Synthesis, characterization and molecular structures of homologated analogs of 2-bromo-3-(n-alkylamino)-1,4-napthoquinone - Salunke-Gawali, Sunita; Pawar, Omkar; Nikalje, Milind; Patil, Rishikesh; Weyhermueller, Thomas; Puranik, Vedavati G.; Konkimalla, V. Badireenath (Journal of Molecular Structure, 2014)
Four analogues of 2-bromo-3-(n-alkylamino)-1,4-napthoquinone (where n-alkyl is methyl in L-1Br, ethyl in L-2Br, propyl in L-3Br and butyl in L-4Br) are synthesized and characterized. A reaction mechanism is proposed for the formation of L-1 Br to L-4Br from the starting material 2,3-dibromo-1,4-naphthoquinone. The v(N-H) frequency in the FT-IR spectra is affected by the intramolecular hydrogen bonding in L-1Br to L-4Br and is observed similar to 3267 cm(-1) in L-2Br. A shift of similar to 25 cm(-1) is observed in the v(C-Br) frequency in all the compounds as compared to 2,3-dibromo-1,4-naphthoquinone (627 cm(-1)). A broad charge transfer band is observed between 400 and 600 nm in the UV-Vis spectra, which imparts red colour to all the compounds. Molecular structures of L-2Br and L-3Br were studied by single crystal X-ray diffraction studies. Molecules of L-2Br crystallize in Pca2(1), whereas the molecule L-3Br crystallizes in the P-1 space group. Molecules of L-2Br forms a polymeric chain through N-H...O interaction and forms beautiful butterfly like arrangement of molecules when viewed down the `a' axis. Ladder like polymeric chain of molecules is observed in L-3Br via C-H...O and N-H...O interactions. Every alternating neighbouring chains of L-3Br, show pi-pi stacking interactions between the quinonoid rings of the molecules, however this interaction is not observed in L-2Br. (C) 2013 Elsevier B.V. All rights reserved.
Keywords: 2; 3-Dibromo-1; 4-naphthoquinone; Aminonaphthoquinone; hydrogen bonding; Michael addition; pi-pi stacking

Synthesis, characterization and photocatalytic behavior of TiO2-SiO2 mesoporous composites in hydrogen generation from water splitting - Niphadkar, P. S.; Chitale, S. K.; Sonar, S. K.; Deshpande, Suvarna S.; Joshi, P. N.; Awate, S. V. (Journal of Materials Science, 2014)
TiO2-SiO2 mesoporous composite photocatalysts with different proportions (in wt%) of TiO2 and SiO2 (TiO2-SiO2 = 20:80, 40:60, 60:40, 80:20 and 100:0) were prepared by loading TiO2 on as-synthesized Si-MCM-41 using sol-gel method. The physicochemical properties of composites were investigated by powder X-ray diffraction, N-2 adsorption-desorption measurements, transmission electron microscopy and UV-Vis diffuse reflectance spectroscopy. It is revealed that the titanium species are dispersed as TiO2 having interaction with the surface of the support. Even at high TiO2 loading, the mesostructural feature of MCM-41 was found to be intact without pore blockages. The change in morphology of TiO2 particle was observed with increase in TiO2 loading which may be due to different environment for the growth of TiO2. The photocatalytic evaluation of composites was carried out in production of hydrogen by water splitting. Among the prepared samples, mesoporous composite containing 60 % TiO2 (MTi60) has shown the best results (0.08805 mmol of H-2/h/g of TiO2) compared to other composite photocatalysts. The catalytic performance of this sample was further enhanced (similar to 8 times) after loading 1 % Pt in water splitting (0.70161 mmol of H-2/h/g of TiO2). 1 % Pt loaded on pure TiO2 (MTi100) showed hydrogen evolution of the magnitude 0.26 mmol of H-2/h/g of TiO2. TiO2-SiO2 mesoporous composite photocatalyst showed much higher activity (similar to 1.9 times) than amorphous silica-embedded titania catalyst having same composition.

Synthesis of ciprofloxacin-conjugated poly(L-lactic acid) polymer for nanofiber fabrication and antibacterial evaluation - Parwe, Sharad P.; Chaudhari, Priti N.; Mohite, Kavita K.; Selukar, Balaji S.; Nande, Smita S.; Garnaik, Baijayantimala (International Journal of Nanomedicine, 2014)
Ciprofloxacin was conjugated with polylactide (PLA) via the secondary amine group of the piperazine ring using PLA and 7-(4-(2-Chloroacetyl) piperazin-1-yl)-1-cyclopropyl-6-fluoro-1, 4-dihydro-4-oxoquinoline-3-carboxylic acid. Zinc prolinate, a biocompatible catalyst was synthesized, characterized, and used in ring opening polymerization of L-lactide. Five different kinds of OH-terminated poly(L-lactide) (two-, three-, four-, six-arm, star-shaped) homopolymers were synthesized by ring opening polymerization of L-lactide in the presence of dodecanol, glycerol, pentaerythritol, dipentaerythritol as initiator and zinc prolinate as a catalyst. The structures of the polymers and conjugates were thoroughly characterized by means of gel permeation chromatography, matrix-assisted laser desorption/ionization-time of flight mass spectrometry, and nuclear magnetic resonance spectroscopy. PLA (molecular weight = 100,000) and ciprofloxacin conjugated PLA were used for fabrication of nonwoven nanofiber mat (diameter ranges; 150-400 nm) having pore size (62-102 nm) using electrospinning. The microbiological assessment shows that the release of ciprofloxacin possesses antimicrobial activity. The drug-release behavior of the mat was studied to reveal potential application as a drug delivery system. The result shows that the ciprofloxacin release rates of the PLA conjugate nonwoven nanofiber mat could be controlled by the drug loading content and the release medium. The development of a biodegradable ciprofloxacin system, based on nonwoven nanofiber mat, should be of great interest in drug delivery systems.
Keywords: antibacterial activity; ciprofloxacin conjugated polylactides; CP-PLA; drug release; electrospinning; MDR; nonwoven nanofibers; zinc prolinate

Synthetic turn mimetics and hairpin nucleators: quo vadimus? - Nair, Roshna V.; Baravkar, Sachin B.; Ingole, Tukaram S.; Sanjayan, Gangadhar J. (Chemical Communications, 2014)
Structural mimicry of peptides has witnessed perceptible progress in the last three decades. Reverse turn and beta-hairpin units are the smallest secondary structural motifs that are some of the most scrutinized functional cores of peptides and proteins. The practice of mimicking, without altering the function of the bioactive core, ranges from conformational locking of the basic skeleton to total replacement of structural architecture using synthetic analogues. Development of heterogeneous backbones - using unnatural residues in place of natural ones - has broadened further opportunities for efficient structural rigidification. This feature article endeavours to trail the path of progress achieved hitherto and envisage the possibilities that lie ahead in the development of synthetic turn mimetics and hairpin nucleators.

(Thio)urea-mediated benzoxazinone opening: mild approach towards synthesis of o-(substituted amido)benzamides - Nair, R. V.; Sanjayan, G. J. (RSC Advances, 2014)
C-terminal activation of N-acylated o-aminobenzoic acids and their derivatives during coupling reactions with amines would often pose a challenge due to the formation of a benzoxazinone intermediate, which may resist reacting with amines. This communication reports a mild approach towards the installation of an amide bond via benzoxazinone ring opening utilizing Schreiner's (thio)urea organocatalyst. Peptide coupling reactions oen encounter major hurdles because of the formation of side products during carbonyl activation of various amino acids, like N-carboxyanhydride, diketopiperazine etc. 1 1,3-benzoxazinones (Fig. 1) are a class of heterocyclic side products obtained upon C-terminal activation of anthranilic acid and their derivatives due to the intra-molecular cyclization of the benzamide oxygen, resulting in trace or no coupling. 2 Strategies meant either to avert its formation in situ or to react it with amines have been attempted through heating the reactants at elevated temperatures 3 and/or in the presence of bases. 2b,c However, such drastic conditions may cause quinazoline formation as well, owing to a second cyclodehydration of the coupled product. Moreover, applying such drastic conditions to amino acids may not be advisable due to the possibility of epimerization. We have been interested for quite some time in the devel-opment of foldamers containing the Ant–Pro reverse-turn motif (Ant ¼ anthranilic acid, Pro ¼ proline), Fig. 1. 4 The striking feature of this motif is its robust 9-membered-ring intra-molecular H-bonding network. Occasionally, the formation of a benzoxazinone intermediate causes a drastic fall in the yield of coupled products. 5 Owing to the reduced reactivity of benzox-azinones towards amine nucleophiles, we attempted different conditions, such as heating the reaction mixture and under microwave conditions. Unfortunately, these procedures led to only partial conversion of the oxazinone into the product. Aer extensive effort, we were successful in developing an efficient method for coupling a range of isolated benzoxazinone inter-mediates via nucleophilic ring-opening utilizing DBU (1,8-dia-zabicycloundec-7-ene) in DMF containing A molecular sieves. 5 However, in a few cases, this method produced only meagre yields of the coupled product. One such instance was the reac-tion of 2-(2-azidopropan-2-yl)-2H-benzo[d][1,3]oxazin-4-one 1a, Table 1 (isolated as the major by-product on activation of 2-(2-azido-2-methylpropanamido)benzoic acid) with H-L Pro-OBn to obtain compound 2a. Scanty yields of the product isolated under DBU-mediated opening conditions impelled us to explore a carbonyl activation route to open the azlactone moiety. Hence, we employed some lactone activating agents, such as Sc(OTf) 3 , Ti(O i Pr) 4 etc., but none of the trials were rewarding.

Two-in-one: inherent anhydrous and water-assisted high proton conduction in a 3D metal-organic framework - Nagarkar, Sanjog S.; Unni, SreeKuttan M.; Sharma, Amitosh; Kurungot, Sreekumar; Ghosh, Sujit K. (Angewandte Chemie-International Edition, 2014)
The development of solid-state proton-conducting materials with high conductivity that operate under both anhydrous and humidified conditions is currently of great interest in fuel-cell technology. A 3Dmetal-organic framework (MOF) with acid-base pairs in its coordination space that efficiently conducts protons under both anhydrous and humid conditions has now been developed. The anhydrous proton conductivity for this MOF is among the highest values that have been reported for MOF materials, whereas its water-assisted proton conductivity is comparable to that of the organic polymer Nafion, which is currently used for practical applications. Unlike other MOFs, which conduct protons either under anhydrous or humid conditions, this compound should represent a considerable advance in the development of efficient solid-state proton-conducting materials that work under both anhydrous and humid conditions.
Keywords: conducting materials; fuel cells; metal-organic frameworks; porous materials; proton conduction

Uptake of Azo dyes into silk glands for production of colored silk cocoons using a green feeding approach - Nisal, Anuya; Trivedy, Kanika; Mohammad, Hasan; Panneri, Suyana; Sen Gupta, Sayam; Lele, Ashish K.; Manchala, Ramesh; Kumar, Nirmal S.; Gadgil, Mugdha; Khandelwal, Harish B.; More, Snehal; Laxman, Ryali Seeta (ACS Sustainable Chemistry & Engineering, 2014)
Dyeing of textile fabrics is considered to be one of the most polluting industries today, and there is a need to develop green processes that can reduce this pollution. A promising technology that can potentially cleanup the dyeing of silk fibers that are widely used for textile applications would involve the generation of intrinsically colored silk cocoons. This can be achieved by feeding of Bombyx mori silkworm larvae with a modified feed of mulberry leaves containing a sprayed dye solution. This process significantly reduces the need for treating toxic dye effluents that are generated in traditional dyeing processes. In this report, we have evaluated a set of seven different azo dyes that are used in the textile industry for dyeing to produce intrinsically dyed silk. The dyes used in the study had similar chemical structures with systematically varying partition coefficients. The results suggest that while some dyes produced intrinsically colored silk other did not. Careful evaluation of the physical properties of these related azo dyes suggest that the balance of hydrophobic and hydrophilic character is necessary for diffusion of the dye from the alimentary canal of the silkworm larva into the hemolymph and later into the silk glands. The partition coefficient of the dye also determines the preferential association of the dye with either sericin or fibroin protein in the silkworm gland and finally into the cocoon. These insights are extremely important in development of novel dye molecules that can be successfully fed to Bombyx mori silkworm larvae for producing intrinsically colored silk of various colors and shades.
Keywords: Azo dyes; Biochemical pathways; Color silk; Dye uptake; `' Green `' silk

Variation of CO2 adsorption in isostructural Cd(II)/Co(II) based MOFs by anion modulation - Singh, Udai P.; Narang, Shikha; Pachfule, Pradip; Banerjee, Rahul (CrystEngComm, 2014)
{A potential multidentate tris-pyridyl ligand has been synthesized, and later employed for the tailoring of four isostructural cadmium(II)/cobalt(II) two dimensional (2D) metal organic frameworks, [[ M(dmpt)(2)(X)(2)].xS](n), where S = solvent

1,2,3-Triazole derivatives as antitubercular agents: synthesis, biological evaluation and molecular docking study - Shaikh, Mubarak H.; Subhedar, Dnyaneshwar D.; Nawale, Laxman; Sarkar, Dhiman; Khan, Firoz A. Kalam; Sangshetti, Jaiprakash N.; Shingate, Bapurao B. (MedChemComm, 2015)
Searching for new active molecules against Mycobacterium tuberculosis (MTB) H37Ra, a small focused library of 1,2,3-triazoles has been efficiently prepared via a click chemistry approach. The newly synthesized compounds were tested against drug-sensitive MTB. Several derivatives were found to be promising inhibitors of MTB characterized by lower MIC values (5.8-29.9 mu g mL(-1)). Among all the synthesized 31 compounds, 15e was the most active compound against MTB. Based on the results from the antitubercular activity, SAR for the synthesized series has been developed. The active compounds from the anti-tubercular study were further tested for anti-proliferative activity against THP-1, A549 and PANC-1 cell lines using MTT assay and showed no significant cytotoxic activity against these three cell lines except THP-1 at the maximum concentration evaluated. Further, the synthesized compounds were found to have potential antioxidant activities with an IC50 range of 10.1-37.3 mu g mL(-1). The molecular docking study of the synthesized compounds was performed against the DprE1 enzyme of MTB to understand the binding interactions. Moreover, the synthesized compounds were also analysed for ADME properties and all the experimental results promote us to consider this series as a starting point for the development of novel and more potent anti-tubercular agents in the future.

Acid stability of the kinetically stable alkaline serine protease possessing polyproline II fold - Rohamare, Sonali; Javdekar, Vaishali; Dalal, Sayli A.; Nareddy, Pavan Kumar; Swamy, Musti J.; Gaikwad, Sushama M. (Protein Journal, 2015)
The kinetically stable alkaline serine protease from Nocardiopsis sp.; NprotI, possessing polyproline II fold (PPII) was characterized for its pH stability using proteolytic assay, fluorescence and Circular Dichroism (CD) spectroscopy, and Differential Scanning Calorimetry (DSC). NprotI was found to be functionally stable when incubated at pH 1.0, even after 24 h, while after incubation at pH 10.0, drastic loss in the activity was observed. The enzyme showed enhanced activity after incubation at pH 1.0 and 3.0, at higher temperature (50-60 A degrees C). NprotI maintained the overall PPII fold in broad pH range as seen using far UV CD spectroscopy. The PPII fold of NprotI incubated at pH 1.0 remained fairly intact up to 70 A degrees C. Based on the isodichroic point and T-m values revealed by secondary structural transitions, different modes of thermal denaturation at pH 1.0, 5.0 and 10.0 were observed. DSC studies of NprotI incubated at acidic pH (pH 1.0-5.0) showed T-m values in the range of 74-76 A degrees C while significant decrease in T-m (63.8 A degrees C) was observed at pH 10.0. NprotI could be chemically denatured at pH 5.0 (stability pH) only with guanidine thiocynate. NprotI can be classified as type III protein among the three acid denatured states. Acid tolerant and thermostable NprotI can serve as a potential candidate for biotechnological applications.
Keywords: Acid stability; DSC; Kinetic stability; Polyproline fold; Protease; Thermal unfolding

Activation by pretreatment of Ag-Au/Al2O3 bimetallic catalyst to improve low temperature HC-SCR of NOx for lean burn engine exhaust - More, Pavan M.; Nguyen, Duy L.; Granger, Pascal; Dujardin, Christophe; Dongare, Mohan K.; Shubhangi B. Umbarkar (Applied Catalysis B-Environmental, 2015)
Bimetallic Ag-Au/Al2O3 catalyst was synthesised by successive impregnation of 1% Au and 1% Ag on in-house prepared high surface area alumina (450 m(2)/g). The corresponding monometallic catalysts were also prepared by loading 1% Ag or 1% Au on the same high surface area alumina for comparison. The catalysts were characterised by various physico-chemical techniques and tested for SCR activity under lean burn engine exhaust conditions. Ag-Au/Al2O3 catalyst prepared by successive impregnation method showed considerably higher NO reduction (100%) to N-2 compared to 1% Au/Al2O3 (70%) whereas the activity was comparable with that of 1% Ag/Al2O3 (96%). The effect of various pretreatments on SCR activity of Ag-Au/Al2O3 was studied and pretreatment at 250 degrees C in flow of hydrogen was found to give the best results with 100% NO conversion to N-2 at 353 degrees C. Further ageing of the catalyst under reaction feed at 500 degrees C resulted in considerable increase in low temperature activity of bimetallic catalyst with similar to 40% NO conversion at 222 degrees C. Even though the SCR activity of pretreated Ag-Au/Al2O3 and Ag/Al2O3 were comparable, after ageing the Ag-Au/Al2O3 showed significantly higher NO conversion (95%) compared to Ag/Al2O3 (83%) and Au/Al2O3 (70%). The formation of H-2 and CO due to steam reforming of higher hydrocarbon (decane) was evidenced at the temperature of highest deNO(x) activity. Detailed investigation of the textural properties of the pretreated and aged catalysts showed presence of well dispersed metallic Au and Ag-n(delta+) clusters after pretreatment in hydrogen at 250 degrees C. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Ag-Au bimetallic catalyst; Catalyst ageing; dispersion; Low temperature HC-SCR; Steam reforming

Analytical and bioanalytical UHPLC-MS method validation for determination of metformin, a bigunaide and sitagliptin, a DPP-4 inhibitor - Nakrani, Mital; Bairagee, Deepika; Goyal, Pradeep; Santhakumari, B. (International Journal of Pharmacy and Pharmaceutical Sciences, 2015)

Antibiofilm activity of tert-BuOH functionalized ionic liquids with methylsulfonate counteranions - Navale, Govinda R.; Dharne, Mahesh S.; Shinde, Sandip S. (RSC Advances, 2015)
A series of varying alkyl chain length substituted tert-BuOH-functionalized-imidazolium mesylate salts [alkyl-(t)OHim][OMs] were synthesized and evaluated for antimicrobial activity and antibiofilm potential on selected pathogenic microorganisms including bacteria (Gram positive and Gram negative), yeast, and fungi. The dodecyl substituted ionic liquid [C-12-(t)OHim][OMs] significantly prevented the biofilm formation of S. epidermidis at 100 mu M concentration as well as showed noteworthy antimicrobial activity. We conclude that the ionic liquids (ILs) bearing chain lengths lower than the dodecyl length were found to be less effective against most of the tested pathogenic microorganisms.

Benzylation of acetic acid to benzyl acetate over highly active and reusable micro/meso-HZSM-5 - Nandiwale, Kakasaheb Y.; Galande, Nitish D.; Raut, Sunil A.; Bokade, Vijay V. (Chemical Engineering Research & Design, 2015)
Catalytic benzylation of acetic acid (AA) with benzyl alcohol (BA) to benzyl acetate was studied over zeolites viz. H-ZSM-5 (microporous, medium pore), Micro/Meso-HZSM-5 (combination of micro- and meso pore), H-Beta (microporous, large pore) to investigate catalytic activity and selectivity towards benzyl acetate. Micro/Meso-HZSM-5 obtained by desilication post-treatment has been employed as a heterogeneous catalyst for benzylation reaction probably for the first time. Micro/Meso-HZSM-5 was found to be a promising catalyst for benzylation with AA conversion of 94%, selectivity towards benzyl acetate of 95%. The detailed optimization of process parameters such as molar ratio, catalyst loading, reaction temperature and time was also presented. Micro/Meso-HZSM-5 catalyst was observed to be stable for six cycles (1 fresh and 5 recycles). The first order reaction kinetics (R-2 >0.98) indicated that reaction rate constants increased with increasing reaction temperature. The activation energy for benzylation of AA with BA over Micro/Meso-HZSM-5 was obtained to be 15.07 kJ mol(-1), which is far less than the reported. (C) 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Acetic acid; Benzyl acetate; Benzyl alcohol; Benzylation; Micro/Meso-HZSM-5; Reaction kinetics

Beta, gamma-Bis-substituted PNA with configurational and conformational switch: preferred binding to cDNA/RNA and cell-uptake studies - Bose, Tanaya; Banerjee, Anjan; Nahar, Smita; Maiti, Souvik; Kumar, Vaijayanti A. (Chemical Communications, 2015)
(S,S)- and (R,R)-beta,gamma-Bis-substituted PNAs were synthesized from the C-2 symmetric vicinal diamine system embedded in 1,4 dihydroxybutane and 1,4-dimethoxybutane scaffolds. (R,R)-beta,gamma-Bis-methoxymethyl-PNA derived from D-tartaric acid was found to be in the right configuration and conformation to be an excellent mimic of PNA, endowed with superior ability to enter into cells.

