediate precursor of mesifuran. The enzyme was also able to convert two highly reactive carbonyls, 3-buten-2-one and 1-penten-3-one, produced by lipid peroxidation in plants, into their saturated derivatives. Expression profiling in various ripening stages of Alphonso fruits depicted an expression maxima at 10 days after harvest stage, shortly before the appearance of the maximum amount of furanones (completely ripe stage, 15 days after harvest). Although no furanones were detected at the 0 day after harvest stage, significant expression of this gene was detected in the fruits at this stage. Overall, the results suggest that this oxidoreductase plays important roles in Alphonso mango fruits.
Keywords: Detoxification; Enone oxidoreductase; Flavor; Mangifera indica; Ripening

Palladium chloride catalyzed photochemical heck reaction - Waghmode, Suresh B.; Arbuj, Sudhir S.; Wani, Bina N.; Gopinath, Chinnakonda S. (Canadian Journal of Chemistry-Revue Canadienne De Chimie, 2013)
PdCl2 catalyzed carbon-carbon bond formation (Heck reaction) between substituted aryl halides and olefins was carried out without a ligand, under irradiation with UV-visible light. The results demonstrated that UV-visible light accelerated the rate of the reaction, leading to an excellent yield of corresponding products. The recovered palladium nanoparticles could be thermally recycled several times. PdCl2 gave excellent conversion up to the fifth addition of substrate.
Keywords: C-C coupling; Heck reaction; iodobenzene; photochemical reaction

PEEK/SiO2 composites with high thermal stability for electronic applications - Goyal, R. K.; Rokade, K. A.; Kapadia, A. S.; Selukar, B. S.; Garnaik, Baijayantimala (Electronic Materials Letters, 2013)
Thermal and mechanical properties of new high performance polymer matrix composites based on poly(etheretherketone) (PEEK) as matrix and crystalline-silica (SiO2) as reinforcement were discussed for application in electronic packaging substrates or printed circuit boards. The content of SiO2 was varied between 0 and 50 wt. %. Scanning electron microscopy showed uniform dispersion of SiO2 particles in the matrix. Thermogravimetry analysis showed significant increase in thermal stability and char yield with increase in SiO2 content in the matrix. Differential scanning calorimetry showed that SiO2 had a heterogeneous nucleating effect on PEEK, leading to an increase in peak temperature of crystallization and onset crystallization temperature of the composites compared to a pure matrix. The microhardness increased approximately 42%. A modified rule of mixtures with a strengthening efficiency factor equal to 0.06 fit the data nicely. The results show that the prepared PEEK/SiO2 composites may have potential applications in electronics.
Keywords: hardness; PEEK; polymer matrix composites; Thermal properties

Perturbative approximations to single and double spin flip equation of motion coupled cluster singles doubles methods - Dutta, Achintya Kumar; Pal, Sourav; Ghosh, Debashree (Journal of Chemical Physics, 2013)
Spin flip equation of motion coupled cluster (EOM-SF-CC) can correctly treat situations involving electronic degeneracies or near degeneracies, e. g., bond breaking, di- and tri-radicals, etc. However, for large systems EOM-SF-CC (even in single and double excitations) is computationally prohibitively expensive. Therefore, earlier approximations to EOM-SF-CC methods such as spin flip configuration interaction singles with perturbative doubles (SF-CIS(D)) have been proposed. In this work, we present a new perturbative approximation to EOM-SF-CC, which has been found to be more accurate than SF-CIS(D). The capabilities, advantages, and timings of the new approach have been demonstrated considering the singlet-triplet gaps in di- and triradicals as well as bond breaking examples. The method is extended to double spin flip EOM-CC and its capabilities have been tested. (C) 2013 AIP Publishing LLC.

Plasticity of protease gene expression in helicoverpa armigera upon exposure to multi-domain capsicum annuum protease inhibitor - Mahajan, Neha S.; Mishra, Manasi; Tamhane, Vaijayanti A.; Gupta, Vidya S.; Giri, Ashok P. (Biochimica et Biophysica Acta (BBA) - General Subjects, 2013)
Background A multi-domain Pin-II type protease inhibitor from Capsicum annuum (CanPI-7) is known to be effective against the insect pest, Helicoverpa armigera. The present study is an attempt to investigate the optimal dose of recombinant CanPI-7 (rCanPI-7) for effective antibiosis to H. armigera and further to characterize the responses of digestive proteases upon rCanPI-7 ingestion. Methods The gut protease activity was assessed biochemically and transcript accumulation pattern for selected trypsin and chymotrypsin genes was analyzed by quantitative Real-Time PCR. Results The growth retardation upon exposure to rCanPI-7 was more prominent in neonates as compared to third instar larvae. Influence of stage and dosage of rCanPI-7 was conspicuous on the expression and regulation of candidate trypsin and chymotrypsin genes in H. armigera. The transcript accumulation pattern correlated with the protease activity in rCanPI-7 exposed larvae. Conclusions We conclude that early exposure and specific dose of protease inhibitor are essential for effective antibiosis despite the large diversity and plasticity in the expression of protease genes in H. armigera. Moreover, it is also evident that the regulation and expression of H. armigera gut proteases are specific to the stage of PI exposure. General significance These results highlight the requirement of optimal PI concentration for effective growth retardation and for inhibiting the major gut proteases of H. armigera.