Bioinspired catecholic flame retardant nanocoating for flexible polyurethane foams - Cho, Joon Hee; Vasagar, Vivek; Shanmuganathan, Kadhiravan; Jones, Amanda R.; Nazarenko, Sergei; Ellison, Christopher J. (Chemistry of Materials, 2015)
An efficient, environmentally friendly, and water-applied flame retardant surface nanocoating based on polydopamine (PDA) was developed for foamed materials such as polyurethane (PU). The PDA nanocoating, deposited by simple dip-coating in an aqueous dopamine solution, consists of a planar sublayer and a secondary granular layer structure that evolve together, eventually turning into a dense, uniform, and conformal layer on all foam surfaces. In contrast to flexible PU foams that are known to be highly flammable without flame retardant additives, micro combustion calorimetry (MCC) and thermogravimetric analysis (TGA) confirm that the neat PDA is relatively inflammable with a strong tendency to form carbonaceous, porous char that is highly advantageous for flame retardancy. By depositing nano coatings of PDA onto flexible PU foams, the flammability of the PU foam was significantly reduced with increasing coating thickness. For the thickest coating (3 days of PDA deposition), the foam quickly self-extinguished and its original shape was completely preserved after exposure to a flame in a torch burn test. In addition to the char forming ability of PDA, it is hypothesized that its catechol units likely scavenge nearby radicals that typically evolve additional fuel for the fire as they attack surrounding materials. This multiple flame retardancy action of PDA (i.e., char formation + radical scavenging) enables flame retardant foams with a peak heat release rate (P-HRR) that is significantly reduced (up to 67%) relative to control foams, representing much better performance than many conventional additives reported in the literature at comparable or higher loadings.

Biosynthesis of silver nanoparticles by using ganoderma-mushroom extract - Ekar, S. U.; Khollam, Y. B.; Koinkar, Pankaj M.; Mirji, S. A.; Mane, R. S.; Naushad, M.; Jadhav, S. S. (Modern Physics Letters B, 2015)
Present study reports the biochemical synthesis of silver nanoparticles (Ag-NPs) from aqueous medium by using the extract of medicinal mushroom Ganoderma, as a reducing and stabilizing agents. The Ag-NPs are prepared at room temperature by the reduction of Ag+ to Ag in aqueous solution of AgNO3. The resultant particles are characterized by using UV-visible spectroscopy, Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM) measurement techniques. The formation of Ag-NPs is confirmed by recording the UV-visible absorption spectra for surface plasmon resonance (SPR) where peak around 427 nm. The prominent changes observed in FTIR spectra supported the reduction of Ag+ to Ag. The morphological features of Ag-NPs are evaluated from HRTEM. The spherical Ag-NPs are observed in transmission electron microscopy (TEM) studies. The particle size distribution is found to be nearly uniform with average particle size of 2 nm. The Ag-NPs aged for 15, 30, 60 and 120 days showed no profound effect on the position of SPR peak in UV-visible studies, indicating the protecting/capping ability of medicinal mushroom Ganoderma in the synthesis of AgNPs.
Keywords: Biosynthesis; Ganoderma; medicinal mushroom; silver nanoparticles; UV-visible spectroscopy

Calculation of P,T-odd interaction constant of PbF using Z-vector method in the relativistic coupled-cluster framework - Sasmal, Sudip; Pathak, Himadri; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Journal of Chemical Physics, 2015)
The effective electric field experienced by the unpaired electron in the ground state of PbF, which is a potential candidate in the search of electron electric dipole moment due to some special characteristics, is calculated using Z-vector method in the coupled cluster single-and double-excitation approximation with four component Dirac spinor. This is an important quantity to set the upper bound limit of the electron electric dipole moment. Further, we have calculated molecular dipole moment and parallel magnetic hyperfine structure constant (A(parallel to)) of Pb-207 in PbF to test the accuracy of the wavefunction obtained in the Z-vector method. The outcome of our calculations clearly suggests that the core electrons have significant contribution to the ``atom in compound'' properties. (C) 2015 AIP Publishing LLC.

Can we shift and/or broaden the catalysis regime towards ambient temperature? - Gopinath, Chinnakonda S.; Roy, Kanak; Nagarajan, Sankaranarayanan (ChemCatChem, 2015)
An attempt was made to shift the temperature regime of oxidation catalysis towards ambient temperatures by employing surface modification (SM) as a handle. Systematic SM of Pd(111) was performed by O-atom diffusion into the subsurfaces. Virgin and modified Pd(111) catalysts were evaluated for CO oxidation. Typical CO poisoning observed on virgin surfaces was partially lifted, and ambient CO oxidation was observed on the modified surfaces. CO oxidation was followed by the molecular beam method and near-ambient pressure (NAP) photoelectron spectroscopy under different pressure regimes. UV valence band spectral analysis of the SM and the CO+O-2 reaction on modified Pd(111) surfaces under NAP conditions demonstrated changes in the electronic structures of the surfaces with a change in surface potential by 0.35eV and directly probed CO2 formation under the reaction conditions. Supported metal catalysts may be subjected to SM and evaluated for a shift in the catalysis regime for many different reactions.
Keywords: heterogeneous catalysis; Oxidation; photoelectron spectroscopy; surface chemistry; surface modification

Catalytic upgrading of citric acid to environmental friendly tri-butyl citrate plasticizer over ultra stable phosphonated Y zeolite - Nandiwale, Kakasaheb Y.; Gogoi, Pranjal; Bokade, Vijay V. (Chemical Engineering Research & Design, 2015)
The catalytic synthesis of non-toxic/eco-friendly tributyl citrate (TBC) plasticizer by esterification of renewable citric acid (CA) with butanol would be completely sustainable route. In this context, catalytic performance of parent ultra stable Y (USY) and phosphonated USY catalysts were investigated for TBC synthesis. Parent USY and phosphonated USY catalysts were characterized by powder X-ray diffraction (XRD), N-2 adsorption-desorption, NH3 temperature programmed desorption (TPD), pyridine-Fourier Transform Infrared Spectroscopy (FTIR), FTIR, SEM, ICP. The influence of various process parameters such as phosphorous (P) loading (0 to 4 wt/%), catalyst loading (5-25%), molar ratio of CA to n-butanol (1:4 to 1:12), reaction temperature (383-423 K) and reaction time (1-5 h) have been investigated over USY catalyst with aim to maximize CA conversion and TBC yield. Amongst the studied catalysts, the 2% (w/w) P/USY was found to be highly potential catalyst with complete CA conversion (100%) and 93% TBC yield. The present method of using 2% (w/w) P/USY catalyst for the synthesis of TBC would be environmentally benign in the context of bio-renewable synthetic route, high catalytic activity, non-toxic product, long term stability and reusability of catalyst (five catalytic cycles). (c) 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved,
Keywords: Butanol; Citric acid; heterogeneous catalysis; Plasticizer; Tributyl citrate

Chemical and biological metal nanoparticles as antimycobacterial agents: a comparative study - Singh, Richa; Nawale, Laxman U.; Arkile, Manisha A.; Shedbalkar, Utkarsha U.; Wadhwani, Sweety A.; Sarkar, Dhiman; Chopade, Balu Ananda (International Journal of Antimicrobial Agents, 2015)
Resistance among mycobacteria leading to multidrug-resistant and extensively drug-resistant tuberculosis is a major threat. However, nanotechnology has provided new insights in drug delivery and medicine development. This is the first comparative report to determine the activity of chemically and biologically synthesised silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) against mycobacteria. Screening data revealed the high mycobactericidal efficiency of AgNPs, with minimum inhibitory concentrations (MICs) of <3 mu g/mL, whereas no such activity was exhibited by AuNPs at concentrations up to 100 mu g/mL. Moreover, in vitro and ex vivo THP-1 infection model assays showed greater efficacy of chemical AgNPs compared with biogenic AgNPs to inhibit active and dormant stage mycobacterial growth. Up to 40% cytotoxicity against human cell lines was observed at a AgNP concentration of 10 x MIC (30 mu g/mL) after 48 h. AgNPs were shown to have more specificity towards mycobacteria than towards other Gram-negative and Gram-positive pathogenic bacteria. The selectivity index was found to be in the range of 11-23, indicating the potential of these nanoparticles for use in developing new therapeutics for tuberculosis. (C) 2015 Elsevier B.V. and the International Society of Chemotherapy. All rights reserved.
Keywords: Antibiotic resistance; Antimycobacterial agent; Cytotoxicity; Mycobacteria; Nanoparticles; tuberculosis

Chemoinformatics approach for building molecular networks from marine organisms - Karthikeyan, Muthukumarasamy; Nimje, Deepika; Pahujani, Rakhi; Tyagi, Kushal; Bapat, Sanket; Vyas, Renu; Padmakumar, Krishna Pillai (Combinatorial Chemistry & High Throughput Screening, 2015)
Natural products obtained from marine sources are considered to be a rich and diverse source of potential drugs. In the present work we demonstrate the use of chemoinformatics approach for the design of new molecules inspired by molecules from marine organisms. Accordingly we have assimilated information from two major scientific domains namely chemoinformatics and biodiversity informatics to develop an interactive marine database named MIMMO (Medicinally Important Molecules from Marine Organisms). The database can be queried for species, molecules, scaffolds, drugs, diseases and associated cumulative biological activity spectrum along with links to the literature resources. Molecular informatics analysis of the molecules obtained from MIMMO was performed to study their chemical space. The distinct skeletal features of the biologically active compounds isolated from marine species were identified. Scaffold molecules and species networks were created to identify common scaffolds from marine source and drug space. An analysis of the entire molecular data revealed a unique list of around 2000 molecules from which ten most frequently occurring distinct scaffolds were obtained.
Keywords: Chemoinformatics; Drug design; marine; virtual library

Chromerid genomes reveal the evolutionary path from photosynthetic algae to obligate intracellular parasites - Woo, Yong H.; Ansari, Hifzur; Otto, Thomas D.; Klinger, Christen M.; Kolisko, Martin; Michalek, Jan; Saxena, Alka; Shanmugam, Dhanasekaran; Tayyrov, Annageldi; Veluchamy, Alaguraj; Ali, Shahjahan; Bernal, Axel; et al. (Elife, 2015)
The eukaryotic phylum Apicomplexa encompasses thousands of obligate intracellular parasites of humans and animals with immense socio-economic and health impacts. We sequenced nuclear genomes of Chromera velia and Vitrella brassicaformis, free-living non-parasitic photosynthetic algae closely related to apicomplexans. Proteins from key metabolic pathways and from the endomembrane trafficking systems associated with a free-living lifestyle have been progressively and non-randomly lost during adaptation to parasitism. The free-living ancestor contained a broad repertoire of genes many of which were repurposed for parasitic processes, such as extracellular proteins, components of a motility apparatus, and DNA-and RNA-binding protein families. Based on transcriptome analyses across 36 environmental conditions, Chromera orthologs of apicomplexan invasion-related motility genes were co-regulated with genes encoding the flagellar apparatus, supporting the functional contribution of flagella to the evolution of invasion machinery. This study provides insights into how obligate parasites with diverse life strategies arose from a once free-living phototrophic marine alga.

Cyclic cationic peptides containing sugar amino acids selectively distinguishes and inhibits maturation of pre-mirnas of the same family - Nahar, Smita; Bose, Debojit; Pal, Sudip; Chakraborty, Tushar Kanti; Maiti, Souvik (Nucleic Acid Therapeutics, 2015)
The discovery of microRNAs (miRNAs) has added a new dimension to the gene regulatory networks, making aberrantly expressed miRNAs as therapeutically important targets. Small molecules that can selectively target and modulate miRNA levels can thus serve as lead structures. Cationic cyclic peptides containing sugar amino acids represent a new class of small molecules that can target miRNA selectively. Upon treatment of these small molecules in breast cancer cell line, we profiled 96 therapeutically important miRNAs associated with cancer and observed that these peptides can selectively target paralogous miRNAs of the same seed family. This selective inhibition is of prime significance in cases when miRNAs of the same family have tissue-specific expression and perform different functions. During these conditions, targeting an entire miRNA family could lead to undesired adverse effects. The selective targeting is attributable to the difference in the three-dimensional structures of precursor miRNAs. Hence, the core structure of these peptides can be used as a scaffold for designing more potent inhibitors of miRNA maturation and hence function.

Design and synthesis of 11 alpha-substituted bile acid derivatives as potential anti-tuberculosis agents - Pore, Vandana S.; Divse, Jaisingh M.; Charolkar, Chaitanya R.; Nawale, Laxman U.; Khedkar, Vijay M.; Sarkar, Dhiman (Bioorganic & Medicinal Chemistry Letters, 2015)
We have synthesized a series of novel 11 alpha-triazoyl bile acid derivatives. In addition, we also have synthesized N-alkyl and N-acyl derivatives of C-11 amino bile acid esters. All the compounds were evaluated for the inhibitory activity against Mycobacterium tuberculosis H37Ra (MTB) at 30 mu g/mL level. Four lead compounds (2b, 3, 7 and 8) were further confirmed from their dose dependent effect against MTB. These compounds were found to be active against Dormant and active stage MTB under both in vitro as well as within THP1 host macrophages. The most promising compound 2b showed strong antitubercular activities against MTB under in vitro and ex vivo (IC90 value of similar to 3 mu g/mL) conditions and almost insignificant cytotoxicity up to 100 mu g/mL against THP-1, A549 and PANC-1 human cancer cell lines. Inactivity of all these compounds against Gram positive and Gram negative bacteria indicates their specificity. Molecular docking studies of these compounds into the active site of DprE1 enzyme revealed a similar binding mode to native ligands in the crystal structure thereby helping to establish a structural basis of inhibition of MTB. The synthesized compounds were analyzed for ADME properties and showed potential to develop good oral drug candidates. Our results clearly indicate the identification of some novel, selective and specific inhibitors against MTB that can be explored further for potential antitubercular drug. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Antituberculosis; Bile acids; Cycloaddition; Docking study; In silico ADME

Diffusion of small solute particles in viscous liquids: cage diffusion, a result of decoupling of solute-solvent dynamics, leads to amplification of solute diffusion - Acharya, Sayantan; Nandi, Manoj K.; Mandal, Arkajit; Sarkar, Sucharita; Bhattacharyya, Sarika Maitra (Journal of Physical Chemistry B, 2015)
We study the diffusion of small solute particles through solvent by keeping the solute solvent interaction repulsive and varying the solvent properties. The study involves computer simulations, development of a new model to describe diffusion of small solutes in a solvent, and also mode coupling theory (MCT) calculations. In a viscous solvent, a small solute diffuses via coupling to the solvent hydrodynamic modes and also through the transient cages formed by the solvent. The model developed can estimate the independent contributions from these two different channels of diffusion. Although the solute diffusion in all the systems shows an amplification, the degree of it increases with solvent viscosity. The model correctly predicts that when the solvent viscosity is high, the solute primarily diffuses by exploiting the solvent cages. In such a scenario the MCT diffusion performed for a static solvent provides a correct estimation of the cage diffusion.

Discovery of new chemical entities against diseases of national importance :an HTS approach - Nawale, Laxman; Sarkar, Dhiman (National Science Day, At CSIR-NCL, 2015)

Effect of alkali and alkaline earth metal ions on benzyl alcohol oxidation activity of titanate nanotube-supported Au catalysts - Nepak, Devadutta; Srinivas, Darbha (RSC Advances, 2015)
Sodium titanate nanotubes (NaTNTs) were prepared by alkali treatment of anatase titania. They were then ion-exchanged with alkali and alkaline earth metal ions to get ATNTs (A = Li+, K+, Cs+, Mg2+, Ca2+, Sr2+ and Ba2+). Gold (1-5 wt%) was supported on these nanotubes by a deposition-precipitation method and investigated as a catalyst for the selective oxidation of benzyl alcohol with air/molecular oxygen (1 atm) under solvent-and alkali-free conditions. Detailed characterization by X-ray powder diffraction, high resolution transmission electron microscopy, N-2-physisorption, diffuse reflectance UV-visible spectroscopy, X-ray photoelectron spectroscopy and CO2-temperature-programmed desorption techniques revealed that the basicity of the catalyst influences the uptake, mean particle size, electronic properties and oxidation activity of the supported gold. Benzaldehyde formed with a selectivity of about 99%. The catalytic activity (turnover frequency) was found to have a direct relationship with the basicity and an inverse relationship with the Au particle size. Among the catalysts investigated, Au/BaTNTs, having higher basicity, smaller Au particles and higher metal dispersion, showed enhanced catalytic activity than the other Au/ATNT catalysts. Pd addition to Au leading to Au-Pd/BaTNTs increased the activity (TOF) but lowered the selectivity for benzaldehyde (80 wt%). Titanate nanotubes donate electron density to Au particles, yielding electron rich Au ions, which are responsible for activating molecular oxygen and oxidizing benzyl alcohol. Au/BaTNTs, having higher basicity and lower size Au nanoparticles than the other Au/ATNT, activates molecular oxygen more easily and thereby enhances the catalytic activity.

Efficacy study of potential anti-tubercular molecules: in-vitro and ex-vivo - Nawale, Laxman; Sarkar, Dhiman (National Science Day, 2015)
Tuberculosis: Infectious disease caused by the bacillus Mycobacterium tuberculosis Second leading infectious killer after HIV/AIDS In 2013, 8.6 million TB cases were reported out of which 1.3 million died Emergence of Multi-drug resistant TB (MDR-TB) and extremely drug resistant TB (XDR) for which no drugs are available. Latency being a cause of recurring TB infection is a major problem in eradication of TB

Enhanced electron field emission from NiCo2O4 nanosheet arrays - Naik, Kusha Kumar; Khare, Ruchita T.; Gelamo, Rogerio V.; More, Mahendra A.; Thapa, Ranjit; Late, Dattatray J.; Rout, Chandra Sekhar (Materials Research Express, 2015)
Electron emission properties of electrodeposited spinel NiCo2O4 nanosheet arrays grown on Ni foam have been studied. The work function of NiCo2O4 was calculated by density functional theory using the plane-wave basis set and used to estimate the field enhancement factor. The NiCo2O4 nanosheet arrays exhibited a low turn-on field of 1.86 V mu m(-1) at 1 mu A cm(-2) and current density of 686 mu A cm(-2) at 3.2 V mu m(-1), with field enhancement factor beta = 1460 and good field emission current stability. The field emission properties of the NiCo2O4 nanosheet arrays showed enhanced performance compared to chemically prepared NiCo2O4 nanosheets. Hence, the nanosheet arrays have great potential as robust high performance vertical structure electron emitters for future flat panel displays and vacuum electronic device applications.
Keywords: Density functional theory; field emission; nanosheets; NiCo2O4; spinel

Environmentally benign catalytic process for esterification of renewable levulinic acid to various alkyl levulinates biodiesel - Nandiwale, Kakasaheb Y.; Bokade, Vijay V. (Environmental Progress & Sustainable Energy, 2015)
This study explores, the use of modified zeolite (Micro/Meso-HZ-5) obtained by desilication post-treatment as heterogeneous catalyst for esterification of biomass derived renewable levulinic acid (LA) with different alkyl alcohols such as methanol, ethanol, n-butanol, and n-octanol aiming to produce corresponding alkyl levulinate. This method of production of alkyl levulinates would be sustainable process, as it can be used as novel miscible diesel biofuels preventing global warming by decreasing atmospheric CO2. The LA conversion obtained over Micro/Meso-HZ-5 was higher than H-ZSM-5, which is due to the combined effect of increase in Bronsted acid sites, total acidity, and other properties such as BET surface area and the generation of mesoporosity. The maximum LA conversion of 91, 95, 96, and 98% with 100% selectivity toward alkyl levulinate was obtained, when LA was being esterified over Micro/Meso-HZ-5 with methanol, ethanol, n-butanol, and n-octanol, respectively, at optimal process parameters. Micro/Meso-HZ-5 catalyst was found to be reusable for six cycles. Furthermore, pseudo homogeneous (P-H) kinetic model of the esterification of LA with the studied four alcohols were established with R-2>0.99, using the experimental data. A P-H kinetic model implies that, the esterification reaction follows second order reversible kinetics. (c) 2014 American Institute of Chemical Engineers Environ Prog, 34: 795-801, 2015
Keywords: biofuels; Esterification; kinetic model; levulinic acid; meso-HZ-5; micro

Esterification of renewable levulinic acid to n-butyl levulinate over modified H-ZSM-5 - Nandiwale, Kakasaheb Y.; Bokade, Vijay V. (Chemical Engineering & Technology, 2015)
The synthesis of n-butyl levulinate, one of the most important biodiesel additives, by catalytic esterification of biomass-derived levulinic acid (LA) with n-butanol over modified H-ZSM-5 (micro/meso-HZ-5) in a closed-batch system is reported for the first time. The optimization of the reaction conditions such as the reactant molar ratio, the catalyst loading, the reaction time and the temperature was performed in view to maximize the yield of n-butyl levulinate. Micro/meso-HZ-5 was found to be the most efficient catalyst, with 98% yield of n-butyl levulinate and a reusability for six cycles, which is higher than reported in the literature. A possible catalytic mechanism for the esterification reaction is also proposed. A second-order pseudo-homogeneous model with R-2 > 0.97 confirmed that the esterification reaction is performed in the kinetic regime due to the high activation energy of 23.84 kJ mol(-1).
Keywords: Esterification; kinetic model; levulinic acid; Micro/meso-HZ-5; n-Butyl levulinate

Experimental signature of microheterogeneity in ionic liquid-H2O systems and their perturbation by adding Li+ salts: a pulsed gradient spin-echo NMR approach - Nanda, Raju; Rajamohanan, P. R.; Kumar, Anil (Chemphyschem, 2015)
Distinct microheterogeneity has been observed in the [OMIM]Br-H2O system, which is interestingly perturbed by the addition of Li+ salts, indicating unusual diffusivity of [OMIM]Br and H2O molecules. However, the diffusional dynamics of water clusters show contrasting salting behavior at higher concentrations of Li+ salts, following the classical salting phenomenon in lower amounts. In contrast, the existing microheterogeneity in the [BMIM]Br-H2O system is weak enough to show any perturbation caused by the Li+ salts on the NMR time scale.
Keywords: ionic liquids; lithium; microheterogeneity; salt effect; viscosity

Fractional photo-current dependence of graphene quantum dots prepared from carbon nanotubes - Kundu, Sumana; Ghosh, Sujoy; Fralaide, Michael; Narayanan, T. N.; Pillai, Vijayamohanan K.; Talapatra, Saikat (Physical Chemistry Chemical Physics, 2015)
We report on the photo-conductivity studies of chemically synthesized graphene quantum dots (GQDs) of average size 12 nm obtained by the oxidative acid treatment of MWCNTs. The dependence of photocurrent I-ph (I-ph = I-ill - I-dark) on the laser intensity P under a wide range of laser intensities (5 mW <= P <= 60 mW) shows a fractional power dependence of I-ph on light intensity. The temperature dependence (300 K < T < 50 K) of I-ph observed in thin films of these GQDs indicates that in the higher temperature region (T > similar to 100 K), as the temperature increases, the number of thermally generated carriers increase resulting in increased I-ph. At sufficiently low temperatures (T <= 100 K), a constant I-ph is observed, indicating a constant photocarrier density. Such a behavior is typically observed in many photoactive disordered semiconductors, which are often used in a variety of applications. We believe that the investigations presented here will enhance our understanding of the photocurrent generation phenomenon in chemically obtained GQDs.