Poly-L-arginine grafted silica mesoporous nanoparticles for enhanced cellular uptake and their application in DNA delivery and controlled drug release - Kar, Mrityunjoy; Tiwari, Neha; Tiwari, Mitali; Lahiri, Mayurika; Sen Gupta, Sayam (Particle & Particle Systems Characterization, 2013)
Mesoporous silica nanoparticles (MSNs), that are capable of delivering gene and drugs to organisms in an effective and selective way have attracted much attention lately for its potential in the treatment of cancer. However, the successful application of MSNs for delivery of plasmid DNA or drugs requires surface modification of the silica with positively charged functional groups so that it binds to the negatively charged nucleic acids and also helps it penetrate through the cell membrane. We report for the first time the synthesis of a hybrid MSN where the cell penetrating cationic polypeptide poly-L-arginine synthesized by NCA polymerization is grafted onto the external surface of MSN using click chemistry. These poly-L-arginine grafted MSNs show low cytotoxity (85% cell viability at 100 g/mL MSN concentration) and high cellular uptake by both HeLa and A549 (>90%). The poly-L-arginine grafted MSNs were used effectively to deliver mCherry DNA plasmid into cells leading to expression of the protein mCherry inside the cells (transfection efficiency 60%). In contrast, poly-L-arginine grafted non-porous silica nanoparticles were unable to express the protein mCherry inside the cells although their uptake into the cells was as efficient as with poly-L-arginine grafted MSNs. We also show preliminary results to demonstrate that these hybrid MSNs can be used as a delivery vehicle for the anticancer drug Doxorubicin towards cancerous cells HeLa and A549. The biocompatibility of poly-L-arginine and its cell penetrating ability are expected to make these MSN conjugates very useful carriers for the delivery of genes and drugs into cancer cells.

Polyproline fold-In imparting kinetic stability to an alkaline serine endopeptidase - Rohamare, Sonali B.; Dixit, Vaishali; Nareddy, Pavan Kumar; Sivaramakrishna, D.; Swamy, Musti J.; Gaikwad, Sushama M. (Biochimica Et Biophysica Acta-Proteins and Proteomics, 2013)
Polyproline II (PPII) fold, an unusual structural element was detected in the serine protease from Nocardiopsis sp. NCIM 5124 (NprotI) based on far UV circular dichroism spectrum, structural transitions of the enzyme in presence of GdnHCl and a distinct isodichroic point in chemical and thermal denaturation. The functional activity and conformational transitions of the enzyme were studied under various denaturing conditions. Enzymatic activity of NprotI was stable in the vicinity of GdnHCl upto 6.0 M concentration, organic solvents viz, methanol, ethanol, propanol (all 90% v/v), acetonitrile (75% v/v) and proteases such as trypsin, chymottypsin and proteinase K (NprotI:protease 10:1). NprotI seems to be a kinetically stable protease with a high energy barrier between folded and unfolded states. Also, an enhancement in the activity of the enzyme was observed in 1 M GdnHCl upto 8 h, in organic solvents (75% v/v) for 72 h and in presence of proteolytic enzymes. The polyproline fold remained unaltered or became more prominent under the above mentioned conditions. However, it diminished gradually during thermal denaturation above 60 degrees C. Thermal transition studies by differential scanning calorimetry (DSC) showed scan rate dependence as well as irreversibility of denaturation, the properties characteristic of kinetically stable proteins. This is the first report of PPII helix being the global conformation of a non structural protein, an alkaline serine protease, from a microbial source, imparting kinetic stability to the protein. (C) 2013 Elsevier B.V. All rights reserved.
Keywords: Conformation; differential scanning calorimetry; Kinetic stability; Nocardiopsis sp.; Polyproline fold; Serine protease