High throughput screening of inhibitors for tuberculosis at NCL : a novel drug discovery initiative from CSIR - Manek, Hardik; Nawale, Laxman; Jadhav, Nandadeep J.; Sarkar, Dhiman (73rd CSIR Foundation Day, at CSIR-National Chemical Laboratory, Pune, 2015)
Discover and develop novel drugs that are effective at curing latent, drug sensitive and drug resistant TB Study the biology of tuberculosis bacilli in great detail to identify new metabolic pathways that may be vulnerable to drugs Test thousands of potential drugs in our screening facility to find new compounds or new compound classes that kill TB bacteria Increase throughput up to 20,000 compounds at a time Develop novel screens using conditions that mimic those the TB bacteria encounters in the human body Utilize medical chemistry to optimize the structures of compounds so that they kill TB bacteria in a more potent fashion and are non-toxic Meet the challenges from industry

Hybrid perovskite films by a new variant of pulsed excimer laser deposition: a room-temperature dry process - Bansode, Umesh P.; Naphade, Rounak; Game, Onkar S.; Agarkar, Shruti A.; Ogale, Satishchandra (Journal of Physical Chemistry C, 2015)
A new variant of the classic pulsed laser deposition (PLD) process is introduced as a room-temperature dry process for the growth and stoichiometry control of hybrid perovskite films through the use of nonstoichiometric single target ablation and off-axis growth. Mixed halide hybrid perovskite films nominally represented by CH(3)NH(3)PbI(3-x)A(x) (A = Cl or F) are also grown and are shown to reveal interesting trends in the optical properties and photoresponse. Growth of good quality lead-free CH3NH3SnI3 films is also demonstrated, and the corresponding optical properties are presented. Finally, perovskite solar cells fabricated at room temperature (which makes the process adaptable to flexible substrates) are shown to yield a conversion efficiency of about 7.7%.

Identification and computational analysis of gene regulatory elements - Taher, Leila; Narlikar, Leelavati; Ovcharenko, Ivan (Cold Spring Harbor Protocols, 2015)
Over the last two decades, advances in experimental and computational technologies have greatly facilitated genomic research. Next-generation sequencing technologies have made de novo sequencing of large genomes affordable, and powerful computational approaches have enabled accurate annotations of genomic DNA sequences. Charting functional regions in genomes must account for not only the coding sequences, but also noncoding RNAs, repetitive elements, chromatin states, epigenetic modifications, and gene regulatory elements. A mix of comparative genomics, high-throughput biological experiments, and machine learning approaches has played a major role in this truly global effort. Here we describe some of these approaches and provide an account of our current understanding of the complex landscape of the human genome. We also present overviews of different publicly available, large-scale experimental data sets and computational tools, which we hope will prove beneficial for researchers working with large and complex genomes. © 2015 Cold Spring Harbor Laboratory Press.

Implementation of the Z-vector method in the relativistic-coupled-cluster framework to calculate first-order energy derivatives: Application to the SrF molecule - Sasmal, Sudip; Pathak, Himadri; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Physical Review A, 2015)
The molecular dipole moment and magnetic hyperfine-structure constant demand an accurate wave function far from the nucleus and in the near nuclear region, respectively. We, therefore, employ the so-called Z-vector method in the domain of relativistic-coupled-cluster theory to calculate the first-order property of molecular systems in their open-shell ground-state configuration. The implemented method is applied to calculate the molecular dipole moment and parallel component of the magnetic hyperfine-structure constant of the SrF molecule. The results of our calculation are compared with the experimental and other available theoretically calculated values. We are successful in achieving good accordance with the experimental results. The result of our calculation of the molecular dipole moment is in the accuracy of similar to 0.5%, which is clearly an improvement over the previous calculation based on the expectation value method in the four-component coupled-cluster framework [V. S. Prasannaa et al., Phys. Rev. A 90, 052507 (2014)]. Thus, it can be inferred that the Z-vector method can provide an accurate wave function in both the near and far nuclear region, which is evident from our calculated results.

Influence of cultivar, ripeness, blanching, drying, irradiation, and pectin recovery on alk(en)ylresorcinols in mango peels - Geerkens, Christian Hubert; Miller-Rostek, Petra; Matejka, Anna Elisabeth; Nene, Sanjay; Kammerer, Dietmar Rolf; Carle, Reinhold; Schweiggert, Ralf Martin (European Food Research and Technology, 2015)
The influence of different technological treatments on alk(en)ylresorcinol (AR) contents and pattern in mango peels was evaluated using peels from six different mango cultivars. AR concentrations were shown to highly depend on the cultivar. While high AR concentrations were observed in the analyzed monoembryonic cultivars, AR contents in the polyembryonic cultivar Nam Dokmai were significantly lower. Furthermore, for monoembryonic cultivars, AR levels in the peels of ripe fruits were found to be higher than in unripe ones, while AR levels in cv. Nam Dokmai were independent of the ripeness degree. Convective oven drying resulted in a significant reduction in AR contents when compared to lyophilization. Blanching prior to drying diminished AR yields, thus being unsuitable for satisfactory AR recovery. Gamma irradiation did not significantly affect the AR contents. Since depectinization of mango peels significantly concentrated AR amounts in the depectinized pomace, the consecutive extraction of pectin and ARs allows the dual valorization of mango peels. Considering the treatments investigated, the retention of ARs carrying saturated and unsaturated side chains did not differ under acidic conditions, heating, and irradiation, respectively. Consequently, the 1,3-dihydroxybenzene structure was concluded to be the most labile moiety of the AR molecule.
Keywords: Alkylresorcinol; By-products; Monoembryonic; Polyembryonic; Pomace; Ultrasound

Insect trehalase: physiological significance and potential applications - Shukla, Ekta; Thorat, Leena J.; Nath, Bimalendu B.; Gaikwad, Sushama M. (Glycobiology, 2015)
Trehalose, a non-reducing disaccharide, is widespread throughout the biological world. It is the major blood sugar in insects playing a crucial role as an instant source of energy and in dealing with abiotic stresses. The hydrolysis of trehalose is under the enzymatic control of trehalase. The enzyme trehalase is gaining interest in insect physiology as it regulates energy metabolism and glucose generation via trehalose catabolism. The two forms of insect trehalase namely, Tre-1 and Tre-2, are important in energy supply, growth, metamorphosis, stress recovery, chitin synthesis and insect flight. Insect trehalase has not been reviewed in depth and the information available is quite scattered. The present mini review discusses our recent understanding of the regulation, mechanism and biochemical characterization of insect trehalase with respect to its physiological role in vital life functions. We also highlight the molecular and biochemical properties of insect trehalase that makes it amenable to competitive inhibition by most glycosidase inhibitors. Due to its crucial role in carbon metabolism in insects, application of inhibitors against trehalose can form a promising area towards formulating strategies for insect pest control.
Keywords: carbohydrate metabolism; glycosidase inhibitor; glycoside hydrolase; trehalase; trehalose

Interesting viscosity changes in the aqueous urea-ionic liquid system: effect of alkyl chain length attached to the cationic ring of an ionic liquid - Nanda, Raju; Rai, Gitanjali; Kumar, Anil (Journal of Solution Chemistry, 2015)
In the present article, we demonstrate the effect of urea on the structure of the ionic liquids in their aqueous solutions through viscometric methods. We unravel the structure altering effect of urea in its aqueous solutions of ionic liquids possessing higher alkyl chains. The finding is an attempt to discern the anomalous behavior of urea as shown in the past with the help of many techniques. Interestingly, in the aqueous solutions of the imidazolium based ionic liquids having substitution of -C4H9 and -C6H13 groups on the imidazolium ring, urea exhibits kosmotropic behavior. Further increase in the substituted alkyl group such as -C8H17 alters the urea behavior to be chaotropic.
Keywords: Alkyl chain length; ionic liquids; Structure-breaker; Structure-maker; Urea; viscosity

Interlinked population balance and cybernetic models for the simultaneous saccharification and fermentation of natural polymers - Ho, Yong Kuen; Doshi, Pankaj; Yeoh, Hak Koon; Ngoh, Gek Cheng (Biotechnology and Bioengineering, 2015)
Simultaneous Saccharification and Fermentation (SSF) is a process where microbes have to first excrete extracellular enzymes to break polymeric substrates such as starch or cellulose into edible nutrients, followed by in situ conversion of those nutrients into more valuable metabolites via fermentation. As such, SSF is very attractive as a one-pot synthesis method of biological products. However, due to the co-existence of multiple biochemical steps, modeling SSF faces two major challenges. The first is to capture the successive chain-end and/or random scission of the polymeric substrates over time, which determines the rate of generation of various fermentable substrates. The second is to incorporate the response of microbes, including their preferential substrate utilization, to such a complex broth. Each of the above-mentioned challenges has manifested itself in many related areas, and has been competently but separately attacked with two diametrically different tools, i.e., the Population Balance Modeling (PBM) and the Cybernetic Modeling (CM), respectively. To date, they have yet to be applied in unison on SSF resulting in a general inadequacy or haphazard approaches to examine the dynamics and interactions of depolymerization and fermentation. To overcome this unsatisfactory state of affairs, here, the general linkage between PBM and CM is established to model SSF. A notable feature is the flexible linkage, which allows the individual PBM and CM models to be independently modified to the desired levels of detail. A more general treatment of the secretion of extracellular enzyme is also proposed in the CM model. Through a case study on the growth of a recombinant Saccharomyces cerevisiae capable of excreting a chain-end scission enzyme (glucoamylase) on starch, the interlinked model calibrated using data from the literature (Nakamura et al., Biotechnol. Bioeng. 53:21-25, 1997), captured features not attainable by existing approaches. In particular, the effect of various enzymatic actions on the temporal evolution of the polymer distribution and how the microbes respond to the diverse polymeric environment can be studied through this framework. Biotechnol. Bioeng. 2015;112: 2084-2105. (c) 2015 Wiley Periodicals, Inc.
Keywords: cybernetic modeling; population balance modeling; simultaneous saccharification and fermentation

Ionic conductivity probed in main chain liquid crystalline azobenzene polyesters - Nardele, Chinmay G.; Dhavale, Vishal M.; Sreekumar, K.; Asha, S. K. (Journal of Polymer Science Part A-Polymer Chemistry, 2015)
Three main chain thermotropic liquid crystalline (LC) azobenzene polymers were synthesized using the azobenzene twin molecule (P4P) having the structure Phenylazobenzene-tetraethyleneglycol-Phenylazobenzene as the AA monomer and diols like diethylene glycol, tetraethylene glycol (TEG), and hexaethylene glycol as the BB comonomer. Terminal C(O)OMe units on P4P facilitated transesterification with diols to form polyesters. All polymers exhibited stable smectic mesophases. One of the polymers, Poly(P4PTEG) was chosen to prepare composite polymer electrolytes with LiCF3SO3 and ionic conductivity was measured by ac impedance spectroscopy. The polymer/0.3 Li salt complex exhibited a maximum ionic conductivity in the range of 10(-5) S cm(-1) at room temperature (25 degrees C), which increased to 10(-4) S cm(-1) above 65 degrees C. The temperature dependence of ionic conductivity was compared with the phase transitions occurring in the sample and it was observed that the glass transition had a higher influence on the ionic conductivity compared to the ordered LC phase. Reversible ionic conductivity switching was observed upon irradiation of the polymer/0.3 Li salt complex with alternate UV and visible irradiation. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 629-641
Keywords: azo polymers; glass transition; liquid-crystalline polymers (LCP)

Lithium-assisted proton conduction at 150 degrees C in a microporous triazine-phenol polymer - Nandi, Shyamapada; Dhavale, Vishal M.; Shalini, Sorout; Werner-Zwanziger, Ulrike; Singh, Harpreet; Kurungot, Sreekumar; Vaidhyanathan, Ramanathan (Advanced Materials Interfaces, 2015)
Keywords: conduction; hydrophobic polar frameworks; lithiated polymers; proton conduction; triazine-phenol polymers

Mathematical modeling of combinatorial regulation suggests that apparent positive regulation of targets by miRNA could be an artifact resulting from competition for mRNA - Nyayanit, Dimpal; Gadgil, Chetan J. (RNA-A Publication of the RNA Society, 2015)
MicroRNAs bind to and regulate the abundance and activity of target messenger RNA through sequestration, enhanced degradation, and suppression of translation. Although miRNA have a predominantly negative effect on the target protein concentration, several reports have demonstrated a positive effect of miRNA, i.e., increase in target protein concentration on miRNA overexpression and decrease in target concentration on miRNA repression. miRNA-target pair-specific effects such as protection of mRNA degradation owing to miRNA binding can explain some of these effects. However, considering such pairs in isolation might be an oversimplification of the RNA biology, as it is known that one miRNA interacts with several targets, and conversely target mRNA are subject to regulation by several miRNAs. We formulate a mathematical model of this combinatorial regulation of targets by multiple miRNA. Through mathematical analysis and numerical simulations of this model, we show that miRNA that individually have a negative effect on their targets may exhibit an apparently positive net effect when the concentration of one miRNA is experimentally perturbed by repression/overexpression in such a multi-miRNA multitarget situation. We show that this apparent unexpected effect is due to competition and will not be observed when miRNA interact noncompetitively with the target mRNA. This result suggests that some of the observed unusual positive effects of miRNA may be due to the combinatorial complexity of the system rather than due to any inherently unusual positive effect of the miRNA on its target.
Keywords: combinatorial binding; mathematical model; miRNA; post-transcriptional regulation

Mechanism of alcohol oxidation by Fe-V(O) at room temperature - Ghosh, Munmun; Nikhil, Y. L. K.; Dhar, Basab B.; Sen Gupta, Sayam (Inorganic Chemistry, 2015)
{Selective oxidation of alcohol to its corresponding carbonyl compound is an important chemical process in biological as well as industrial reactions, The heme containing enzyme CytP450 has been known to selectively oxidize akohols to their corresponding carbonyl compounds. The mechanism of this reaction, which involves high-valent Fe-IV(O)-porphyrin(center dot+) intermediate with alcohol, has been well-studied extensively both with the native enzyme and with model complexes. In this paper, we report for the first time the mechanistic insight of, alcohol oxidation with Fe-V(O) complex of biuret TAML (bTAML), Which is isoelectronic with Fe-IV(O)-porphyrin(center dot+) intermediate form in CytP450. The oxidations displayed saturation kinetics, which allowed us to determine both the binding constants and first-order rate constants for the reaction. The K and k values observed for thel oxidation of benzyl alcohol by Fe-V(O) at room temperature (K = 300 M-1

Mechanistic understanding of rapid gelation of silk fibroin using a biosurfactant – sophorolipid - Dubey, Parul; Nawale, Laxman; Sarkar, Dhiman; Nisal, Anuya; Prabhune, Asmita (National Science Day, At CSIR-NCL, 2015)
3D polymeric hydrogels find use in biomedical applications as scaffolds and drug delivery vehicle • Silk fibroin a structural protein is a promising candidate (excellent thermo-mechanicals, biocompatibility, biodegradability) • Sophorolipid (SL)-a biosurfactant is known to exhibit antimicrobial, anti cancerous and cell differentiating. • Use of SL as gelling agent can enhance the applicability of SF hydrogels • SF-SL scaffolds obtained by lyophilization of hydrogels can find application in tissue regeneration

Molecular sieves and ultrasound-assisted synthesis of novel 1,3,4-oxadiazole-2-thiones derivatives as potential antifungal agents - Nikalje, Anna Pratima G.; Nimbalkar, Ms Urja D.; Tupe, Santosh; Vazquez, Julio A. Seijas; Tato, Maria Pilar Vazquez (19TH INTERNATIONAL ELECTRONIC CONFERENCE ON SYNTHETIC ORGANIC CHEMISTRY, 2015)
In the category of microorganism, fungi are considered as the special class of microbes responsible for opportunistic pathogenic infections in humans species. Due to the side effects of commercially available antifungal drugs and the emergence of new drug resistant fungal species in the past few years, has forced the researchers to search for novel and efficient antifungal drug molecules. The 1,3,4-oxadiazoles scaffold is associated with diverse biological activities. The multipurpose use of the Mannich bases in pharmaceutical chemistry promote us to prepare a new series of 5-(4-(benzyloxy)substituted phenyl)-3-((phenyl amino)methyl)-1,3,4oxadiazole-2(3H)-thione as antifungal agents. Herein, we report molecular sieves and ultrasound assisted synthesis of novel series of Mannich bases of the 5-substituted 1,3,4-oxadiazole-2-thiones by amino methylation with paraformaldehyde and substituted primary / secondary amines and their evaluation for antifungal activity. The structures of the newly synthesized compounds were determined by IR, NMR and Mass spectral study. The synthesized compounds exhibited interesting moderate to excellent antifungal activity against Candida albicans (NCIM 3557), Candida albicans(NCIM3471), Candida glabrata(NCIM3237), Cryptococcus neoformans (NCIM 3542), Cryptococcus neoformans(NCIM 3378), Aspergillus fumigates(NCIM 902), Aspergillus niger(NCIM 628) using Flucanazole as a standard reference drug. The synthesised compounds 6d, 6f,6g, 6h and 6j exhibited promising antifungal activity as antifungal agents.
Keywords: 1; 3; 4-oxadiazoles; Antifungal activity; Mannich reaction; Molecular sieves; Ultrasound -assisted

Multifaceted core-shell nanoparticles: superparamagnetism and biocompatibility - Sardar, Debasmita; Neogi, S. K.; Bandyopadhyay, Sanjoy; Satpati, Biswarup; Ahir, Manisha; Adhikary, Arghya; Jain, Ruchi; Gopinath, Chinnakonda S.; Bala, Tanushree (New Journal of Chemistry, 2015)
NicoreAgshell nanoparticles were synthesized by redox transmetallation reaction. Reduction potential match was encouraging to attempt the synthesis of the NicoreAushell system too. However, it could be achieved only after an effective surface modification on the Ni-core. Thorough characterization (UV-Vis spectroscopy, fluorescence spectroscopy, XRD, XPS, FTIR, TEM, and EDX) proved the necessity of surface modification and the success of synthesis of both types of core-shell structures. The chemical composition and topography were determined using STEM-HAADF analysis and EFTEM imaging. Fourier transform infrared (FTIR) spectroscopy confirmed the surface modification of Ni nanoparticles and the interactions involved between the ligands and metals (in the core and/or the shell) at various steps of the synthetic process. Even after the formation of the noble metal shell, the magnetic core was found to retain its superparamagnetic nature. In addition, the Au-shell protected the core from aerial oxidation and decreased toxicity as compared to pristine Ni nanoparticles as observed by MTT assay on normal cells (PBMCs).