Preparation-method-dependent morphological, band structural, microstructural, and photocatalytic properties of noble metal-GaNbO4 nanocomposites - Devi, Suman; Kelkar, Sarika A.; Kashid, Vikas; Salunke, Hemant G.; Gupta, Narendra M. (RSC Advances, 2013)
We report the distinct physicochemical and photophysical properties of gallium niobate photocatalysts (bandgap: similar to 3.1 eV), prepared by a solid-state (SS) reaction and sol-gel (SG) method and dispersed with a noble metal (similar to 0.5% of Pt, Au, or RuOx) cocatalyst. SG-GaNbO4 comprised smaller size particles (similar to 20-50 nm) and a larger surface area (similar to 160 m(2) g(-1)) compared to SS-GaNbO4 (particle size similar to 30-150 nm, surface area similar to 27 m(2) g(-1)). XRD patterns revealed a preparation-dependent variation in the relative intensity of prominent reflections. In TEM examination, SG samples exhibited small-range grain boundaries and heterogeneous metal/substrate interfacial contacts, while SS-GaNbO4 had long-range ordering. Laser-Raman and thermoluminescence investigations revealed that lattice distortion, defect-induced inter-bandgap charge trapping states, and the local environment around the metal/semiconductor interfaces may also depend on the preparation method. Metal-GaNbO4 nanocomposites showed no activity for the dissociation of pure water under UV (>250 nm) irradiation, despite the favourable conduction and valence band potentials. This was attributed to the sharp Ga and Nb d-levels in the narrow conduction band of GaNbO4, as confirmed by ab initio electronic structure calculation. These photocatalysts, however, showed good activity for semiconductor-mediated photo-dissociation of aqueous methanol to produce H-2; a cocatalyst-dependent activity trend, Pt > RuOx > Au, was observed. Doping of S at similar to 5% of the oxygen sites led to decreased photoactivity, ascribed to the presence of localized S 3p states just above the O 2p valence level. In conclusion, besides band characteristics, certain morphological and microstructural properties play a crucial role in the photoactivity of the metal/oxide nanocomposites.

Probing the active site of cinnamoyl CoA reductase 1 (Ll-CCRH1) from Leucaena leucocephala - Sonawane, Prashant; Patel, Krunal; Vishwakarma, Rishi Kishore; Srivastava, Sameer; Singh, Somesh; Gaikwad, Sushama M.; Khan, Bashir Mohammad (International Journal of Biological Macromolecules, 2013)
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

Proline-catalyzed asymmetric synthesis of syn- and anti-1,3-diamines - Kumar, Pradeep; Jha, Vishwajeet; Gonnade, Rajesh G. (Journal of Organic Chemistry, 2013)
A general organocatalytic strategy for asymmetric synthesis of both syn/anti-1,3-diamines has been developed. The strategy employs proline-catalyzed sequential alpha-amination and Horner-Wadsworth-Emmons (HWE) olefination of aldehydes as the key step where syn-1,3-diamine was obtained as the most favorable product.

Promising stability of gold-based catalysts prepared by direct anionic exchange for DeNO (x) applications in lean burn conditions - Nguyen, D. -L.; Shubhangi B. Umbarkar; Dongare, Mohan K.; Lancelot, Christine; Girardon, J. S.; Dujardin, Christophe; Granger, P. (Topics in Catalysis, 2013)
Supported gold catalysts on gamma-Al2O3 have been investigated in the catalytic reduction of NO (x) in simulated Diesel exhaust gas conditions. Different parameters have been examined essentially the mode of gold incorporation via classical deposition-precipitation and anionic exchange methods and the nature of the pre-activation thermal treatment. The resistance to thermal ageing under reactive conditions at 500 A degrees C was found completely different with a significant rate enhancement on anionic-exchange samples. Further comparisons also show that the nature of the pre-activation thermal treatment influences the extent of surface reconstructions during thermal ageing with a detrimental effect of reductive pre-treatment on the catalytic performances.
Keywords: Anionic-exchange; Au/Al2O3 catalyst; Deposition-precipitation; NOx abatement; Selective catalytic reduction

Proteome wide reduction in AGE modification in streptozotocin induced diabetic mice by hydralazine mediated transglycation - Kesavan, Suresh K.; Bhat, Shweta; Golegaonkar, Sandeep B.; Jagadeeshaprasad, Mashanipalya G.; Deshmukh, Arati B.; Patil, Harshal S.; Bhosale, Santosh D.; Shaikh, Mahemud L.; Thulasiram, Hirekodathakallu V.; Boppana, Ramanamurthy; Kulkarni, Mahesh J. (Scientific Reports, 2013)
The non-enzymatic reaction between glucose and protein can be chemically reversed by transglycation. Here we report the transglycation activity of hydralazine using a newly developed MALDI-TOF-MS based assay. Hydralazine mediated transglycation of HbA1c, plasma proteins and kidney proteins was demonstrated in streptozotocin (STZ) induced diabetic mice, as evidenced by decrease in protein glycation, as well as presence of hydralazine-glucose conjugate in urine of diabetic mice treated with hydralazine. Hydralazine down regulated the expression of Receptor for Advanced Glycation End products (RAGE), NADPH oxidase (NOX), and super oxide dismutase (SOD). These findings will provide a new dimension for developing intervention strategies for the treatment of glycation associated diseases such as diabetes complications, atherosclerosis, and aging.

Proteomic analysis of protease resistant proteins in the diabetic rat kidney - Bansode, Sneha B.; Chougale, Ashok D.; Joshi, Rakesh S.; Giri, Ashok P.; Bodhankar, Subhash L.; Harsulkar, Abhay M.; Kulkarni, Mahesh J. (Molecular & Cellular Proteomics, 2013)
Glycation induced protein aggregation has been implicated in the development of diabetic complications and neurodegenerative diseases. These aggregates are known to be resistant to proteolytic digestion. Here we report the identification of protease resistant proteins from the streptozotocin induced diabetic rat kidney, which included enzymes in glucose metabolism and stress response proteins. These protease resistant proteins were characterized to be advanced glycation end products modified and ubiquitinated by immunological and mass spectrometry analysis. Further, diabetic rat kidney exhibited significantly impaired proteasomal activity. The functional analysis of identified physiologically important enzymes showed that their activity was reduced in diabetic condition. Loss of functional activity of these proteins was compensated by enhanced gene expression. Aggregation prone regions were predicted by in silico analysis and compared with advanced glycation end products modification sites. These findings suggested that the accumulation of protein aggregates is an inevitable consequence of impaired proteasomal activity and protease resistance due to advanced glycation end products modification. Molecular & Cellular Proteomics 12: 10.1074/mcp.M112.020651, 228-236, 2013.

Proteomic profiling and interactome analysis of ER-positive/HER2/neu negative invasive ductal carcinoma of the breast: towards proteomics biomarkers - Korwar, Arvind M.; Bhonsle, Hemangi S.; Ghole, Vikram S.; Gawai, Kachru R.; Koppikar, Chaitanyananda B.; Kulkarni, Mahesh J. (OMICS-A Journal of Integrative Biology, 2013)
Breast cancer, especially ER positive/HER2/neu negative IDC, is the predominant subtype of invasive ductal carcinoma. Although proteomic approaches have been used towards biomarker discovery in clinical breast cancer, ER positive/HER2/neu negative IDC is the least studied subtype. To discover biomarkers, as well as to understand the molecular events associated with disease progression of estrogen receptor positive/HER2/neu negative subtype of invasive ductal carcinoma, differential protein expression profiling was performed by using LC-MSE (MS at elevated energy). A total of 118 proteins were identified, of which 26 were differentially expressed. These identified proteins were functionally classified and their interactions and coexpression were analyzed by using bioinformatic tools PANTHER (Protein Analysis THrough Evolutionary Relationships) and STRING (Search Tool for the Retrieval of Interacting Genes). These proteins were found to be upregulated and were involved in cytoskeletal organization, calcium binding, and stress response. Interactions of annexin A5, actin, S100 A10, glyceraldehyde 3 phosphate dehydrogenase, superoxide dismutase 1, apolipoprotein, fibrinogen, and heat shock proteins were prominent. Differential expression of these proteins was validated by two-dimensional gel electrophoresis and Western blot analysis. The cluster of these proteins may serve as a signature profile for estrogen receptor positive/ HER2/neu negative subtype.

Purification and characterization of a thermolysin like protease from thermoactinomyces thalpophilus MCMB-380 - Majumder, Devipriya R.; Kanekar, Pradnya P.; Gaikwad, Sushama M. (Protein and Peptide Letters, 2013)
The extracellular thermolysin like protease (TLP) was purified and characterized from Thermoactinomyces thalpophilus MCMB-380 (Genbank Accession No. EF397000). The enzyme was purified to homogeneity by successive ultra filtration steps using 50 kDa and 10 kDa membrane filters followed by anion exchange chromatography. The molecular mass and isoelectric point of the enzyme were found to be 34.4 kDa and 9.5, respectively. The proteolytic activity was inhibited by EDTA and the enzyme required Ca2+ to show the full activity as well as thermostability. The T-50 of the enzyme at 80 degrees C was 1 h and the activation energy was estimated to be 11.02 Kcal / mol. Atomic absorption spectrophotometric analysis revealed the presence of Zn2+ ion in the protein core indicating that it is a metalloprotease. This protease has commercial potential in catalyzing the condensation reaction of two amino acids for production of the dipeptide aspartame, an artificial sweetener. The one hour time-frame is significantly faster than that of the enzyme thermolysin from Bacillus thermoproteolyticus. Moreover the TLP was stable at 80 degrees C for one hour which makes it industrially robust. The Zn2+ ion in the T. thalpophilus protease appears to be necessary for maintaining the active conformation of the enzyme molecule.
Keywords: Metalloprotease; Thermostability; TLP