Multifunctional silica nanoparticles for pancreatic cancer specific drug delivery and bioimaging - Nigam, Preeti; Sarkar, Dhiman (Journal of Chemistry & Applied Biochemistry, 2015)
Mesoporous silica nanoparticles (MSN) have attracted increasing interest as drug carriers due to their biocompatibility and robustness. In this analysis we explored the potential of MSN as nanotheranostic platform for pancreatic cancer specific drug delivery and bioimaging. Pancreatic cancer is the most fatal cancer and due to its high mortality and low prognosis it is imperative to develop new methods for early diagnosis and therapy of this cancer. Though traditionally organic dyes, quantum dots and fluorescent agents are used for bioimaging but here we have utilized graphene quantum dots (GQDs) for bioimaging due to their superior biocompatibility and fluorescence properties. MSN were loaded with gemcitabine; the most preferred drug for pancreatic cancer. MSN and GQDs were characterized by SEM, TEM, FT-IR etc and the efficacy of nanoformulation was determined by MTT assay.

Nanocrystalline Fe-Fe2O3 particle-deposited N-doped graphene as an activity-modulated Pt-free electrocatalyst for oxygen reduction reaction - Dhavale, Vishal M.; Singh, Santosh K.; Nadeema, Ayasha; Gaikwad, Sachin S.; Kurungot, Sreekumar (Nanoscale, 2015)
The size-controlled growth of nanocrystalline Fe-Fe2O3 particles (2-3 nm) and their concomitant dispersion on N-doped graphene (Fe-Fe2O3/NGr) could be attained when the mutually assisted redox reaction between NGr and Fe3+ ions could be controlled within the aqueous droplets of a water-in-oil emulsion. The synergistic interaction existing between Fe-Fe2O3 and NGr helped the system to narrow down the overpotential for the oxygen reduction reaction (ORR) by bringing a significant positive shift to the reduction onset potential, which is just 15 mV higher than its Pt-counterpart. In addition, the half-wave potential (E-1/2) of Fe-Fe2O3/NGr is found to be improved by a considerable amount of 135 mV in comparison to the system formed by dispersing Fe-Fe2O3 nanoparticles on reduced graphene oxide (Fe-Fe2O3/RGO), which indicates the presence of a higher number of active sites in Fe-Fe2O3/NGr. Despite this, the ORR kinetics of Fe-Fe2O3/NGr are found to be shifted significantly to the preferred 4-electron-transfer pathway compared to NGr and Fe-Fe2O3/RGO. Consequently, the H2O2% was found to be reduced by 78.3% for Fe-Fe2O3/NGr (13.0%) in comparison to Fe-Fe2O3/RGO (51.2%) and NGr (41.0%) at -0.30 V (vs. Hg/HgO). This difference in the yield of H2O2 formed between the systems along with the improvements observed in terms of the oxygen reduction onset and E-1/2 in the case of Fe-Fe2O3/NGr reveals the activity modulation achieved for the latter is due to the coexistence of factors such as the presence of the mixed valancies of iron nanoparticles, small size and homogeneous distribution of Fe-Fe2O3 nanoparticles and the electronic modifications induced by the doped nitrogen in NGr. A controlled interplay of these factors looks like worked favorably in the case of Fe-Fe2O3/NGr. As a realistic system level validation, Fe-Fe2O3/NGr was employed as the cathode electrode of a single cell in a solid alkaline electrolyte membrane fuel cell (AEMFC). The system could display an open circuit voltage (OCV) of 0.73 V and maximum power and current densities of 54.40 mW cm(-2) and 200 mA cm(-2), respectively, which are comparable to the performance characteristics of a similar system derived by using 40 wt% Pt/C as the cathode electrode.

Nanostructured 2D MoS2 honeycomb and hierarchical 3D CdMoS4 marigold nanoflowers for hydrogen production under solar light - Kadam, Sunil R.; Late, Dattatray J.; Panmand, Rajendra P.; Kulkarni, Milind V.; Nikam, Latesh K.; Gosavi, Suresh W.; Park, Chan J.; Kale, Bharat B. (Journal of Materials Chemistry A, 2015)
Unique two dimensional (2D) honeycomb layered MoS2 nanostructures and hierarchical 3D marigold nanoflowers of CdMoS4 were designed using a template free and facile solvothermal method. The MoS2 structure is depicted with a sheet like morphology with lateral dimensions of 5-10 mu m and a thickness of similar to 200 nm and a honeycomb nanostructure architecture produced via the self-assembling of vertically grown thin hexagonal nanosheets with a thickness of 2-3 nm. The 3D CdMoS4 marigold nanoflower architecture comprised thin nanopetals with lateral dimensions of 1-2 mu m and a thickness of a few nm. The CdMoS4 and MoS2 structures displayed hydrogen ( H-2) production rates of 25 445 and 12 555 mu mol h(-1) g(-1), respectively. The apparent quantum yields of hydrogen production were observed to be 35.34% and 17.18% for CdMoS4 and MoS2, respectively. The 3D nanostructured marigold flowers of CdMoS4 and honeycomb like 2D nanostructure of MoS2 were responsible for higher photocatalytic activity due to inhibition of the charge carrier recombination. The prima facie observation of H-2 production showed that the ternary semiconductor confers enhanced photocatalytic activity for H-2 generation due to its unique structure. Such structures can be designed and implemented in other transition metal dichalcogenide based ternary materials for enhanced photocatalytic and other applications.

New butenolide cinnamate and other biological active chemical constituents from Polygonum glabrum - Said, Madhukar S.; Chinchansure, Ashish A.; Nawale, Laxman; Durge, Ankita; Wadhwani, Ashish; Kulkarni, Smita S.; Sarkar, Dhiman; Joshi, Swati P. (Natural Product Research, 2015)
Phytochemical investigation of the methanol extract of the aerial parts of Polygonum glabrum afforded one new natural product (-)-2-methoxy-2-butenolide-3-cinnamate (1) along with six known compounds, -hydroxyfriedalanol (2), 3-hydroxy-5-methoxystilbene (3), (-) pinocembrin (4), sitosterol-(6-O-palmitoyl)-3-O–d-glucopyranoside (5), (-) pinocembrin-5-methyl ether (6) and sitosterol-3-O–d-glucopyranoside (7). Compound 1 showed promising in vitro anti-HIV-1 activity against primary isolates HIV-1(UG070) (X4, subtype D) and HIV-1(VB59) (R5, subtype C) assayed using TZM-bl cell line with IC50 in the range of 15.68-22.43g/mL. The extract showed TI in the range of 19.19-27.37 with IC50 in the range of 10.90-15.55g/mL. Compounds 1, 3 and 4 exhibited in vitro anti-mycobacterium activity against Mycobacterium tuberculosis H37Ra with IC50 values of 1.43, 3.33 and 1.11g/mL in dormant phase and 2.27, 3.33 and 1.21g/mL in active phase, respectively. Compound 4 was found to be the most active antiproliferative with IC50 values of 1.88-11.00g/mL against THP-1, A549, Panc-1, HeLa and MCF7 cell lines.
Keywords: anti-HIV-1; anti-mycobacterium; antiproliferative; phytochemicals; Polygonaceae; Polygonum glabrum

Nonconventional chemical inhibitors of microRNA: therapeutic scope - Jayaraj, Gopal Gunanathan; Nahar, Smita; Maiti, Souvik (Chemical Communications, 2015)
MicroRNAs (miRNAs) are a class of genomically encoded small RNA molecules (similar to 22nts in length), which regulate gene expression post transcriptionally. The term microRNA or miRNA was coined in 2001, and research in the past decade has shed light on their widespread occurrence, evolutionary conservation and tissue specific functions. It is estimated that they modulate the gene expression of approximately 60% of the mammalian genes by regulating the levels of target mRNAs to which they can bind on the basis of sequence complementarities. miRNAs are produced in a well coordinated series of steps from being transcribed in the nucleus to exerting their function in the cytoplasm. miRNAs are now implicated in diverse biological phenomena ranging from development to stress response which makes miRNAs one of the central regulatory molecules which modulate information flow along the central dogma of gene expression. More importantly, like any regulatory molecule, deregulation of miRNAs is causally associated with several diseases (mainly cancer) and is directly involved in a variety of pathophysiologies owing to their aberrant expression. Thus, modulation of miRNA levels is of prime therapeutic importance. Conventional methods of miRNA knockdown using chemically modified antisense-oligonucleotides have been explored extensively but face the challenges of modes of delivery, biostability and biodistribution. This calls for the development of more alternative and non-conventional methods to target miRNA. Small molecules targeting RNA chemical and structural space provide one such timely opportunity. In this article we first provide a brief overview of miRNA biogenesis and its disease associations. We then summarize the major developments in conventional oligonucleotide based approaches to miRNA knockdown and its status. We then focus on the more non-conventional methods like oligonucleotide enzymes and small molecules and provide an outlook on the future of such methods.

Nonomuraea indica sp nov., novel actinomycetes isolated from lime-stone open pit mine, India - Quadri, Syed Raziuddin; Tian, Xin-Peng; Zhang, Jing; Li, Jie; Nie, Guo-Xing; Tang, Shu-Kun; Al Ruwaili, Jamal; Agsar, Dayanand; Li, Wen-Jun; Dastager, Syed Gulam (Journal of Antibiotics, 2015)
A Gram-positive, aerobic, nonmotile actinomycete strain designated DRQ-2(T) was isolated from the soil sample collected from limestone open pit mine from the Gulbarga region, Karnataka province, India. Strain DRQ-2(T) was identified as a member of the genus Nonomuraea by a polyphasic approach. Strain DRQ-2(T) could be differentiated from other members of the genus Nonomuraea on the basis of physiology and 16S rRNA gene sequence analysis. The 16S rRNA gene sequence similarity of strain DRQ-2(T) showed highest sequence similarity to Nonomuraea muscovyensis DSM 45913(T) (99.1%), N. salmonea DSM 43678(T) (98.2%) and N. maheshkhaliensis JCM 13929(T) with 98.0%, respectively. Chemotaxonomic properties showing predominant menaquinones of MK-9 (H-4), MK-9(H-2) and MK-9(H-6), major polar lipids comprised diphosphatidylglycerol, phosphatidylmono methyl ethanolamine (PME), phosphatidylethanolamine (PE), hydroxy-PME (OH-PME), hydroxy PE (OH-PEE), phosphatidylglycerol (PG), ninhydrin-positive phosphoglycolipid and unknown phospholipid, fatty acids with major amounts of i-C-16:0, ai-C-15:0 and ai-C-17:0 supported allocation of the strain to the genus Nonomuraea. Results of DNA-DNA hybridization and physiological tests allowed genotypic and phenotypic differentiation of strain DRQ-2(T) from closely related species. The genomic DNA G+C content of the organism was 72.5 mol%. On the basis of phenotypic, chemotypic and molecular characteristics, strain DRQ-2(T) represents a novel species of the genus Nonomuraea, for which the name N. indica sp. nov. is proposed, with type strain DRQ-2(T) (= NCIM 5480(T) = CCTCC AA 209050(T)).

One step synthesis of ethyl levulinate biofuel by ethanolysis of renewable furfuryl alcohol over hierarchical zeolite catalyst - Nandiwale, Kakasaheb Y.; Pande, Ashwini M.; Bokade, Vijay V. (RSC Advances, 2015)
Ethanolysis of renewable furfuryl alcohol (FAL) to ethyl levulinate (EL) biofuel over various zeolites viz. H-ZSM-5 (microporous, medium pore), Hierarchical-HZ-5 (combination of micro-and meso pore), H-Beta (microporous, large pore) and Ultra Stable Y (USY, microporous, large pore) was studied in detail. To the best of our knowledge, probably for the first time, Hierarchical-HZ-5 synthesized by desilication post-treatment has been employed as a heterogeneous catalyst for ethanolysis of FAL. The synthesized catalysts were characterized by powder X-ray diffraction (PXRD), temperature programmed NH3 desorption (TPAD), Energy dispersive X-ray analysis (EDAX), etc. Response surface methodology (RSM) with Box-Behnken experimental design (BBD) was used to investigate the influence of three crucial process variables of ethanolysis such as ethanol to FAL molar ratio, percent catalyst loading and reaction temperature on EL yield. The optimization tool of design expert software was employed to obtain the optimum reaction parameters for FAL ethanolysis over Hierarchical-HZ-5 catalyst. Three intermediates of FAL ethanolysis reaction such as, ethoxymethylfuran (EMF), 4,5,5-triethoxypentan-2-one and diethyl ether (DEE) have been identified and quantified from the product mixture with the aid of Gas Chromatography-Mass Spectroscopy (GC-MS). Hierarchical-HZ-5 was found to be a potential catalyst for ethanolysis of FAL with 73% EL yield and 26% EMF yield at optimized process parameters.

OpenFOAM computational fluid dynamic simulations of single-phase flows in an advanced-flow reactor - Nieves-Remacha, Maria Jose; Kukarni, Amok A.; Jensen, Klavs F. (Industrial & Engineering Chemistry Research, 2015)
Computational fluid dynamic (CFD) simulations are carried out for single-Phase flow in an, advanced-flow reactor (AFR) using the open source software OpenFOAM. Excellent agreement of Simulations with experimental pressure drop and residence time distribution (RTD) is obtained. Streamlines, stagnant zones, Velocity profiles, and pressure fields are,obtained at different flow rates ranging from 5 to 100 mL/min. A change in the flow behavior with the presence of recirculation zones is observed with a 40 mL/min flow rate. The extent of the recirculation zones increases with increasing flow rate from 40 to 60 mL/min and is limited further by the presence of a second cylindrical post inside the heart cell, remaining almost constant in the flow rate range of 60-100 mL/min. The RTD is also determined for all flow rates, and a. comparison between different reactor designs (two-post, single-post, and low-flow-reactor-like single-post) is presented. The APR Shows a plug-flow behavior with a small degree of dispersion, which broadens the RTD. Symmetric RTD curves are obtained for the single-post designs, whereas the Gen 1 APR design experiences asymmetry in the RTD at flow rates in the range between 20 and 60 mL/min.

Oxidative and membrane stress-mediated antibacterial activity of WS2 and rGO-WS2 nanosheets - Navale, Govinda R.; Rout, Chandra Sekhar; Gohil, Kushal N.; Dharne, Mahesh S.; Late, Dattatray J.; Shinde, Sandip S. (RSC Advances, 2015)
Graphene-based materials have strong cytotoxic attributes against bacteria due to their unique physicochemical properties. We examined the antibacterial activities of nanosheets of the graphene analogue tungsten disulphide (WS2) and a composite of reduced graphene oxide-tungsten disulphide (rGO-WS2), comparing them with reduced graphene oxide (rGO) by a time and concentration dependent viability assay and growth curve studies against four bacterial strains: Gram negative Escherichia coli (E. coli) and Salmonella typhimurium (S. typhimurium), and Gram positive Bacillus subtilis (B. subtilis) and Staphylococcus epidermidis (S. epidermidis). The nanosheets of the rGO-WS2 composite caused a more significant retardation in bacterial growth and inhibitory effect on the tested bacterial strains than WS2, followed by rGO. The tested E. coli and B. subtilis strains were more susceptible than the other strains. A mechanistic study revealed that rGO and WS2 did not produce the superoxide anion (O-2(-)) or reactive oxygen species (ROS), but the nanocomposite of rGO-WS2 did produce both. However, all these materials did oxidize glutathione, which serves as a redox state mediator in bacteria. We conclude that the antimicrobial mechanism is due to the combined effect of initial cell deposition on the rGO-WS2 materials, the membrane stress due to direct contact with the nanosheets, and the produced superoxide anion-independent oxidation mechanisms. The beneficial aspects of the physicochemical properties of rGO-WS2, such as its size and conductivity, can be precisely customized to reduce its health and environmental risk factors.

Pd loaded amphiphilic COF as catalyst for multi-fold Heck reactions, C-C couplings and CO oxidation - Mullangi, Dinesh; Nandi, Shyamapada; Shalini, Sorout; Sreedhala, Sheshadri; Vinod, Chathakudath P.; Vaidhyanathan, Ramanathan (Scientific Reports, 2015)
COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd-0 nanoparticles into it. An 18-20% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) < 0.05 mol%, average TON 1500) catalyzing simultaneous multiple site Heck couplings and C-C couplings using `non-boronic acid' substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100% conversion of CO to CO2 at 150 degrees C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable.

Pharmacophore and docking based virtual screening of validated mycobacterium tuberculosis targets - Vyas, Renu; Karthikeyan, Muthukumarasamy; Nainaru, Ganesh; Muthukrishnan, Murugan (Combinatorial Chemistry & High Throughput Screening, 2015)
Target based virtual screening has surpassed ligand based virtual screening methods in the recent past mainly as it provides more clues regarding intermolecular interactions and takes into consideration the flexible receptor as well. The current methodology describes a computational strategy of predicting Mycobacterium tuberculosis (M. tuberculosis) binders for five well studied targets representing M. tuberculosis proteome encompassing most of the known mechanisms of action. The diversity of the targets was affirmed by their active site analysis and structural studies. The current approach employed pharmacophore searching, docking and clustering techniques in tandem and was validated by enrichment studies using the available Schrodinger data set consisting of 1000 decoys. The application of this methodology was demonstrated by predicting potential molecular targets for fifty newly synthesized compounds. Cross docking studies on the targets were carried out with 4512 known inhibitors utilizing a high performance computing platform to reveal underlying affinity and promiscuity patterns. Optimum binding energy range for all targets as determined by high throughput docking was found to be -3 to -13 kcal/mol.
Keywords: Binding energy; docking; Mycobacterium tuberculosis; open source drug discovery (OSDD); pharmacophore; structure based drug design (SBDD)

Phase behavior, diffusion, structural characteristics, and pH of aqueous hydrophobic ionic liquid confined media: insights into microviscosity and microporsity in the [C(4)C(4)im][NTf2] + water system - Nanda, Raju; Kumar, Anil (Journal of Physical Chemistry B, 2015)
We present our studies on the physicochemical properties of water confined in Dibutylimidazolium bis(trifluoromethanesulfonylimide) ([C(4)C(4)im][NTf2]) reverse micelles through the NMR relaxation measurements that provide us an understanding of microviscosity and pH in the confined condition. We present experimental results on phase behavior, diffusion, structural characteristics and pH in aqueous ionic liquid-confined media. The ternary phase diagram was constructed by the cloud point measurements and the microheterogeneous regions were detected by the measurement of bulk viscosity and diffusion coefficients of K-4[Fe(CN)(6)] inside the homogeneous microemulsion systems through the cyclic voltammetric (CV) measurements. The size of the microemulsion systems was characterized by the dynamic light scattering (DLS) method. The H-1 NMR spectra of homogeneous microemulsion systems were taken which indicates the presence of bound and free water molecules inside the microemulsion system. The NMR spinlattice relaxation time (T-1) of water molecules in its homogeneous microemulsion systems were measured and the reorientational correlation time (t(c)) of water molecules obtained from it indicates that the fluidity of homogeneous confined media decreases with the decrease in the composition of water. Microviscosity of the aqueous confined media was calculated from the measured T-1 relaxation time values by applying the DebyeStokes equation and correlated with the bulk viscosity of the samples. It was observed that both the microviscosity and bulk viscosity show inverse relationship. The fraction of bound and free water molecules were calculated from the measured T-1 values. NMR spinspin relaxation time (T-2) of water molecules in its homogeneous microemulsion systems were measured with the varying pH of the aqueous core. A change in the T-2 relaxation time of the water proton was observed proposing an exchange of proton between the H2O and -OH group of the TX-100 molecules. Finally, methyl orange (MO) was used as a UVvis spectrophotometric molecular probe and the measured lambda(max) values of the probe were used for the detection of micropolarity of the homogeneous aqueous confined media and was found to be increase with the increase in the size of the confined media.

Phosphonated USY, a promising catalyst for the development of environmentally benign biodiesel (methyl acetate) process - Nandiwale, Kakasaheb Y.; Gopal, Gahana C.; Bokade, Vijay V. (Journal of Energy Chemistry, 2015)
The present study focuses on the evaluation of the potential applicability of Ultra Stable Y (USY) and phosphonated USY (1 wt%-4 wt% phosphorous loading) as heterogeneous catalysts for biodiesel (methyl acetate) production. The synthesized catalysts were characterized by powder X-ray diffraction (XRD), Brunaer-Emmett-Teller (BET) surface area, total acidity by temperature-programmed desorption of ammonia (TPD-NH3) and Fourier Transform Infrared (FTIR) spectra. The performances of catalysts were evaluated for the transesterification of butyl acetate with methanol (a model reaction in biodiesel production). In view to obtain a maximum yield of methyl acetate, the optimization of process parameters such as reactant molar ratio, catalyst loading, reaction temperature and reaction time was performed. All the phosphonated USY catalysts showed higher catalytic activity than the parent USY, which can be attributed to the increase of total acidity due to phosphonation. 2 wt% P/USY (2% phosphorous loaded on USY) exhibited 92% methyl acetate yield with 100% selectivity, which was proved to be a potential catalyst for biodiesel production. The invented catalyst was found to be stable and reusable for five catalytic cycles, demonstrating that it might be a environmentally benign catalytic process.
Keywords: Biodiesel; methyl acetate; phosphonated USY; transesterification

Potent inhibition of miR-27a by neomycin-bisbenzimidazole conjugates - Nahar, Smita; Ranjan, Nihar; Ray, Arjun; Arya, Dev P.; Maiti, Souvik (Chemical Science, 2015)
miRNAs are important components of regulatory networks that control gene expression and have implications in various diseases including cancer. Targeting oncogenic miRNAs with small molecules is currently being explored to develop cancer therapeutics. Here, we report the development of dual binding neomycin-bisbenzimidazole conjugates that target oncogenic miR-27a with high affinity (K-a = 1.2 to 7.4 x 10(8) M-1). These conjugates bring significant reduction (similar to 65% at 5 mu M) in mature miRNA levels and penetrate easily in the cells where they localise both in the cytoplasm and the nucleus. Cell cycle analysis showed significant increase in the G0/G1 phase (similar to 15%) and decrease in the S phase (similar to 7%) upon treatment with neomycin-bisbenzimidazole conjugates, suggesting inhibition of cell proliferation. Using the conjugation approach, we show that moderately binding ligands can be covalently combined into high affinity binders. This study also highlights the role of linker optimization in designing high affinity ligands for miR-27a targeting.

Preparation and characterization of flexible ferromagnetic nanocomposites for microwave applications - Thomas, Teena; Kanoth, Bipinbal P.; Nijas, C. M.; Joy, Pattayil Alias; Joseph, Joseph M.; Kuthirummal, Narayanan; Thachil, Eby T. (Materials Science and Engineering B-Advanced Functional Solid-State Materials, 2015)
Magnetic Fe3O4 nanoparticles (similar to 20 nm) were synthesized using the chemical co-precipitation method with a view of developing flexible and easily processable ferromagnetic materials with high mouldability to be used as microwave absorbers. The nanoparticles prepared were incorporated into natural rubber through latex stage processing. This novel processing method gives better dispersion of particles in the rubber matrix. The composites were characterized using XRD, SEM, vibrating sample magnetometer, dynamic mechanical analyzer, cavity perturbation, thermogravimetry (TGA), and Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS). A notable improvement in the mechanical properties of composites was observed upon adding Fe3O4 particles. Magnetic and microwave characteristics of the composites indicate the formation of a flexible ferromagnetic material with good microwave absorption characteristics. (C) 2015 Published by Elsevier B.V.
Keywords: Fe3O4; Ferromagnetic; FTIR-PAS; Microwave absorption; Natural rubber; SEM; XRD

Process optimization by response surface methodology for transesterification of renewable ethyl acetate to butyl acetate biofuel additive over borated USY zeolite - Nandiwale, Kakasaheb Y.; Galande, Nitish D.; Bokade, Vijay V. (RSC Advances, 2015)
Butyl acetate, a renewable biofuel additive was synthesized by transesterification of butanol with ethyl acetate via a renewable and sustainable route. Use of fermentation derived bio-butanol and bio-ethyl acetate for synthesis of butyl acetate would be a more advantageous route over conventional Fischer Esterification. For the first time, a heterogeneous zeolite catalyst such as Ultra Stable Y (USY) and its modified versions obtained by borating on parent USY were used for the synthesis of butyl acetate. Response surface methodology (RSM) was employed to optimize the process parameters for transesterification of butanol with ethyl acetate over a 4% (w/w) B-USY catalyst. The influence of three crucial process variables such as catalyst loading, molar ratio, and reaction temperature on yield of butyl acetate were addressed by Box-Behnken experimental design (BBD). 4% (w/w) B-USY was proved to be a potential catalyst with 96% yield of butyl acetate at optimum process parameters. The 4% (w/w) B-USY catalyst was found to be reusable for 6 catalytic cycles.

Production of polyunsaturated fatty acids in recombinant lipomyces starkeyi through submerged fermentation - Salunke, Devyani; Manglekar, Rupali; Gadre, Ramchandra V.; Nene, Sanjay; Harsulkar, Abhay M. (Bioprocess and Biosystems Engineering, 2015)
Long chain polyunsaturated fatty acids (LCPUFA) are known to play an important role in human health and nutrition. Considering the limitation of LCPUFA sources, it is necessary to search new avenues for their production. Oleaginous yeasts are an attractive target for harvesting single cell oil, mainly because of the ease of cultivation with cheaper raw material. Lipomyces starkeyi is one such oleaginous yeast, which can accumulate oil to the extent of 60 % of its biomass and where genetic transformation can be achieved. In our earlier work, Delta 15 desaturase gene (AEP37840) from flax was transformed into L. starkeyi. In the present work, we report optimization of medium for the production of omega-3 enriched oil from this transformed yeast. A basic medium containing 20 g/l glucose as a carbon source and 10 g/l yeast extract as a nitrogen source was used during fermentation. At regular time intervals, glucose was fed to maintain high C:N ratio (65:10) during fermentation. Under the most favorable conditions, dry biomass and total lipid content were 18 and 7.29 g/l, respectively. Prior to genetic transformation, L. starkeyi contained 56.03 mg/l DHA along with 71.4 mg/l EPA and 42.2 mg/l ALA. Genetic engineering of this yeast resulted in a strain that produced 1080 mg/l DHA (17.4 %) along with 74.28 mg/l EPA and 126.72 mg/l ALA possibly through modification of PUFA biosynthetic pathway. To the best of our knowledge, this is a first report of DHA enrichment and opens up avenues for LCPUFA production through L. starkeyi.
Keywords: Fermentation; LCPUFA; Lipid production; Oleaginous yeast

Purification and characterization of an agglutinin from datura innoxia with antineoplastic activity - Singh, Ruby; Nawale, Laxman; Gaikwad, Sushama M.; Suresha, C. G. (National Science Day, At CSIR-NCL, 2015)
Lectins are carbohydrate binding proteins of non-immune origin. Due to their multivalency, lectins can be easily detected using agglutination. Lectins are reported to induce cytotoxicity or inhibition of growth in various cancer cells., hence good therapeutic startegy against cancer. Factors such as specificity, stability, assay rapidity, and costs combine to make lectins attractive diagnostic reagents. Datura innoxia belongs to family of Solanaceae.All parts of the plant are hallucinogenic, hypnotic and narcotic. Application: at low dose acts as pain killer, relieves asthma and rheumatism.

Quantitative, automated, high content screening assay approach to anti-angiogenicdrug discovery - Nawale, Laxman; Sarkar, Dhiman (National Science Day, At CSIR-NCL, 2015)
Angiogenesisenhancescancer,maculardegeneration,etc.. Currentangiogenicassays--indirect,manual,timeconsuming,laborintensive,difficulttoquantify,andexpensive. Wedevelopedanautomated,quantitative,HighContentScreeningangiogenictubeformationassaywouldbenefitdrugdiscoveryforseveraltherapeuticareas. Humanendothelialcellswereseededwithpro-oranti-angiogeniccompoundsonaMatrigelTMlayerina96-wellplate.Afterangiogenictubesformation,thepositivecontrolsandthetestsampleswerefixed,fluorescentlylabeled,automaticallyimagedonCellomics’ArrayScan®HCSReader,andquantitativelyanalyzedon-the-flybytheTubeFormationBioApplicationsoftwaremodule. Multiplefeaturesrelevantforangiogenesisandangiogenictubeformationwereautomaticallymeasured. Thisrobustandreliableassaythusenabledthelarge-scale,quantitative,screeningandcharacterizationofcompoundsaffectingbothpro-andanti-angiogenicpathways.

Rational drug design, synthesis and biological evaluation of dihydrofolate reductase inhibitors as antituberculosis agents - Tawari, Nilesh R.; Bag, Seema; Raju, Archana; Lele, Arundhati C.; Bairwa, Ranjeet; Ray, Mukti Kanta; Rajan, M. G. R.; Nawale, Laxman U.; Sarkar, Dhiman; Degani, Mariam S. (Future Medicinal Chemistry, 2015)
Background: A series of 2,4-diamino-s-triazines was designed, with potential for activity against Mycobacterium tuberculosis (Mtb) dihydrofolate reductase enzyme, on the basis of virtual screening results and structure-based drug design. Results: The compounds were evaluated against Mtb (H(37)Rv) and their cytotoxicity was assessed using VERO cell lines. Of particular note, two compounds were found to have the most promising antituberculosis activity (6b minimum inhibitory concentration: 1.76 mu M and 6i minimum inhibitory concentration: 1.57 mu M) along with low cytotoxicity (CC50 : > 300 mu M). The enzyme assay results of these two indicated significant inhibition of Mtb dihydrofolate reductase along with selectivity. Selected derivatives were tested against dormant tubercle bacilli in vivo and ex vivo indicating potential inhibition. Conclusion: This study provides promising antituberculosis dihydrofolate reductase inhibitors that can act as potential leads for further development.

Rational preparation of Ag and Au bimetallic catalysts for the hydrocarbon-SCR of NOx: sequential deposition vs. coprecipitation method - More, Pavan M.; Nguyen, D. L.; Dongare, Mohan K.; Shubhangi B. Umbarkar; Nuns, N.; Girardon, J. S.; Dujardin, Christophe; Lancelot, Christine; Mamede, Anne-Sophie; Granger, P. (Applied Catalysis B-Environmental, 2015)
This study emphasizes the importance of the preparation method for bimetallic Au-Ag catalysts supported on alumina in the selective reduction of NOx by hydrocarbons with gas feed compositions representative of diesel fuelled engine exhaust gas. An optimal balance between oxidative and reductive surface properties is obtained when Au and Ag are successively introduced. Significant re-dispersion processes take place when the catalyst runs at 500 degrees C leading to a gain in activity at low temperature and ascribed to a better interaction between Au and Ag species. Co-precipitation leads to a preferential formation of intermetallic Au-Ag particles which is detrimental to the catalytic performances. Aging at 500 degrees C leads to a significant particle sintering and a strengthening of the metallic character. (C) 2014 Elsevier B.V. All rights reserved.
Keywords: Au-Ag particles; Co-precipitation; DeNO(x) reaction; HC-SCR

Recent advances in employing homoenolates generated by N-heterocyclic carbene (NHC) catalysis in carbon-carbon bond-forming reactions - Menon, Rajeev S.; Biju, Akkattu T.; Nair, Vijay (Chemical Society Reviews, 2015)
The use of NHCs for generating homoenolate species has gained widespread popularity in recent years. A number of highly stereoselective processes of NHC-homoenolates have emerged. Homoenolate reactions have also been employed as key steps in the total synthesis of a number of natural products. The use of compatible co-catalysts, improved NHC-catalyst design and the use of novel precursors for homoenolate generation are among the major developments in this area that were disclosed recently. This tutorial review organises and presents the advancements in this rapidly growing area of catalysis and in the process updates a previous account published in 2011 in this journal.

Relativistic extended coupled cluster method for magnetic hyperfine structure constant - Sasmal, Sudip; Pathak, Himadri; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Physical Review A, 2015)

Release of a guest by disassembling a capsule through a photo triggering process - Nithyanandhan, Jayaraj; Jagadesan, P.; Samanta, S. R.; Da Silva, J. P.; Ramamurthy, V. (Organic Letters, 2015)

Renewable fuels from biomass-derived compounds: Ru-containing hydrotalcites as catalysts for conversion of HMF to 2,5-dimethylfuran - Nagpure, Atul S.; Venugopal, Ashok Kumar; Lucas, Nishita; Manikandan, Marimuthu; Thirumalaiswamy, Raja; Chilukuri, Satyanarayana V. (Catalysis Science & Technology, 2015)
Production of transportation fuels from renewable biomass is hugely important considering the current ecological concerns over CO2 built up in the atmosphere. Ruthenium-containing hydrotalcite (HT) catalysts were applied for the selective hydrogenolysis of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF). Structural and morphological features of the catalysts were examined using various physico-chemical characterization techniques. The influence of various reaction parameters, such as reaction temperature, solvent, Ru content of the catalyst, etc., was investigated with respect to HMF conversion and DMF yield. The study clearly shows that well-dispersed Ru nanoparticles are highly active and selective in the conversion of HMF to DMF. A catalyst containing only 0.56 wt% Ru converted 100 mol% HMF to yield 58 mol% DMF. This catalyst was found to be recyclable as the activity was retained even after five cycles of reaction. 2-Propanol was found to be a good solvent as it helped to improve DMF yield through transfer hydrogenation. Based on the results of the investigations, a reaction pathway for the conversion of HMF to DMF was proposed for the present Ru-based catalyst system.

Reversal of H-bonding direction by N-sulfonation in a synthetic reverse-turn peptide motif - Vijayadas, Kuruppanthara N.; Kotmale, Amol S.; Thorat, Shridhar H.; Gonnade, Rajesh G.; Nair, Roshna V.; Rajamohanan, Pattuparambil R.; Sanjayan, Gangadhar J. (Organic & Biomolecular Chemistry, 2015)
This communication depicts an intriguing example of hydrogen-bonding reversal upon introduction of a sulfonamide linkage at the N-terminus of a synthetic reverse-turn peptide motif. The ready availability of two sulfonyl oxygen atoms, as hydrogen-bonding acceptors, combined with the inherent twisted conformation of sulfonamides are seen to act as switches that engage/disengage the hydrogen-bond at the sticky ends/termini.

Reverse-hydroformylation: a missing reaction explored - Nandakumar, Avanashiappan; Sahoo, Manoj Kumar; Balaraman, Ekambaram (Organic Chemistry Frontiers, 2015)
Recent progress in transition-metal catalysed acceptor- and acceptorless-reverse hydroformylation of aldehydes for the conversion of olefins has been discussed. The aldehyde feedstock serves as a source for production of syngas and valuable alkenes.

Role of methyl jasmonate in the expression of mycorrhizal induced resistance against Fusarium oxysporum in tomato plants - Nair, Aswathy; Kolet, Swati P.; Thulasiram, Hirekodathakallu V.; Bhargava, Sujata (Physiological and Molecular Plant Pathology, 2015)
Arbuscular mycorrhiza (AM) colonization led to a decrease in the severity of fusarium wilt disease caused by Fusarium oxysporum f. sp. lycopersici in tomato plants. The involvement of two plant defense hormones, namely methyl jasmonate (MeJA) and salicylic acid (SA), in the expression of mycorrhiza induced resistance (MIR) against this vascular pathogen was studied in the AM colonized and non-colonized (controls) plants. Activity of lipoxygenase (LOX), which plays a role in jasmonic acid (JA) biosynthesis, as well as levels of methyl jasmonate (MeJA) increased in AM colonized plants as compared to controls, but did not show any further changes in response to F. oxysporum inoculation. On the other hand, activity of phenylalanine ammonia lyase (PAL), which is an enzyme from salicylic acid (SA) biosynthetic pathway, as well as SA levels, increased in both controls and AM colonized plants in response to application of F. oxysporum spores. Hence the JA and not the SA signalling pathway appeared to play a role in the expression of MIR against this vascular pathogen. The resistance observed in AM colonized plants was completely compromised when plants were treated with the JA biosynthesis inhibitor salicylhydroxamic acid (SHAM). This confirmed that the AM-induced increase in JA levels was involved in the expression of resistance toward F. oxysporum. The SA response gene pathogenesis-related 1 (PR1) showed an increased expression in response to F. oxysporum infection in SHAM treated AM colonized plants as compared to plants that were not treated with this JA inhibitor. This suggested the possibility that JA inhibited SA responses, at least in the roots. AM colonization therefore appeared to prime plants for improved tolerance against the vascular pathogen F. oxysporum, which was mediated through the JA signalling pathway. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Fusarium wilt; Glomus fasciculatum; Methyl jasmonate; Mycorrhiza induced resistance; Salicylic acid; Tomato

Role of N-terminal proline in stabilizing the Ant-Pro zipper motif - Kheria, Sanjeev; Nair, Roshna V.; Kotmale, Amol S.; Rajamohanan, Pattuparambil R.; Sanjayan, Gangadhar J. (New Journal of Chemistry, 2015)
Hetero-chiral hybrid peptides of the general sequence (L)alpha beta(D)(n)alpha beta(n) featuring proline (Pro, a constrained alpha-amino acid) and anthranilic acid (Ant, a constrained beta-amino acid) as building blocks, where n = 2, 4 etc., form a three-dimensional zipper-like architecture. These zipper peptides attain stable conformation by balancing the co-operative contribution of two competing non-covalent forces, namely hydrogen bonding and aromatic stacking. However, the selection of the N-terminal residue also stands to be one of the key contributors in stabilising the unusually long-range intramolecular hydrogen bond, featuring 26 atoms in the H-bonded ring observed at the termini. This article deals with the substitution alterations at the N-terminus of the zipper motif and their consequent influences on its structure and stability. In this study, the N-terminal Pro residue of the zipper motif was substituted with a flexible amino acid, alanine, and a constrained acyclic amino acid, 2-aminoisobutyric acid, to investigate the role of N-terminal proline in stabilizing the Ant-Pro zipper motif, and its stabilities were assessed by employing solution-state NMR and restrained MD simulation studies.

RXR-carbamate - a novel molecular transporter for skin - Natarajan, Poornemaa; Patil, Kiran M.; Vij, Manika; Yadav, Amit K.; Kumar, Vaijayanti A.; Ganguli, Munia; Fernandes, Moneesha (Molecular Therapy, 2015)

Selective aerobic oxidation of alcohols over Au-Pd/sodium titanate nanotubes - Nepak, Devadutta; Darbha, Srinivas (Catalysis Communications, 2015)
catalytic application of Au-Pd nanoparticles supported on sodium titanate nanotubes (NaTNTs) for liquid-phase aerobic oxidation of alcohols is reported, for the first time. This reaction occurs at 80-120 degrees C, 1 atm and solvent-/alkali-free conditions yielding the corresponding carbonyls in high selectivity. This catalyst was reusable and found to be more active/selective than the corresponding monometallic Au and Pd catalysts and Au-Pd/TiO2. Higher dispersion, smaller particle size and higher amount of electron density at gold are the causes for the superior activity of Au-Pd/NaTNT catalyst. (C) 2014 Elsevier B.V. All rights reserved.
Keywords: aerobic oxidation; Alcohol; Bimetallic Au-Pd catalyst; Sodium titanate nanotubes; TiO2

Selective inhibition of miR-21 by phage display screened peptide - Bose, Debojit; Nahar, Smita; Rai, Manish Kumar; Ray, Arjun; Chakraborty, Kausik; Maiti, Souvik (Nucleic Acids Research, 2015)
miRNAs are nodal regulators of gene expression and deregulation of miRNAs is causally associated with different diseases, including cancer. Modulation of miRNA expression is thus of therapeutic importance. Small molecules are currently being explored for their potential to downregulate miRNAs. Peptides have shown to have better potency and selectivity toward their targets but their potential in targeting and modulating miRNAs remain unexplored. Herein, using phage display we found a very selective peptide against pre-miR-21. Interestingly, the peptide has the potential to downregulate miR-21, by binding to pre-miR-21 and hindering Dicer processing. It is selective towards miR-21 inside the cell. By antagonising miR-21 function, the peptide is able to increase the expression of its target proteins and thereby increase apoptosis and suppress cell proliferation, invasion and migration. This peptide can further be explored for its anti-cancer activity in vivo and may be even extended to clinical studies.

Sodium periodate mediated oxidative transformations in organic synthesis - Sudalai, Arumugam; Khenkin, Alexander; Neumann, Ronny (Organic & Biomolecular Chemistry, 2015)
The investigation of new oxidative transformations for the synthesis of carbon-heteroatom and heteroatom-heteroatom bonds is of fundamental importance in the synthesis of numerous bioactive molecules and fine chemicals. In this context, NaIO4, an exciting reagent, has attracted increasing attention enabling the development of these unprecedented oxidative transformations that are difficult to achieve otherwise. Thus, NaIO4 has been successfully explored as a versatile oxidant for a variety of fundamental organic transformations such as C-H activation, oxidative functionalization of alkenes and other interesting oxidative transformations and its application in the synthesis of bioactive natural products. This review summarizes recent developments in this area with NaIO4 as a versatile oxidant and brings out many challenges that still remain elusive for the future.