Rational design of highly active “hybrid” phosphine-phosphinite pincer iridium catalysts for alkane metathesis - Nawara-Hultzsch, Agnieszka J.; Hackenberg, Jason D.; Punji, Benudhar; Supplee, Carolyn; Emge, Thomas J.; Bailey, Brad C.; Schrock, Richard R.; Brookhart, Maurice; Goldman, Alan S. (ACS Catalysis, 2013)
Both the bisphosphine and bisphosphinite pincer complexes (tBu4PCP)IrH2 and (tBu4POCOP)IrH2 can cocatalyze alkane metathesis in tandem with olefin metathesis catalysts, but the two complexes have different resting states during catalysis, suggesting that different steps are turnover-limiting in each case. This led to the hypothesis that a complex with intermediate properties would be catalytically more active than either of these two species. Accordingly, “hybrid” phosphine–phosphinite pincer ligands (PCOP) and the corresponding iridium complexes were synthesized (3c–e). In tandem with olefin-metathesis catalyst MoF12, (tBu4PCOP)IrH2 displays significantly higher activity for the metathesis of n-hexane than does (tBu4PCP)IrH2 or (tBu4POCOP)IrH2. (tBu2PCOPiPr2)IrH4 (3d) is even more active (>30-fold more active than (tBu4POCOP)IrH2) and affords nearly 4.6 M alkane products after 8 h at 125 °C.

Rationally designed CuFe2O4-mesoporous Al2O3 composite towards stable performance of high temperature water-gas shift reaction - Subramanian, Vijayanand; Gnanakumar, Edwin S.; Jeong, Dae-Woon; Han, Won-Bi; Gopinath, Chinnakonda S.; Roh, Hyun-Seog (Chemical Communications, 2013)
High temperature water-gas shift reaction was demonstrated for the first time on a CuFe2O4-mesoporous alumina nanocomposite between 350 and 550 degrees C with 70-80% CO-conversion using simulated waste derived syngas under realistic conditions. Despite high Al-content, the catalyst exhibited stable activity, which was attributed to the nano-architectured robust porous nature of alumina integrated with surrounding CuFe2O4.

Reactivity of thiophenes, oligothiophenes and benzothiophenes - Rajappa, Srinivasachari; Gumaste, Vikas K. (Advances in Heterocyclic Chemistry, 2013)
This article surveys the literature on the reactivity of thiophenes and benzothiophenes published since the appearance of the third edition of Comprehensive Heterocyclic Chemistry. Two areas that have received maximum attention are: (1) homo- and cross-coupling reactions leading to C C bond formation with high site selectivity and under mild reaction conditions, as well as the regioselective introduction of heteroatom substituents and (2) dithienylethenes and their symmetry-allowed photocyclized isomers, with special reference to the use of this photochromic system as photoswitching units.
Keywords: Benzothiophenes and oligothiophenes; Newer results on the reactivity of thiophenes; Pericyclic reactions; Transition metal-catalyzed bond formation

Resistome analysis of mycobacterium tuberculosis: identification of aminoglycoside 2’-nacetyltransferase (AAC) as co-target for drug desigining - Joshi R. S.; Jamdhade M. D.; Sonawane M. S.; Giri, Ashok P. (Bioinformation, 2013)
The emergence of multidrug resistant tuberculosis (MDRTB) highlights the urgent need to understand the mechanisms of resistance to the drugs and to develop a new arena of therapeutics to treat the disease. Ethambutol, isonazid, pyrazinamide, rifampicin are first line of drugs against TB, whereas aminoglycoside, polypeptides, fluoroquinolone, ethionamide are important second line of bactericidal drugs used to treat MDRTB, and resistance to one or both of these drugs are defining characteristic of extensively drug resistant TB. We retrieved 1,221 resistant genes from Antibiotic Resistance Gene Database (ARDB), which are responsible for resistance against first and second line antibiotics used in treatment of Mycobacterium tuberculosis infection. From network analysis of these resistance genes, 53 genes were found to be common. Phylogenetic analysis shows that more than 60% of these genes code for acetyltransferase. Acetyltransferases detoxify antibiotics by acetylation, this mechanism plays central role in antibiotic resistance. Seven acetyltransferase (AT-1 to AT-7) were selected from phylogenetic analysis. Structural alignment shows that these acetyltransferases share common ancestral core, which can be used as a template for structure based drug designing. From STRING analysis it is found that acetyltransferase interact with 10 different proteins and it shows that, all these interaction were specific to M. tuberculosis. These results have important implications in designing new therapeutic strategies with acetyltransferase as lead co-target to combat against MDR as well as Extreme drug resistant (XDR) tuberculosis.