Sophorolipid assisted tunable and rapid gelation of silk fibroin to form porous biomedical scaffolds - Dubey, Parul; Nawale, Laxman; Sarkar, Dhiman; Nisal, Anuya; Prabhune, Asmita (RSC Advances, 2015)
Three dimensional polymer hydrogels, based on both natural and synthetic polymers, are increasingly being used as scaffolds and drug delivery vehicles for biomedical applications. Fibrous protein, silk fibroin (SF), obtained from the Bombyx mori silkworm is a promising candidate in this area. However, SF has a long gelation time of about a few weeks that can only be reduced by non-physiological treatments (e. g. high temperature, ultrasonication and low pH) or by addition of a chemical and non-biodegradable polymer and/or surfactant. We report here accelerated gelation of SF under physiological conditions using a biosurfactant, sophorolipid (SL) as a gelling agent. SL and SF are completely miscible and form a very clear solution upon mixing. Hence it is interesting to see that this clear solution gels in a time span of just a few hours. The hydrogels so formed have pore architecture, porosities and mechanical stability ideally suited for tissue culture applications. Here we also demonstrate that mouse fibroblast cells not only adhere to but also extensively proliferate on these SF-SL scaffolds.

Synthesis and evaluation of thieno[2,3-d]pyrimidin-4(3H)-ones as potential antitubercular agents - Borate, Hanumant B.; Annadate, Ritesh A.; Vagh, Sandip S.; Pisal, Mahesh M.; Deokate, Sagar B.; Arkile, Manisha A.; Jadhav, Nandadeep J.; Nawale, Laxman U.; Sarkar, Dhiman (MedChemComm, 2015)
A number of thieno[2,3-d]pyrimidin-4(3H)-ones were designed, synthesized and screened against Mycobacteria as a part of our program to develop new antitubercular agents. It was observed that some of the compounds have significant antimycobacterial activity against Mycobacterium tuberculosis H37Ra (ATCC 25177) and Mycobacterium bovis BCG (ATCC 35743). The active compounds were studied for cytotoxicity against four cell lines and were found to be non-cytotoxic. The results showed that compounds 13b and 29e were found to exhibit very good antimycobacterial activity (MIC in the range of 6-8 mu M) and the thienopyrimidinones as a class have potential to be developed as antitubercular agents.

Synthesis, antioxidant, anti-inflammatory, and antimicrobial screening of newer thiophene-fused arylpyrazolyl 1,3,4-oxadiazoles - Mahajan, Pravin S.; Nikam, Mukesh; Chate, Asha; Nimbalkar, Urja; Patil, Vrushali; Bobade, Anil; Chaudhari, Abhay; Deolankar, Dattatray; Javale, Balasaheb; Gill, Charansingh H. (Phosphorus Sulfur and Silicon and the Related Elements, 2015)
A series of newer 1,3,4-oxadiazole derivatives 3a-h, 5a-h containing a thiophene fused with pyrazole moiety of pharmacological significance have been synthesized. The compounds were characterized by H-1 NMR, IR, and mass spectral techniques. The compounds were screened for their in vitro antioxidant, anti-inflammatory and antimicrobial activities. Among them, Compounds 3b (EC50-14.98) and 3f (EC50-12.21) showed significant antioxidant activity. Compound 3a (EC50-15.23) showed good anti-inflammatory activity. Compound 3d was found as the most active derivative against bacterial and fungal strains.
Keywords: 1; 3; 4-Oxadiazole; Anti-inflammatory; Antimicrobial; Antioxidant; EC50; Thiophene-fused pyrazole

Synthesis of (+/-) debenzoyl analogs of norsampsones as potential anticancer agents - Jadhav, Amol R.; Thombal, Raju S.; Nigam, Preeti; Jadhav, Vrushali H. (Tetrahedron Letters, 2015)
Synthesis of (+/-) debenzoyl analogs of norsampsones 1 and 2 is reported starting from commercially available 1,3-cyclohexadione in six steps with overall yields of 37% and 36%, respectively. Compounds 1 and 2 were tested for their anticancer activity and showed moderate anticancer activity against HeLa cell lines. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Acylphloroglucinols; Anticancer; Debenzoyl; Norsampsones

Synthesis of N, F and S co-doped graphene quantum dots - Kundu, Sumana; Yadav, Ram Manohar; Narayanan, T. N.; Shelke, Manjusha V.; Vajtai, Robert; Ajayan, Pulickel M.; Pillai, Vijayamohanan K. (Nanoscale, 2015)
Graphene quantum dots (GQDs) are a promising category of materials with remarkable size dependent properties like tunable bandgap and photoluminescence along with the possibility of effective chemical functionalization. Doping of GQDs with heteroatoms is an interesting way of regulating their properties. Herein, we report a facile and scalable one-step synthesis of luminescent GQDs, substitutionally co-doped with N, F and S, of similar to 2 nm average size by a microwave treatment of multi-walled carbon nanotubes in a customized ionic liquid medium. The use of an ionic liquid coupled with the use of a microwave technique enables not only an ultrafast process for the synthesis of co-doped GQDs, but also provides excellent photoluminescence quantum yield (70%), perhaps due to the interaction of defect clusters and dopants.

Synthesis of non-toxic triethyl citrate plasticizer by esterification of renewable citric acid using modified zeolite - Nandiwale, Kakasaheb Y.; Borikar, Sanjay P.; Bokade, Vijay V. (Clean-Soil Air Water, 2015)
Triethyl citrate (TEC), a non-toxic plasticizer, was synthesized by esterification of renewable citric acid (CA, from entire waste of oranges) with ethanol over modified H-ZSM-5 (HZ-5) zeolite. Different micro-meso composites (M-HZ-5) with varying crystallinities were prepared by alkaline treatment of HZ-5. M-HZ-5(0.6) (87% crystallinity) was observed to be a potential and environmentally benign catalyst with 96% CA conversion, 64% TEC selectivity (61.44% TEC yield), and a reusability of six cycles. The probable catalytic mechanism of esterification was also proposed.
Keywords: Biowaste; Catalysts; green chemistry; Micro-mesopre composites; reusability

Systemic jasmonic acid modulation in mycorrhizal tomato plants and its role in induced resistance against alternaria alternata - Nair, A.; Kolet, Swati P.; Thulasiram, H. V.; Bhargava, S. (Plant Biology, 2015)
Tomato plants colonised with the arbuscular mycorrhizal (AM) fungus Glomus fasciculatum show systemic induced resistance to the foliar pathogen Alternaria alternata, as observed in interactions of other AM-colonised plants with a range of pathogens. The role of jasmonic (JA) and salicylic (SA) acid in expression of this mycorrhiza-induced resistance (MIR) against A.alternata was studied by measuring: (i) activity of enzymes reported to be involved in their biosynthesis, namely lipoxygenase (LOX) and phenylammonia lyase (PAL); and (ii) levels of methyl jasmonate (MeJA) and SA. Transcript abundance of some defence genes associated with JA and SA response pathways were also studied. Both LOX and PAL activity increased twofold in response to pathogen application to control plants. AM-colonised plants had three-fold higher LOX activity compared to control plants, but unlike controls, this did not increase further in response to pathogen application. Higher LOX activity in AM-colonised plants correlated with four-fold higher MeJA in leaves of AM-colonised plants compared to controls. Treatment of plants with the JA biosynthesis inhibitor salicylhydroxamic acid (SHAM) led to 50% lower MeJA in both control and AM-colonised plants and correlated with increased susceptibility to A.alternata, suggesting a causal role for JA in expression of MIR against the pathogen. Genes involved in JA biosynthesis (OPR3) and response (COI1) showed six- and 42-fold higher expression, respectively, in leaves of AM-colonised plants compared to controls. AM-colonised plants also showed increased expression of the SA response gene PR1 and that of the wound-inducible polypeptide prosystemin. Our results suggest that the systemic increase in JA in response to AM colonisation plays a key role in expression of MIR against A. alternata.
Keywords: Alternaria alternata; AM colonisation; induced resistance; Methyl jasmonate; salicylhydroxamic acid; Salicylic acid; Solanum lycopersicum

Terahertz spectroscopy and solid-state density functional theory calculations of cyanobenzaldehyde isomers - Dash, Jyotirmayee; Ray, Shaurnik; Nallappan, Kathirvel; Kaware, Vaibhav; Basutkar, Nitin B.; Gonnade, Rajesh G.; Ambade, Ashootosh V.; Joshi, Kavita; Pesala, Bala (Journal of Physical Chemistry A, 2015)
Spectral signatures in the terahertz (THz) frequency region are mainly due to bulk vibrations of the molecules. These resonances are highly sensitive to the relative position of atoms in a molecule as well as the crystal packing arrangement. To understand the variation of THz resonances, THz spectra (2-10 THz) of three structural isomers: 2-, 3-, and 4-cyanobenzaldehyde have been studied. THz spectra obtained from Fourier transform infrared (FTIR) spectrometry of these isomers show that the resonances are distinctly different especially below 5 THz. For understanding the intermolecular interactions due to hydrogen bonds, four molecule cluster simulations of each of the isomers have been carried out using the B3LYP density functional with the 6-31G(d,p) basis set in Gaussian09 software and the compliance constants are obtained. However, to understand the exact reason behind the observed resonances, simulation of each isomer considering the full crystal structure is essential. The crystal structure of each isomer has been determined using X-ray diffraction (XRD) analysis for carrying out crystal structure simulations. Density functional theory (DFT) simulations using CRYSTAL14 software, utilizing the hybrid density functional B3LYP, have been carried out to understand the vibrational modes. The bond lengths and bond angles from the optimized structures are compared with the XRD results in terms of root-mean-square-deviation (RMSD) values. Very low RMSD values confirm the overall accuracy of the results. The simulations are able to predict most of the spectral features exhibited by the isomers. The results show that low frequency modes (<3 THz) are mediated through hydrogen bonds and are dominated by intermolecular vibrations.

Total synthesis of (+)-petromyroxol via tandem alpha-aminoxylation-allylation and asymmetric dihydroxylation-S(N)2 cyclization approach - Nookaraju, U.; Kumar, Pradeep (RSC Advances, 2015)
The total synthesis of (+)-petromyroxol, a tetrahydrofuran (THF)-diol fatty acid, isolated from sea lamprey larvae (Petromyzon marinus) is reported. The present synthesis employs a tandem alpha-aminoxylationallylation, cross metathesis and tandem asymmetric dihydroxylation-S(N)2 cyclization as key steps.

Transition-metal-catalyzed hydrogen-transfer annulations: access to heterocyclic scaffolds - Nandakumar, Avanashiappan; Midya, Siba Prasad; Landge, Vinod Gokulkrishna; Balaraman, Ekambaram (Angewandte Chemie-International Edition, 2015)
The ability of hydrogen-transfer transition-metal catalysts, which enable increasingly rapid access to important structural scaffolds from simple starting materials, has led to a plethora of research efforts on the construction of heterocyclic scaffolds. Transition-metal-catalyzed hydrogen-transfer annulations are environmentally benign and highly atom-economical as they release of water and hydrogen as by-product and utilize renewable feedstock alcohols as starting materials. Recent advances in this field with respect to the annulations of alcohols with various nucleophilic partners, thus leading to the formation of heterocyclic scaffolds, are highlighted herein.

Unraveling the success and failure of mode coupling theory from consideration of entropy - Nandi, Manoj Kumar; Banerjee, Atreyee; Sengupta, Shiladitya; Sastry, Srikanth; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2015)
We analyze the dynamics of model supercooled liquids in a temperature regime where predictions of mode coupling theory (MCT) are known to be valid qualitatively. In this regime, the Adam-Gibbs (AG) relation, based on an activation picture of dynamics, also describes the dynamics satisfactorily, and we explore the mutual consistency and interrelation of these descriptions. Although entropy and dynamics are related via phenomenological theories, the connection between MCT and entropy has not been argued for. In this work, we explore this connection and provide a microscopic derivation of the phenomenological Rosenfeld theory. At low temperatures, the overlap between the MCT power law regime and AG relation implies that the AG relation predicts an avoided divergence at T-c, the origin of which can be related to the vanishing of pair configurational entropy, which we find occurring at the same temperature. We also show that the residual multiparticle entropy plays an important role in describing the relaxation time. (C) 2015 AIP Publishing LLC.

Viridians group streptococci in patients undergoing tooth extraction - Dhotre, Shree V.; Dharne, Mahesh S.; Potdar, S.; Suklikar, J.; Suryawanshi, Namdev; Nagoba, Basavraj (European Journal of General Medicine, 2015)
The aerobic microflora of the oral cavity consists of viridians group of streptococci (VGS). The present study was carried out with an objective to evaluate the prevalence of VGS in patients undergoing tooth extraction and to study their antibiotic susceptibility pattern. Samples of subgingival dental plaques for microbiological studies were collected from 80 patients undergoing tooth extraction. The isolated streptococci were identified along with their antibacterial susceptibilities by automated Vitek 2 (bioMérieux) system in accordance with CLSI standards. A total of 260 VGS strains belonging to 05 phenotypic groups, namely mutans, salivarius, anginosus, sanguinus and mitis groups; along with few strains of Granulicatella like G. adiacens and G. elegans. Altogether a total of 15 species were isolated from the subgingival plaque of 80 patients undergoing tooth extraction. Among the 15 antibiotics tested, highest resistance was observed to lincosamides (36.2%) followed by macrolides (29.7%), tetracyclines (17.7%), cephems (15.1%), fluoroquinolones (14.4%), oxazolidinones (13.5%), streptogramins (12.7 %) and penicillins (7.9%). However, all the 260 VGS strains were found susceptible to vancomycin and linezolid. In the subgingival plaque of patients undergoing tooth extraction, approximately 70% of streptococci belonged to three VGS groups, i.e. mitis, sanguinis and mutans groups. Streptococci of salivarus and anginosus groups were isolated sporadically (5%). Highest resistance was observed to lincosamides and macrolides (29.7%). Multiple antibiotic resistance was observed in mitis and salivarius group.

Water-promoted diels-alder reaction in quaternary ammonium salts - Nagare, Amit S.; Manna, Arpan; Sonawane, Pramod D.; Kumar, Anil (Journal of Physical Organic Chemistry, 2015)
{Prevailing classification of salts based on their effect in solubility and stability of proteins in aqueous solution predicts that tetraalkylammonium salts, guanidinium chloride (GnCl), LiClO4 act as salting-in (S/I) and LiCl, NaCl act as salting-out (S/O) in aqueous conditions. In the same context the behaviour of GnCl, LiClO4 and LiCl are contradictory in polar solvents like ethylene glycol and formamide. In these solvents, expected salt effect shows just opposite nature from their usual expectation. However, in the aqueous solution salts like tetraalkylammonium halide (R4NX
Keywords: Delta G(solvation); Diels-Alder reaction; k(s); kinetic study; solubility; tetraalkylammonium salts; viscosity

Amelioration of excision wounds by topical application of green synthesized, formulated silver and gold nanoparticles in albino Wistar rats - Naraginti, Saraschandra; Kumari, P. Lakshmi; Das, Raunak Kumar; Sivakumar, A.; Patil, Sagar Hindurao; Andhalkar, Vaibhav Vilas (Materials Science & Engineering C-Materials for Biological Applications, 2016)
Wound healing, a complex biological process, has attained a lot of attention as dermatologists are primarily interested in stimulated wound closure without formation of scar or a faint scar. The recent upsurgence of nanotechnology has provided novel therapeutic materials in the form of silver and gold nanoparticles which accelerate the wound healing process. The effect of formulated nanoparticles using Coleus forskohlii root extract (green synthesized) has been tried out for ameliorating full thickness excision wounds in albino Wistar male rats. The evaluation of in vivo activity of nanoparticles in wound healing was carried out on open wounds made by excision on the dorsal sides of albino Wistar rats under anesthesia, and the healing of the wounds was assessed. Histological aspects of the healing process were studied by a HE (Hematoxylin and Eosin) staining method to assess various degrees of re-epithelialization and the linear alignment of the granulation tissue whereas Van Gieson's histochemical staining was performed to observe collagen fibers. The healing action shown by the formulated nanoparticles was remarkable during the early stages of wound healing, which resulted in the substantial reduction of the whole healing period. Topical application of formulated gold nanoparticles was found to be more effective in suppressing inflammation and stimulating re-epithelialization compared to silver nanoparticles during the healing process. The results throw light on the amelioration of excision wounds using nanoparticles which could be a novel therapeutic way of improving wound healing in clinical practice. The mechanism of advanced healing action of both types of nanoparticles could be due to their antimicrobial, antioxidant and anti-inflammatory properties. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: collagen; Gold; green synthesis; Nanopraticles; wound Healing

Ammonium catalyzed cyclitive additions: evidence for a cation-pi interaction with alkynes - Nagy, Edith; St Germain, Elijah; Cosme, Patrick; Maity, Pradip K.; Terentis, Andrew C.; Lepore, Salvatore D. (Chemical Communications, 2016)
The addition of carbamate nitrogen to a non-conjugated carbon-carbon triple bond is catalyzed by an ammonium salt leading to a cyclic product. Studies in homogeneous systems suggest that the ammonium agent facilitates nitrogen-carbon bond formation through a cation-p interaction with the alkyne unit that, for the first time, is directly observed by Raman spectroscopy.

Calculation of hyperfine structure constants of small molecules using Z-vector method in the relativistic coupled-cluster framework - Sasmal, Sudip; Talukdar, Kaushik; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Journal of Chemical Sciences, 2016)
The Z-vector method in the relativistic coupled-cluster framework is employed to calculate the parallel and perpendicular components of the magnetic hyperfine structure constant of a few small alkaline earth hydrides (BeH, MgH, and CaH) and fluorides (MgF and CaF). We have compared our Z-vector results with the values calculated by the extended coupled-cluster (ECC) method reported in Phys. Rev. A 91 022512 (2015). All these results are compared with the available experimental values. The Z-vector results are found to be in better agreement with the experimental values than those of the ECC values.

Can a diels-alder reaction accelerate in a supersaturated solvent at room temperature? - Nagare, Amit S.; Manna, Arpan; Kumar, Anil (New Journal of Chemistry, 2016)
A new supersaturated solvent is proposed to accelerate the Diels–Alder reaction between cyclopentadiene and methyl acrylate by several times. The proposed supersaturated solvent consists of various carbohydrates, organic acid and organic ketone in water, beyond their solubility limits in water, at room temperature. The results demonstrate that the presence of excess –OH groups from the carbohydrates plays a pivotal role leading to the increased reactivity and selectivity of the Diels–Alder reaction. The role of hydrogen bond accelerators and polarity of the solvent have been analyzed through a comparative study of the same reaction in similar green solvents. Collision-controlled reaction theory has been invoked to understand the role of encounter complexes to accelerate such a reaction at the molecular level in such highly viscous supersaturated solvent. No detrimental effects from the high viscosity of the new solvent medium on the reaction kinetics was been noted.

Capsicum annuum proteinase inhibitor ingestion negatively impacts the growth of sorghum pest Chilo partellus and promotes differential protease expression - Jadhav, A. R.; War, A. R.; Nikam, A. N.; Adhav, A. S.; Gupta, V. S.; Sharma, H. C.; Giri, A. P.; Tamhane, V.A. (Biochemistry and Biophysics Reports, 2016)
Background Chilo partellus is an important insect pest infesting sorghum and maize. The larvae internalize in the stem, rendering difficulties in pest management. We investigated the effects of Capsicum annuum proteinase inhibitors (CanPIs) on C. partellus larvae by in-vitro and in-vivo experiments. Methods Recombinant CanPI-7 (with four-Inhibitory Repeat Domains, IRDs), -22 (two-IRDs) and insect proteinase activities were estimated by proteinase assays, dot blot assays and in gel activity assays. Feeding bioassays of lab reared C. partellus with CanPI-7 and -22 were performed. C. partellus proteinase gene expression was done by RT-PCR. In-silico structure prediction of proteinases and CanPI IRDs was carried out, their validation and molecular docking was done for estimating the interaction strength. Results Larval proteinases of C. partellus showed higher activity at alkaline pH and expressed few proteinase isoforms. Both CanPIs showed strong inhibition of C. partellus larval proteinases. Feeding bioassays of C. partellus with CanPIs revealed a dose dependent retardation of larval growth, reduction of pupal mass and fecundity, while larval and pupal periods increased significantly. Ingestion of CanPIs resulted in differential up-regulation of C. partellus proteinase isoforms, which were sensitive to CanPI-7 but were insensitive to CanPI-22. In-silico interaction studies indicated the strong interaction of IRD-9 (of CanPI-22) with Chilo proteinases tested. Conclusions Of the two PIs tested, CanPI-7 prevents induction of inhibitor insensitive proteinases in C. partellus so it can be explored for developing C. partellus tolerance in sorghum. General significance Ingestion of CanPIs, effectively retards C. partellus growth; while differentially regulating the proteinases.