Rhenium(I) tricarbonyl complex of 5,20-bis(p-tolyl)-10,15-bis(p-methoxyphenyl)-21-selenaporphyrin: first X-ray structural characterization of metal complex of 21-selenaporphyrin - Ghosh, Avijit; Gonnade, Rajesh G.; Ravikanth, Mangalampalli (Dalton Transactions, 2013)
Synthesis and first structural characterization of hexa coordinated rhenium(I)tricarbonyl complex of 5,20-bis( p-tolyl)-10,15-bis(p-methoxyphenyl)-21-selenaporphyrin 3 are described. The Re(I)complex of 21-selenaporphyrin 3 was synthesized by treating free base 21-selenaporphyrin in 1,2-dichlorobenzene with Re(CO)(5)Cl at reflux for 7 h and analyzed using mass, NMR, FT-IR, UV-vis and electrochemical techniques. The first structure of metal complex of 21-selenaporphyrin was determined by X-ray single crystal analysis. The crystal structure revealed that the Re(CO)(3) coordinates to two of the three inner nitrogens and one selenium to produce compound 3. The selenophene ring bent towards the Re(I)ion and the selenium is displaced by 0.41 angstrom from the mean plane of 24-atoms to coordinate with Re(I)ion in eta(1)-fashion. The 21-selenaporphyrin is distorted in compound 3 compared to free base 21-selenaporphyrin. H-1 and C-13 NMR studies indicated that compound 3 exhibits fluxional behaviour in coordination mode of binding in solution. The compound 3 is highly stable and does not undergo decomplexation under acidic conditions. The absorption spectra showed three broad Q-bands and splitted Soret band and electrochemical studies indicated that compound 3 is stable under redox conditions.

Role of metal ion in specific recognition of pyrophosphate ion under physiological conditions and hydrolysis of the phosphoester linkage by alkaline phosphatase - Das, Priyadip; Chandar, Nellore Bhanu; Chourey, Shishir; Agarwalla, Hridesh; Ganguly, Bishwajit; Das, Amitava (Inorganic Chemistry, 2013)
Complexes synthesized from Zn(II), Cu(II), and Cd(II), using a dipicolyl amine derivative (L), showed unique specificity toward pyrophosphate ion (PPi or P4O74-) among all other common anionic analytes, including different biologically significant phosphate ion (PO43-, H2PO42-) or phosphate-ion-based nucleotides, such as AMP, ADP, ATP, and CTP. However, the relative affinities of PPi toward these three metal complexes were found to vary and follow the order K-a(L.Zn-PPi) > are given in units of (L.Cu-PPi)(a) >= K-a(L.Cd-PPi). Luminescence responses of the receptor L were substantial on binding to Zn2+ and Cd2+, while relatively a much smaller luminescence response was observed in the presence of Cu2+. Luminescence responses of L.M-PPi (M is Zn2+, Cd2+, and Cu2+) were further modified on binding to the PPi ion. This could be utilized for quantitative detection of PPi in physiological condition as well as for developing a real time ``turn-on'' (for L.Zn and L.Cu) and ``turn-off'' (for L.Cd) fluorescence assay for evaluating the enzymatic activity of alkaline phosphatase (ALP). Experimental results revealed how the subtle differences in the binding affinities between PPi and M in L.M (M is Zn2+, Cd2+, and Cu2+), could influence the cleavage of the phosphoester linkage in PPi by ALP. The DFT calculations further revealed that the hydrolytic cleavage of the metal ion coordinated phosphoester bond is kinetically faster than that for free PPi and thus, rationalized the observed difference in the cleavage of the phosphoester bond by an important mammalian enzyme such as ALP in the presence of different metal complexes.

Self-assembly to function: design, synthesis and broad spectrum antimicrobial properties of short hybrid E-vinylogous lipopeptides - Shankar, S. Shiva; Benke, Sushil N.; Nagendra, Narem; Srivastava, Prabhakar Lal; Thulasiram, Hirekodathakallu V.; Gopi, Hosahudya N. (Journal of Medicinal Chemistry, 2013)
Nonribosomal E-vinylogous gamma-amino acids are widely present in many peptide natural products and have been exploited as inhibitors for serine and cysteine proteases. Here, we are reporting the broad spectrum antimicrobial properties and self-assembled nanostructures of various hybrid lipopeptides composed of 1:1 alternating alpha-and E-vinylogous residues. Analysis of the results revealed that self-assembled nanostructures also play a significant role in the antimicrobial and hemolytic activities. In contrast to the alpha-peptide counterparts, vinylogous hybrid peptides displayed excellent antimicrobial properties against various bacterial and fungal strains. Peptides that adopted nanofiber structures displayed less hemolytic activity, while peptides that adopted nanoneedle structures displayed the highest hemolytic activity.

Silencing an N-acyltransferase-like involved in lignin biosynthesis in nicotiana attenuata dramatically alters herbivory-induced phenolamide metabolism - Gaquerel, Emmanuel; Kotkar, Hemlata; Onkokesung, Nawaporn; Galis, Ivan; Baldwin, Ian T. (Plos One, 2013)
In a transcriptomic screen of Manduca sexta-induced N-acyltransferases in leaves of Nicotiana attenuata, we identified an N-acyltransferase gene sharing a high similarity with the tobacco lignin-biosynthetic hydroxycinnamoyl-CoA: shikimate/quinate hydroxycinnamoyl transferase (HCT) gene whose expression is controlled by MYB8, a transcription factor that regulates the production of phenylpropanoid polyamine conjugates (phenolamides, PAs). To evaluate the involvement of this HCT-like gene in lignin production as well as the resulting crosstalk with PA metabolism during insect herbivory, we transiently silenced (by VIGs) the expression of this gene and performed non-targeted (UHPLC-ESI/TOF-MS) metabolomics analyses. In agreement with a conserved function of N. attenuata HCT-like in lignin biogenesis, HCT-silenced plants developed weak, soft stems with greatly reduced lignin contents. Metabolic profiling demonstrated large shifts (up to 12% deregulation in total extracted ions in insect-attacked leaves) due to a large diversion of activated coumaric acid units into the production of developmentally and herbivory-induced coumaroyl-containing PAs (N', N `'-dicoumaroylspermidine, N', N `'-coumaroylputrescine, etc) and to minor increases in the most abundant free phenolics (chlorogenic and cryptochlorogenic acids), all without altering the production of well characterized herbivory-responsive caffeoyl-and feruloyl-based putrescine and spermidine PAs. These data are consistent with a strong metabolic tension, exacerbated during herbivory, over the allocation of coumaroyl-CoA units among lignin and unusual coumaroyl-containing PAs, and rule out a role for HCT-LIKE in tuning the herbivory-induced accumulation of other PAs. Additionally, these results are consistent with a role for lignification as an induced anti-herbivore defense.

Solution and in silico studies on the recombinant lectin from Cicer arietinum seeds - Wakankar, Madhurima S.; Krishnasastry, Musti V.; Jaokar, Tulika M.; Patel, Krunal A.; Gaikwad, Sushama M. (International Journal of Biological Macromolecules, 2013)
The Cicer arietinum seed lectin was cloned and expressed in Escherichia coli and purified in active form. Conformational characterization of the recombinant lectin (rCAL) was performed using biophysical and bioinformatics tools. Thermal denaturation of rCAL caused rapid secondary structural rearrangements above 50 degrees C and transient exposure of hydrophobic residues at 55 degrees C, leading to aggregation. Treatment of rCAL with GdnHCl resulted in unfolding followed by dissociation of the dimer. The single tryptophan in rCAL present on the surface of the protein is surrounded by hydrophobic and acidic amino acids and exists as different conformers. The experimental observations correlated well with the structural information revealed from the homology model of rCAL. (C) 2013 Elsevier B.V. All rights reserved.
Keywords: Aggregation; BL21-CodonPlus (DE3)-RIL cells; Cicer lectin; Homology model; Steady-state and time resolved fluorescence; Unfolding

Spatial and temporal changes in the volatile profile of alphonso mango upon exogenous ethylene treatment - Chidley, Hemangi G.; Kulkarni, Ram S.; Pujari, Keshav H.; Giri, Ashok P.; Gupta, Vidya S. (Food Chemistry, 2013)
Alphonso is a highly favoured and exported mango cultivar among the vast mango germplasm of India. Being a climacteric fruit, ethylene plays an important role in ripening of mango. For deeper understanding of effect of pre-climacteric ethylene treatment on volatile profiles of Alphonso mango, 26 volatiles were tracked through six ripening stages of pulp and skin of ethylene-treated and control Alphonso fruits. The study revealed accelerated ripening in terms of early appearance of ripening-specific compounds, lactones and mesifuran, upon ethylene treatment. While the level of lactones remained unaffected, the mesifuran level vastly increased upon ethylene treatment. Skin showed high terpene content while pulp had higher amount of lactones compared to skin. This work points towards involvement of ethylene as a natural hormone in the biosynthesis of lactones and furanones in naturally ripened fruits; whereas, an increase in the terpene level during ripening appears to be independent of ethylene. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Ethylene; Flavour; Mango; Pre-climacteric; Ripening; Volatiles