CeCl3 center dot 7H(2)O-NaI promoted regioselective sulfenylation of indoles with sulfonylhydrazides - Nookaraju, U.; Begari, Eeshwaraiah; Yetra, Ravikiran Reddy; Kumar, Pradeep (Chemistryselect, 2016)
A simple and highly efficient method has been developed for the regioselective sulfenylation of a wide variety of indoles with alkyl and aryl sulfonylhydrazides as a sulphur source and CeCl3 center dot 7H(2)O-Nal as an inexpensive and readily available reagent system. This method involves the breaking of sulfur-oxygen and sulfur-nitrogen bonds and making of carbon-sulfur bond. The method provides high yields of the products with enhanced regioselectivity. We studied the reactivity of various electron rich and electron deficient indoles towards the sulfe-nylation reaction. The indoles containing electron donating group reacts fast towards the sulfenylation reaction as compared to the indoles containing electron withdrawing groups. More over functional groups like alkoxy, aryloxy, bromo, nitro, cyano, ester, were well tolerated under the established reaction conditions. We also proposed a plausible mechanism for this transformation. The experimental simplicity and environmentally benign nature of the reagent system makes this method an attractive alternative to established methods.

CH3NH3Pb(BF4)(3) and (C4H9NH3)2Pb(BF4)(4) family of 3D and 2D perovskites without and with iodide and bromide ions substitution - Nagane, Satyawan; Ogale, Satishchandra B. (Journal of Physical Chemistry Letters, 2016)
We report the synthesis of fully molecular ion (BF4 )-based organicinorganic hybrid perovskite CH3NH3Pb(BF4)(3), which is a wide band gap semiconductor, and the same can be easily tuned toward the visible by the incorporation of bromide or iodide ions in the crystal framework simply by changing lead precursors. We have also successfully transformed the distorted 3D molecular-ion-induced perovskite to 2D (C4H9NH3)(2)Pb(BF4)(4), (C4H9NH3)(2)PbBr(4x)(BF4)(x), and (C4H9NH3)(2)PbI(4x)(BF4)(x) perovskites that exhibit the optical absorption over the UV to visible region. The thin films of molecular-ion-containing 2D perovskites with Br and I anions show blue and green luminescence, respectively, under UV illumination.

Chemically delaminated free-standing ultrathin covalent organic nanosheets - Khayum, M. Abdul; Kandambeth, Sharath; Mitra, Shouvik; Nair, Sanoop B.; Das, Anuja; Nagane, Samadhan S.; Mukherjee, Rabibrata; Banerjee, Rahul (Angewandte Chemie-International Edition, 2016)
Covalent organic nanosheets (CONs) are a new class of porous thin two-dimensional (2D) nanostructures that can be easily designed and functionalized and could be useful for separation applications. Poor dispersion, layer restacking, and difficult postsynthetic modifications are the major hurdles that need to be overcome to fabricate scalable CON thin films. Herein, we present a unique approach for the chemical exfoliation of an anthracene-based covalent organic framework (COF) to N-hexylmaleimide-functionalized CONs, to yield centimeter-sized free-standing thin films through layer-by-layer CON assembly at the air-water interface. The thinlayer fabrication technique presented here is simple, scalable, and does not require any surfactants or stabilizing agents.

"Click" polymerization: a convenient strategy to prepare designer fullerene materials - Krishnamurthy, Munusamy; Krishnamoorthy, Kothandam; Arulkashmir, Arulraj; Raghavendra, V.; Murali, Adhigan; Jaisankar, Sellamuthu N.; Murugan, P.; Gurusamy-Thangavelu, Senthil A.; Nasar, A. Sultan; Mandal, Asit Baran; Samanta, Debasis (Materials & Design, 2016)
"Click" polymeric assemblies of fullerenes, thiophenes and aryl compounds were prepared for the first time to study their spectroscopic/chemical/electronic characteristics and possible applications in photovoltaic cells. The GPC and NMR spectroscopic data confirmed a moderate to high degree of polymerization while microscopic pictures showed well-defined arrangements of fullerenes. The FTIR studies indicated that the product is free from starting azide materials, whereas thermogravimetric analysis data suggested a good stability. Band gap of the material was determined using UV-Vis spectroscopy, cyclic voltammetric techniques and compared with computational investigation. The fullerene copolymer was fabricated as acceptor material in a bulk heterojunction photovoltaic cell. (C) 2016 Elsevier Ltd. All rights reserved.

CO2 Laser direct written MOF-based metal-decorated and heteroatom-doped porous graphene for flexible all-solid-state microsupercapacitor with extremely high cycling stability - Basu, Aniruddha; Roy, Kingshuk; Sharma, Neha; Nandi, Shyamapada; Vaidhyanathan, Ramanathan; Rane, Sunit; Rode, Chandrashekhar V.; Ogale, Satishchandra B. (ACS Applied Materials & Interfaces, 2016)
Over the past decade, flexible and wearable microelectronic devices and systems have gained significant importance. Because portable power source is an essential need of such wearable devices, currently there is considerable research emphasis on the development of planar interdigitated micro energy-torage devices by employing diverse precursor materials to obtain functional materials (functional carbon, oxides, etc.) with the desirable set of properties. Herein we report for the first time the use of metal organic framework (MOF) and zeolitic imidazolate framework (ZIF-67) for high-wavelength photothermal laser direct writing of metal-decorated, heteroatom-doped, porous few-layer graphene electrodes for microsupercapacitor application. We argue that the specific attributes of MOF as a precursor and the high-wavelength laser writing approach (which creates extremely high localized and transient temperature (>2500 degrees C) due to strong absorption by lattice vibrations) are together responsible for the peculiar interesting properties of the carbon material thus synthesized, thereby rendering extremely high cycling stability to the corresponding microsupercapacitor device. Our device exhibits near 100% retention after 200 000 cycles as well as stability under 150 degrees bending.

Comparative study of dG affinity vs. DNA methylation modulating properties of side chain derivatives of procainamide: insight into its DNA hypomethylating effect - Gawade, Rupesh L.; Chakravarty, Debamitra K.; Debgupta, Joyashish; Sangtani, E.; Narwade, S.; Gonnade, Rajesh G.; Puranik, Vedavati G.; Deobagkar, D. D. (RSC Advances, 2016)
Procainamide derivatives have been synthesized to investigate the role of side chains in modulating the DNA methylation level in cancer cells and gain insight into its mechanism of action. The synthesized derivatives comprised of flexible (dimethyl), constrained (pyrrolidine, piperidine, morpholine) and planar aromatic (pyridine, phenyl) side chain motifs. The affinity of procainamide and its derivatives towards the deoxyguanosine (dG) base in neutral form has been assessed by performing Differential Pulse Voltammetry (DPV) under physiological conditions. Further, molecular docking with hemimethylated CpG rich DNA acquired from an active mDNMT-1-DNA (PDB ID-4DA4) crystal structure, reveals their preferential non-covalent interaction with dG nucleobase in the intercalation cavity of the minor groove. Differential affinity of the derivatives to dG base in neutral and bound forms (DNA) is correlated with their DNA methylation modulating properties at sub-lethal concentrations. Among all the derivatives, a compound with an aromatic phenyl side chain (1) has shown a highest binding affinity for dG nucleobase in neutral form as well as for partially denatured CpG rich DNA which is attributed to the formation of p/p stacking interaction in addition to N-H/O hydrogen bonding with the pyrimidine ring of dG base. It also shows the highest cytotoxicity and global hypomethylation at a sub-lethal level in the MCF-7 cancer cell line compared to other derivatives and procainamide. A docking study has also illustrated the plausible structural basis of DNA methylation modulating a property of procainamide. Strong association of procainamide with dG bases of partially denatured CpG rich DNA via H-bonding and other non-covalent interactions may alter the active topology of DNA required by the DNA-binding regulatory proteins (e. g. DNMT-1) which is validated by a DNMT-1 inhibition assay. This systematic investigation leads to a new potent alternative to procainamide being found and gives a plausible insight into the DNA hypomethylating effect of procainamide.

Composition dependence of the glass forming ability in binary mixtures: the role of demixing entropy - Nandi, Ujjwal Kumar; Banerjee, Atreyee; Chakrabarty, Suman; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2016)
We present a comparative study of the glass forming ability of binary systems with varying composition, where the systems have similar global crystalline structure (CsCl+fcc). Biased Monte Carlo simulations using umbrella sampling technique show that the free energy cost to create a CsCl nucleus increases as the composition of the smaller particles is decreased. We find that systems with comparatively lower free energy cost to form CsCl nucleus exhibit more pronounced pre-crystalline demixing near the liquid/crystal interface. The structural frustration between the CsCl and fcc crystal demands this demixing. We show that closer to the equimolar mixture, the entropic penalty for demixing is lower and a glass forming system may crystallize when seeded with a nucleus. This entropic penalty as a function of composition shows a non-monotonic behaviour with a maximum at a composition similar to the well known Kob-Anderson (KA) model. Although the KA model shows the maximum entropic penalty and thus maximum frustration against CsCl formation, it also shows a strong tendency towards crystallization into fcc lattice of the larger ``A'' particles which can be explained from the study of the energetics. Thus for systems closer to the equimolar mixture although it is the requirement of demixing which provides their stability against crystallization, for KA model it is not demixing but slow dynamics and the presence of the ``B'' particles make it a good glass former. The locally favoured structure around ``B'' particles is quite similar to the CsCl structure and the incompatibility of CsCl and fcc hinders the fcc structure growth in the KA model. Although the glass forming binary systems studied here are quite similar, differing only in composition, we find that their glass forming ability cannot be attributed to a single phenomenon. Published by AIP Publishing.

Crystal engineering of a zwitterionic drug to neutral cocrystals: a general solution for floxacins - Gunnam, Anilkumar; Suresh, Kuthuru; Ganduri, Ramesh; Nangia, Ashwini (Chemical Communications, 2016)
The transformation of zwitterionic Sparfloxacin (SPX) to the neutral form is achieved by cocrystallization. Neutral forms of drugs are important for higher membrane permeability, while zwitterions are more soluble in water. The twin advantages of higher solubility/dissolution rate and good stability of neutral SPX are achieved in a molecular cocrystal compared to its zwitterionic SPX hydrate. The amine-phenol supra-molecular synthon drives cocrystal formation, with the paraben ester acting as a "proton migrator'' for the ionic to neutral transformation.

Detection of clostridium tetani in human clinical samples using tetX specific primers targeting the neurotoxin - Ganesh, Madhu; Sheikh, Nasira K.; Shah, Pooja; Mehetre, Gajanan T.; Dharne, Mahesh S.; Nagoba, Basavraj S. (Journal of Infection and Public Health, 2016)
Tetanus resulting from ear injury remains an important health problem, particularly in the developing world. We report the successful detection of Clostridium tetani using tetX specific primers targeting the Cl. tetani neurotoxin. The sample was obtained from an ear discharge of a case of otogenic tetanus in a 2-year-old male child. Based on the culture results of the ear discharge, Gram staining and virulence testing by genotyping, a diagnosis of tetanus was confirmed. This is the first report from India on the successful detection of Cl. tetani in a human clinical sample using tetX specific primers targeting the Cl. tetani neurotoxin. (C) 2015 King Saud Bin Abdulaziz University for Health Sciences. Published by Elsevier Limited. All rights reserved.
Keywords: Cl. tetani; Neurotoxin; Otogenic tetanus; Trismus

Draft genome sequence of arthrobacter enclensis NCIM 5488T for secondary metabolism - Neurgaonkar, P. S.; Dharne, M. S.; Dastager, S. G. (Genome Announcements, 2016)
Here, we report the draft genome sequence of Arthrobacter enclensis NCIM 5488T, an actinobacterium isolated from a marine sediment sample from Chorao Island, Goa, India. This draft genome sequence consists of 4,226,231 bp with a G+C content of 67.08%, 3,888 protein-coding genes, 50 tRNAs, and 10 rRNAs. Analysis of the genome using bioinformatics tools such as antiSMASH and NaPDoS showed the presence of many unique natural product biosynthetic gene clusters.

Effect of out-of-plane alkyl group's position in dye-sensitized solar cell efficiency: a structure-property relationship utilizing indoline-based unsymmetrical squaraine dyes - Alagumalai, Ananthan; Fairoos, Munavvar M. K.; Vellimalai, Punitharasu; Sil, Manik Chandra; Nithyanandhan, Jayaraj (ACS Applied Materials & Interfaces, 2016)
Squaraine dyes are promising chromophores to harvest visible and near-infrared (NIR) photons. A series of indoline-based unsymmetrical squaraine (SQ) dyes that contain alkyl chains at sp(3) C- and N- atoms of indoline moieties with a carboxylic acid anchoring group were synthesized. The optical and electrochemical properties of the SQ dyes in solution were nearly identical as there was no change in the D-A-D SQ framework; however, remarkable changes with respect to the power conversion efficiencies (PCE) were observed depending upon the position of alkyl groups in the dye. Introduction of alkyl groups to the indoline unit that was away from anchoring unit were helped in more dye loading with controlled organization of dyes on surface, increased charge transfer resistance, long electron lifetime, and hence higher PCE than that of the corresponding isomer in which the alkyl groups funtionalized indoline unit contains the carboxylic acid anchoring group. Careful analysis of incident photon-to current conversion efficiency (IPCE) profiles indicated the presence of aggregated structure on the TiO2 surface that contributes to the charge injection in the presence of a coadsorbent. A dye-sensitized solar cell (DSSC) device made out of SQ5 was achieved an efficiency of 9.0%, with an open-circuit potential (V-oc) of 660 mV and short-circuit current density (J(sc)) of 19.82 mA/cm 2, under simulated AM 1.5G illumination (100 mW/cm(2)). The IPCE profile of SQ5 shows an onset near to 750 nm with a good quantum efficiency (>80%) in the range of 550-700 nm, indicating the importance of self-organization of dyes on the TiO2 surface for an efficient charge injection. This present investigation revealed the importance of position of alkyl groups in the squaraine-based dyes for the better PCE.

Effect of total and pair configurational entropy in determining dynamics of supercooled liquids over a range of densities - Banerjee, Atreyee; Nandi, Manoj Kumar; Sastry, Srikanth; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2016)
In this paper, we present a study of supercooled liquids interacting with the Lennard Jones potential and the corresponding purely repulsive (Weeks-Chandler-Andersen) potential, over a range of densities and temperatures, in order to understand the origin of their different dynamics in spite of their structures being similar. Using the configurational entropy as the thermodynamic marker via the Adam Gibbs relation, we show that the difference in the dynamics of these two systems at low temperatures can be explained from thermodynamics. At higher densities both the thermodynamical and dynamical difference between these model systems decrease, which is quantitatively demonstrated in this paper by calculating different parameters. The study also reveals the origin of the difference in pair entropy despite the similarity in the structure. Although the maximum difference in structure is obtained in the partial radial distribution function of the B type of particles, the rdf of AA pairs and AB pairs gives rise to the differences in the entropy and dynamics. This work supports the observation made in an earlier study [A. Banerjee et al., Phys. Rev. Lett. 113, 225701 (2014)] and shows that they are generic in nature, independent of density. Published by AIP Publishing.

Efficient cellular entry of (r-x-r)-type carbamate-plasmid DNA complexes and its implication for noninvasive topical DNA delivery to skin - Vij, Manika; Natarajan, Poornemaa; Yadav, Amit K.; Patil, Kiran M.; Pandey, Tanuja; Gupta, Nidhi; Santhiya, Deenan; Kumar, Vaijayanti A.; Fernandes, Moneesha; Ganguli, Munia (Molecular Pharmaceutics, 2016)
Arginine-rich cell penetrating peptides are powerful tools for in vitro as well as in vivo delivery of a wide plethora of biomolecules. However, presence of consecutive arginine residues leads to enhanced amenability for proteolytic degradation as well as steric hindrances for membrane interactions which compromise its bioavailability. In order to overcome these limitations we previously reported a safe and stable octaarginine based oligomer, i.e., (r-x-r)4-carbamate, where the backbone amide linkages were replaced by carbamate linkages and 6-aminohexanoic acid based spacer moieties were incorporated for better flexibility, hydrophobicity, optimal spacing of guanidinium groups, and protection against proteolytic cleavage; resulting in improved transfection efficiency over its amide counterpart. In the present work we have investigated the mechanism behind this enhanced transfection efficiency and, based on our observations, demonstrate how the synergistic effect of rationalized oligomer designing, complex characteristics, and cell type contributes to overall effective intracellular delivery. Our results indicate that the (r-x-r)4-carbamate plasmid DNA complexes primarily utilize lipid raft dependent pathway of cellular entry more than other pathways, and this possibly facilitates their increased entry in the lipid raft rich milieu of skin cells. We also emphasize the utility of oligomer (r-x-r)4-carbamate as an efficient carrier for topical delivery of nucleic acids in skin tissue. This carrier can be utilized for safe, efficient, and noninvasive delivery of therapeutically relevant macromolecular hydrophilic cargo like nucleic acids to skin.
Keywords: Cell penetrating peptides; endocytosis; nucleic acid delivery; skin penetration; transfection

Electronic structure and properties of layered gallium telluride - Shenoy, U. Sandhya; Gupta, Uttam; Narang, Deepa S.; Late, Dattatray J.; Waghmare, Umesh V.; Rao, C. N. R. (Chemical Physics Letters, 2016)
Layer-dependent electronic structure and properties of gallium monochalcogenides, GaX where X=S, Se, Te, have been investigated using first-principles calculations based on various functionals, with a motivation to assess their use in photocatalytic water splitting. Since hydrogen evolution by water splitting using visible light provides a promising way for solar energy conversion, both theoretical and experimental studies have been carried out on the photochemical hydrogen evolution by GaTe. We also present the Raman spectra of GaTe examined by both theory and experiment. (C) 2016 Elsevier B.V. All rights reserved.

[Et3NH][HSO4] catalyzed efficient synthesis of 5-arylidene-rhodanine conjugates and their antitubercular activity - Subhedar, Dnyaneshwar D.; Shaikh, Mubarak H.; Nawale, Laxman; Yeware, Amar; Sarkar, Dhiman; Shingate, Bapurao B. (Research on Chemical Intermediates, 2016)
We have described a highly efficient, safer protocol for the synthesis of 5-arylidene-rhodanine conjugates catalyzed by Bronsted acidic ionic liquid [Et3NH][HSO4] in excellent yields. The protocol offers cost-effective, environmentally benign, solvent-free conditions and recycle-reuse of the catalyst. The synthesized 5-arylidene-rhodanine conjugates were characterized on the basis of (1) H NMR, C-13 NMR and HRMS spectral data. A series of 5-arylidene-rhodanine derivatives 3a-h, 4a-h were synthesized and evaluated for their in vitro antitubercular activity against dormant Mycobacterium tuberculosis H37Ra and M. bovis BCG strains. Moreover, compounds 3a, 3b, 3e, 3f, 3g, 3h and 4f exhibited good antitubercular activity and were also evaluated for anti-proliferative activity against MCF-7, A549 and HCT116 cell lines using modified MTT assay and found to be noncytotoxic. Compounds 3a-h and 4f were further screened for their antibacterial activity against four bacteria strains to assess their selectivity towards M. tuberculosis. Furthermore, in silico ADME prediction of all the tested compounds followed the criteria for orally active drug and, therefore, these compounds may have a good potential for eventual development as oral agents.

Evaluation of uttroside B, a saponin from Solanum nigrum Linn, as a promising chemotherapeutic agent against hepatocellular carcinoma - Nath, Lekshmi R.; Gorantla, Jaggaiah N.; Thulasidasan, Arun Kumar T.; Vijayakurup, Vinod; Shah, Shabna; Anwer, Shabna; Joseph, Sophia M.; Antony, Jayesh; Veena, Kollery Suresh; Sundaram, Sankar; Marelli, Udaya K.; Lankalapalli, Ravi S.; et al. (Scientific Reports, 2016)
We report, for the first time, the remarkable efficacy of uttroside B, a potent saponin from Solanum nigrum Linn, against liver cancer. The compound has been isolated and characterized from the leaves of Solanum nigrum Linn, a plant widely used in traditional medicine and is a rich resource of several anticancer molecules. Uttroside B, that comprises of beta-D-glucopyranosyl unit at C-26 of the furostanol and beta-lycotetraosyl unit at C-3, is ten times more cytotoxic to the liver cancer cell line, HepG2 (IC50: 0.5 mu M) than sorafenib (IC50: 5.8 mu M), the only FDA-approved drug for liver cancer. Moreover, it induces cytotoxicity in all liver cancer cell lines, irrespective of their HBV status, while being non-toxic to normal immortalized hepatocytes. It induces apoptosis in HepG2 cells by down-regulating mainly the activation of MAPK and mTOR pathways. The drastic reduction in HepG2-xenograft tumor size achieved by uttroside B in NOD-SCID mice and substantiation of its biological safety through both acute and chronic toxicity studies in Swiss albino mice warrants clinical validation of the molecule against hepatic cancer, for which, the chemotherapeutic armamentarium currently has limited weapons.