Static and dynamic magnetic properties and effect of surface chemistry on the morphology and crystallinity of DyCrO3 nanoplatelets - Gupta, Preeti; Bhargava, Richa; Das, Raja; Poddar, Pankaj (RSC Advances, 2013)
In this contribution, the structural and magnetic properties of DyCrO3 nanoplatelets, synthesized by a hydrolytic sol-gel method, have been investigated. The crystalline phase of DyCrO3 was attained at the decomposition temperature of 800 degrees C for citric acid and oxalic acid, respectively and their structural analysis indicates a distorted orthorhombic perovskite structure of the DyCrO3 nanoplatelets. The dc-magnetization curve shows the Neel temperature of similar to 144 and similar to 146 K for DyCrO3 nanoplatelets synthesized using citric acid (DCO (C)) and oxalic acid (DCO (O)), respectively. In addition, DCO (O) shows weak anomalies at similar to 22 and similar to 6 K in the zero-field-cooled and field-cooled magnetization curves. Below the Neel temperature, DCO (C) and DCO (O) exhibit cross-over from positive to negative magnetization at similar to 143 and similar to 145 K, respectively. This was attributed to a Dy3+-Cr3+ interaction, which resulted in a weak ferromagnetic coupling (seen as a small opening in the M-H curves). The low temperature transition observed at similar to 6 K can be assigned to the onset of Dy3+-Dy3+ antiferromagnetic interaction.

Structural variations of D-pi-A dyes influence on the photovoltaic performance of dye-sensitized solar cells - Marszalek, Magdalena; Nagane, Satyawan; Ichake, Amol; Humphry-Baker, Robin; Paul, Vincent; Zakeeruddin, Shaik M.; Gratzel, Michael (RSC Advances, 2013)
Two new organic D-pi-A dyes containing identical pi-conjugated spacer and anchoring/acceptor moieties but different donor groups were designed and synthesized. These dyes containing didodecylcyclopentadithiophene (CPDT) as a spacer, cyanoacrylic acid as an acceptor and N-butyl-carbazole or N-butyl-phenothiazine moieties as electron donor groups are labelled as V4 and V11 dyes, respectively. The variation in the donor group of these two dyes, that influences the photophysical, electrochemical and photovoltaic parameters, was investigated. The highest photovoltaic conversion efficiency of 7.5% was obtained with V4 dye at AM 1.5 G full sunlight intensity (100 mWcm(-2)). Comparison of phenothiazine donor dyes with two different pi-conjugated spacers, CPDT (V11) and vinyl thiophene (V7) containing devices shows that the V-oc of V7 dye is lower than that of V11 due to the downward shift of the conduction band edge. Transient photovoltage and electrochemical impedance spectroscopy measurements were performed to explain the differences in the PV parameters by varying the donors and/or spacer groups.

Structural-functional insights of single and multi-domain capsicum annuum protease inhibitors - Mishra, Manasi; Joshi, Rakesh S.; Gaikwad, Sushama M.; Gupta, Vidya S.; Giri, Ashok P. (Biochemical and Biophysical Research Communications, 2013)
Pin-II protease inhibitors (PIs) are the focus of research interest because of their large structural-functional diversity and relevance in plant defense. Two representative Capsicum annuum PI genes (CanPI-15 and -7) comprising one and four inhibitory repeat domains, respectively, were expressed and recombinant proteins were characterized. beta-Sheet and unordered structure was found predominant in CanPI-15 while -7 also displayed the signatures of polyproline fold, as revealed by circular dichroism studies. Inhibition kinetics against bovine typsin indicated three times higher potency of CanPI-7 (K-i similar to 57 mu M) than -15 (similar to 184 mu M). Activity and structural stability of these CanPIs were revealed under various conditions of pH, temperature and denaturing agent. Structure prediction, docking studies with proteases and mass spectroscopy revealed the organization of multiple reactive site loops of multi domain PIs in space as well as the steric hindrances imposed while binding to proteases due to their close proximity. (C) 2012 Elsevier Inc. All rights reserved.
Keywords: CanPI; Circular dichroism; Disulfide bonding; Potato type-II protease inhibitors; Protein stability

Study of grafting of polylactic acid and its copolymer with 12-hydroxy stearic acid on the surface of MWCNT by 13CCP/MAS and AFM - Pandey, Asutosh K.; Garnaik, Baijayantimala (International Journal of Research in Pharmacy and Chemistry, 2013)
The purpose of this study to study the structure property relationship of grafted material on MWCNT, the determination of NMR nuclei spin-lattice (T1) and spin-spin (T2) relaxation times suggest that the broaden signals are associated with diamagnetic species namely the nanotube attached polymer moieties. the AFM image of PLA oligomer grafted MWCNTs and topography patterns comprised of height from 0-250 nm and the side lengths ranging from 0.0 to 7.7 µm. Surface patches are formed randomly distributed employing that the presence of side chain hanged at 12-postion in the copolymer grafted on MWCNTs.