Fluorescent carbon nanodots for targeted in vitro cancer cell imaging - Aiyer, Sandhya; Prasad, Rajendra; Kumar, Manoj; Niryikar, K.; Jain, Bhanprakash; Kushwaha, Omkar S. (Applied Materials Today, 2016)
Carbon quantum dots (CQDs or C-dots, <= 10nm in size) are tiny carbon nanoparticles being envisaged in biosensing, bio-imaging and biomolecular/drug delivery. In the present investigation, green fluorescent carbon quantum/nano dots (GCQDs, similar to 3 nm in size) were synthesized through facile chemical slicing method. Further, folic acid (FA) functionalized GCQDs (GCQDs-FA) were obtained to enhance their targeting ability. FA is known to positively influence the binding potential and penetration into the cancer cells because of high abundance of folate receptors (FR) on various cancer cell membranes. We report high biocompatibility, photoluminescence stability and excellent in vitro cancer cell cytoplasm and nucleus targeting performance of GCQDs-FA on MCF-7 breast cancer cells. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: Cancer cell bio-imaging; Carbon quantum/nano dots; Cell cytoplasm and nucleus targeting; Green fluorescence; Photoluminescence stability; Targeting ability

Glucose sensing and low-threshold field emission from MnCo2O4 nanosheets - Naik, Kusha Kumar; Khare, Ruchita T.; More, Mahendra A.; Late, Dattatray J.; Rout, Chandra Sekhar (RSC Advances, 2016)
Manganese cobalt oxide (MnCo2O4) nanosheets were grown on nickel (Ni) foam by a simple electrodeposition method. The as-synthesized nanosheets were characterized using X-ray diffraction and scanning electron microscopy. The Ni foam supports the growth of MnCo2O4 nanosheets without any aggregation, thereby increasing its catalytic and electronic properties. The electrochemical studies show that MnCo2O4 exhibits excellent electrocatalytic activity towards glucose sensing applications. The MnCo2O4 based glucose sensor shows a good sensitivity value of 8.2 mA mM(-1) cm(-2), with a response time of 19 s. In addition to this, field emission studies of as-synthesized MnCo2O4 reveal a low turn-on field value of 1.9 V mm(-1) and good emission current stability, demonstrating MnCo2O4 nanosheets as a good field emitter material.

Graphene oxide sheathed ZIF-8 microcrystals: engineered precursors of nitrogen-doped porous carbon for efficient oxygen reduction reaction (ORR) electrocatalysis - Thomas, Minju; Illathvalappi, Rajith; Kurungot, Sreekumar; Nair, Balagopal N.; Mohamed, Abdul Azeez Peer; Anilkumar, Gopinathan M.; Yamaguchi, Takeo; Hareesh, U. S. (ACS Applied Materials & Interfaces, 2016)
Nitrogen containing mesoporous carbon obtained by the pyrolysis of graphene oxide (GO) wrapped ZIF-8 (Zeolitic Imidazolate Frameworks-8) micro crystals is demonstrated to be an efficient catalyst for the oxygen reduction reaction (ORR). ZIF-8 synthesis in the presence of GO sheets helped to realize layers of graphene oxide over ZIF-8 microcrystals and the sphere-like structures thus obtained, on heat treatment, transformed to highly porous carbon with a nitrogen content of about 6.12% and surface area of 502 m(2)/g. These catalysts with a typical micromeso porous architecture exhibited an onset potential of 0.88Vvs RHE in a four electron pathway and also demonstrated superior durability in alkaline medium compared to that of the commercial Pt/C catalyst. The N-doped porous carbon derived from GO sheathed ZIF-8 core shell structures could therefore be employed as an efficient electrocatalyst for fuel cell applications.
Keywords: alkaline fuel cell; graphene oxide; N-doped carbon; oxygen reduction reaction; porous carbon; ZIF-8

Heterotriangulene-based unsymmetrical squaraine dyes: synergistic effects of donor moieties and out-of-plane branched alkyl chains on dye cell performance - Karjule, Neeta; Munavvar, Fairoos M. K.; Nithyanandhan, Jayaraj (Journal of Materials Chemistry A, 2016)
Unsymmetrical squaraine sensitizers with two different donor moieties, triphenylamine (NSQR) and heterotriangulene (NSQ1–3), for dye-sensitized solar cells (DSSCs) have been designed and synthesized. These dyes utilize the indolium moiety to control charge recombination dynamics at the TiO2-dye-electrolyte interface by connecting linear and branched alkyl functionalities. In the present study, an efficient heterotriangulene (HT) donor and a branched alkyl group at sp3-C atoms were strategically incorporated to increase the power conversion efficiency (PCE) of zwitterionic dyes by improving photo-current density (Jsc) and open-circuit potential (Voc) of the cell. Among these four dyes, NSQ3 exhibited the highest efficiency of 6.73% with a Jsc of 18.74 mA cm−2, Voc of 0.53 V, and fill factor (ff) of 68.3%, without any co-adsorbent under an irradiance of 100 mW cm−2 (simulated AM 1.5G sunlight). In the presence of 3α,7α-dihydroxy-5β-cholanic acid (CDCA), NSQ1, NSQ2 and NSQ3 showed an efficiency of 7.07%, 7.38% and 7.17%, respectively. Despite the low Voc, far red light harvesting efficiency, reduced dye aggregation, long lifetime (τ) of injected electrons and high quantum efficiency of NSQ1–3 played constructive roles in achieving high PCE efficiency. Deceleration of charge recombination for NSQ dye cells was further studied by electrochemical impedance spectroscopy (EIS) and open-circuit photo-voltage decay (OCVD) measurements.

Hierarchical K/LTL zeolites: synthesis by alkali treatment, characterization and catalytic performance in knoevenagel condensation reaction - Tangale, Nilesh P.; Sonar, Shilpa K.; Niphadkar, Prashant S.; Joshi, Praphulla N. (Journal of Industrial and Engineering Chemistry, 2016)
The hierarchical K/LTL zeolites prepared by post-synthesis modification with aqueous 1.5 M KOH solution by varying alkali volume to K/LTL zeolite (10-70 ml/g) ratios, were examined in Knoevenagel condensation. The physico-chemical properties of the catalysts were thoroughly evaluated by PXRD, ICP, CO2-TPD, XPS, N-2 adsorption/desorption and Si-29 and Al-22 MAS-NMR. Among all the samples, hierarchical K/LTL prepared by treating K/LTL with 50 ml aqueous 1.5 M KOH solution per gram of K/LTL displayed about 1.5 fold higher catalytic activity as compared to parent K/LTL, presumably because of combined effect of enhanced basicity and molecular diffusion through pore channels. (C)2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
Keywords: Basicity; Hierarchical zeolite; K/LTL; Knoevenagel condensation; Micro-mesoporous composite

High hydroxide conductivity in a chemically stable crystalline metal-organic framework containing a water-hydroxide supramolecular chain - Nagarkar, Sanjog S.; Anothumakkool, Bihag; Desai, Aamod V.; Shirolkar, Mandar M.; Kurungot, Sreekumar; Ghosh, Sujit K. (Chemical Communications, 2016)
A chemically stable cationic MOF encapsulating an in situ formed water-hydroxide supramolecular anionic chain is realized for high hydroxide (OH-) ion conductivity in the solid-state (Type A). High OH- ion conductivity and low activation energy of the MOF demonstrate the advantage of the in situ incorporation of OH- ions to achieve efficient OH- ion conduction in the solid-state.

Highly efficient nitrogen-doped hierarchically porous carbon supported Ni nanoparticles for the selective hydrogenation of furfural to furfuryl alcohol - Kotbagi, Trupti V.; Gurav, Hanmant R.; Nagpure, Atul S.; Chilukuri, Satyanarayana V.; Bakker, Martin G. (RSC Advances, 2016)
Nickel nanoparticles supported on nitrogen doped hierarchically porous carbon (Ni/CN) are found to be highly efficient and reusable catalysts for the selective hydrogenation of biomass-derived furfural to furfuryl alcohol (FA). Various characterization methods were used to study the structural and morphological features of the catalysts. Furfural conversion of 96% and 95% FA selectivity was obtained using a 5 wt% Ni/CN catalyst. This catalyst showed excellent recyclability without any loss in activity and FA selectivity when it was reused four times. The higher catalytic performance is attributed to the nitrogen incorporated hierarchical porous 3D carbon network.

Hybrid perovskite quantum nanostructures synthesized by electrospray antisolvent-solvent extraction and intercalation - Naphade, Rounak; Nagane, Satyawan; Shanker, G. Shiva; Fernandes, Rohan; Kothari, Dushyant; Zhou, Yuanyuan; Padture, Nitin P.; Ogale, Satishchandra (ACS Applied Materials & Interfaces, 2016)
Perovskites based on organometal lead halides have attracted great deal of scientific attention recently in the context of solar cells and optoelectronic devices due to their unique and tunable electronic and optical properties. Herein, we show that the use of electrospray technique in conjunction with the antisolventsolvent extraction leads to novel low-dimensional quantum structures (especially 2-D nanosheets) of CH3NH3PbI3- and CH3NH3PbBr3-based layered perovskites with unusual luminescence properties. We also show that the optical bandgaps and emission characteristics of these colloidal nanomaterials can be tuned over a broad range of visible spectral region by compositional tailoring of mixed-halide (I- and Br-based) perovskites.
Keywords: 2D nanostructure systems; antisolvent-solvent extraction; bandgap tuning; electrospray; nanosheets; perovskite; quantum dots

Hydrogenation of cinnamaldehyde to hydrocinnamaldehyde over Pd nanoparticles deposited on nitrogen-doped mesoporous carbon - Nagpure, Atul S.; Gurrala, Lakshmiprasad; Gogoi, Pranjal; Chilukuri, Satyanarayana V. (RSC Advances, 2016)
Palladium nanoparticles deposited on nitrogen-doped mesoporous carbon (NMC) were synthesized by simple ultrasonic-assisted method. This novel Pd-NMC catalyst was highly active and selective for the hydrogenation of cinnamaldehyde (CA) to hydrocinnamaldehyde (HCA) at room temperature (30 degrees C) under low H-2 pressure. The nitrogen-free mesoporous carbon (MC) and activated carbon (AC) were also employed as the support for Pd in the liquid-phase hydrogenation of CA. The incorporation of nitrogen into carbon matrix remarkably enhanced the catalytic activity and C=C bond hydrogenation selectivity (HCA selectivity of 93% with 100% CA conversion for Pd-NMC) in CA hydrogenation compared to the catalysts with no nitrogen (HCA selectivity of 66 and 47% for Pd-MC and Pd-AC, respectively). Moreover, Pd-NMC catalyst demonstrated an excellent recyclability without any loss in activity and HCA selectivity when it was reused for six times. The superior catalytic performance of Pd-NMC catalyst in CA hydrogenation is attributed to the small size of Pd nanoparticles due to presence of high nitrogen content (11.6 wt%) and mesoporous nature of NMC support.

Identification of unintuitive features of sumoylation through mathematical modeling - Puntambekar, Shraddha S.; Nyayanit, Dimpal; Saxena, Priyanka; Gadgil, Chetan J. (Journal of Biological Chemistry, 2016)
Sumoylation is a multistep, multienzymatic post-translational modification in which a small ubiquitin-like modifier protein (SUMO) is attached to the target. We present the first mathematical model for sumoylation including enzyme mechanism details such as autosumoylation of E2 and multifunctional nature of SENP. Simulations and analysis reveal three nonobvious properties for the long term response, modeled as an open system: (i) the steady state sumoylation level is robust to variation in several enzyme properties; (ii) even when autosumoylation of E2 results in equal or higher activity, the target sumoylation levels are lower; and (iii) there is an optimal SENP concentration at which steady state target sumoylation level is maximum. These results are qualitatively different for a short term response modeled as a closed system, where e.g. sumoylation always decreases with increasing SENP levels. Simulations with multiple targets suggest that the available SUMO is limiting, indicating a possible explanation for the experimentally observed low fractional sumoylation. We predict qualitative differences in system responses at short post-translational and longer transcriptional time scales. We thus use this mechanism-based model to explain system properties and generate testable hypotheses for existence and mechanism of unexpected responses.

In vitro and ex vivo antitubercular activity of diarylheptanoids from the rhizomes of alpinia officinarum hance - Honmore, Varsha S.; Rojatkar, Supada R.; Nawale, Laxman U.; Arkile, Manisha A.; Khedkar, Vijay M.; Natu, Arun D.; Sarkar, Dhiman (Natural Product Research, 2016)
Phytochemical investigation of methanol extract of the rhizomes of Alpinia officinarum Hance afforded four known diarylheptanoids 1,7-diphenylhept-4-en-3-one (1), 5-hydroxy-1,7-diphenyl-3-heptanone (2), 5-hydroxy-7-(4 ''-hydroxy-3 ''-methoxyphenyl)-1-phenyl-3-heptanone (3), and 7-(4 ''-hydroxy-3 ''-methoxyphenyl)-1-phenyl heptan-3-one (4).The acetate derivative of (4), 7-(4 ''-actetate-3 ''-methoxy phenyl)-1-phenyl heptan-3-one (5), was prepared. These diarylheptanoids exhibited promising in vitro and ex vivo antitubercular activity for the first time against dormant Mycobacterium tuberculosis H37Ra with the IC50 values between 0.3447.69 and 0.1322.91 mu M, respectively. All compounds showed comparable activity against Mycobacterium bovis BCG (dormant phage) and did not show any activity against two gram + ve and two gram -ve bacterial strains. These compounds were also weakly cytotoxic up to 300 mu M against three human cancer cell lines THP-1, Panc-1 and A549.

Inhibition of miR-21 by 3 `/5 `-serinyl-capped 2 `-O-Methyl RNA Interspersed with 2 `-O-(2-Amino-3-Methoxypropyl) uridine units - Nahar, Smita; Kotikam, Venubabu; Kumar, Vaijayanti A.; Maiti, Souvik (Nucleic Acid Therapeutics, 2016)
miRNAs are highly conserved class of small ncRNAs whose involvement in human pathophysiologies is extensively investigated. MiR-21 is a well established oncogenic miRNA whose deregulation plays a significant role in onset and progression of cancer. The need of novel approaches to downregulate miR-21 is rapidly expanding. Potent inhibition of miR-21 is achieved by chemically modified 2-O-methyl RNA oligonucleotide. The serinol capping at 3 and 5ends and the interspersed 2-O-(R-2-amino-3-methoxypropyl) uridine units enhance the nuclease resistance and efficacy of 2-O-methyl RNA for the inhibition of miR-21. This represents a simple and novel modification for developing oligonucleotide-based therapeutics.
Keywords: antagomirs; cancer; microRNA; noncoding RNA; oligonucleotides

Inverse high internal phase emulsion polymerization (i-HIPE) of GMMA, HEMA and GDMA for the preparation of superporous hydrogels as a tissue engineering scaffold - Nalawade, Archana C.; Ghorpade, Ravindra V.; Shadbar, Sadiqua; Qureshi, Mohammed Shadbar; Chavan, Nayaku; Khan, Ayesha A.; Ponrathnam, S. (Journal of Materials Chemistry B, 2016)
A series of novel superporous hydrogels for regenerative medicine were prepared by oil-in-water (o/w) or inverse high internal phase emulsion (i-HIPE) copolymerization of glycerol monomethacrylate (GMMA), 2-hydroxy ethyl methacrylate (HEMA) and glycerol dimethacrylate (GDMA) as a cross-linker using a non toxic solvent and a redox initiator system at the physiological temperature (37 degrees C). The monomer GMMA was synthesized from glycidyl methacrylate (GMA) by an alternative facile method using Amberlyst-15. The described i-HIPEs showed a significantly wider stability window. The polyHIPE hydrogels were characterized by FTIR, BET method for surface area, mercury porosimetry, SEM, DSC, TGA, XRD, compressive strain and strain recovery. The swelling ratio of the hydrogels and their degradation in 0.007 M NaOH and lipase B (Candida antarctica) solutions were determined gravimetrically and the rate of degradation was explained in terms of the molecular structure of the hydrogels. The morphological studies showed that the pore diameter varied between 20 and 30 mu m and the pore throats (interconnecting windows) diameter was in the range of 4-8 mu m. The described polyHIPE hydrogels were found to have an open cell morphology and interconnected pore architecture, which are important characteristics for scaffold applications. The initial cytotoxicity study performed according to ISO-10993-5 indicated cytocompatibility (97% cell viability) and the subsequent cell seeding and proliferation study exhibited 55-88% cell viability (increased monotonously from GHG-1 to GHG-5), which could be attributed to modulation of the physical and chemical properties of the hydrogels. The described super porous hydrogels are considered as potential candidates for scaffold materials in tissue engineering applications.

Isolates of alpinia officinarum hance as COX-2 inhibitors: evidence from anti-inflammatory, antioxidant and molecular docking studies - Honmore, Varsha S.; Kandhare, Amit D.; Kadam, Parag P.; Khedkar, Vijay M.; Sarkar, Dhiman; Bodhankar, Subhash L.; Zanwar, Anand A.; Rojatkar, Supada R.; Natu, Arun D. (International Immunopharmacology, 2016)
Background: Inflammation triggered by oxidative stress can cause various ailments, such as cancer, rheumatoid arthritis, asthma, diabetes etc. In the last few years, there has been a renewed interest in studying the antioxidant and anti-inflammatory action of plant constituents such as flavonoids and diarylheptanoids. Aim: To evaluate the antioxidant, anti-inflammatory activity and the total phenolic content of isolated compounds from Alpinia officinarum rhizomes. Furthermore, molecular docking was performed to study the binding mode of these compounds into the active site of cyclooxygenase-2 (COX -2). Methods: A. officinarum rhizomes were extracted by maceration, using methanol. This extract was further fractionated by partitioning with hexane, chloroform and ethyl acetate and these fractions on further purification resulted in isolation of five pure compounds. Characterization was carried out by using H-1 NMR, C-13 NMR and MS. They were further evaluated for antioxidant and anti-inflammatory activity using carrageenan-induced paw edema model in rats. Molecular docking study was performed using Glide module integrated in Schrodinger molecular modeling software. Results: The compounds were identified as 1,7-diphenylhept-4-en-3-one (1), 5-hydroxy-1,7-diphenyl-3-heptanone (2), 3,5,7-trihydroxyflavone (Galangin, 3), 3,5,7-trihydroxy-4'-methoxyflavone (Kaempferide, 4) and 5-hydroxy-7-(4 `'-hydroxy-3 `'-methoxyphenyl)-1-phenyl-3-heptanone (5). The compound-3 and compound-5 (10 mg/kg) showed significant (p < 0.001) antioxidant and anti-inflammatory potential. Moreover, total phenolic content was detected as 72.96 mg and 51.18 mg gallic acid equivalent respectively. All the five isolates were found to be good binders with COX-2 (average docking score -9.03). Conclusions: Galangin and 5-hydroxy-7-(4 `'-hydroxy-3 `'-methoxyphenyl)-1-phenyl-3-heptanone exhibited anti-inflammatory and in-vitro antioxidant activity which may be due to presence of phenolic content in it. The molecular docking study revealed that these compounds have affinity towards COX-2 active site which can further be explored as selective COX-2 inhibitors. The results obtained in this work justify the use of A. officinarum in the treatment of inflammatory disorders like rheumatoid arthritis and inflammatory bowel diseases. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: 5-Hydroxy-7-(4 `'-hydroxy-3 `'-methoxyphenyl)-1-phenyl-3-heptanone; Alpinia officinarum; Anti-inflammatory; Antioxidant; COX-2 inhibitors; Galangin

Kinetic studies on an algal biofilm reactor for raw sewage water treatment - Gera, Gayatri S.; Yewalkar, Swati N.; Nene, Sanjay; Kulkarni, Bhaskar D.; Kamble, Sanjay P. (Chemical Engineering & Technology, 2016)
A packed-bed algae biofilm reactor was developed using porous and nonporous dual packings. The biofilm was cultivated on reticulated polyurethane foam cubes. The nonporous glass Raschig rings were taken as bed support that helps to remove generated gas from the system. The effect of variables such as column length-to-diameter ratio, catalyst cube dimension, and feed flow rate on the treatment of sewage water was studied. The reaction kinetics indicates that the nutrients uptake rate is dependent on both pore and film diffusion. The kinetics of uptake of nutrients follows a pseudo first-order reaction. From the pseudo reaction rate constant, Thiele modulus and effectiveness factor were calculated and a kinetic model equation for fractional nutrient uptake was developed in terms of operating variables. The model can predict the reaction rate with low deviation. The results obtained may be valuable for large-scale treatment of sewage water.

Low band gap benzimidazole COF supported Ni3N as highly active OER catalyst - Nandi, Shyamapada; Singh, Santosh Kumar; Mullangi, Dinesh; Illathvalappil, Rajith; George, Leena; Vinod, Chathakudath P.; Kurungot, Sreekumar; Vaidhyanathan, Ramanathan (Advanced Energy Materials, 2016)
Covalent organic frameworks (COFs) have structures and morphologies closely resembling graphenes, whose modular construction permits atomiclevel manipulations. This, combined with their porous structure, makes them excellent catalyst supports. Here, the high electrocatalytic activity of a composite, formed by supporting Ni3N nanoparticles on a benzimidazole COF, for oxygen evolution reaction is shown. The composite oxidizes alkaline water with a near-record low overpotential of 230 mV @ 10 mA cm(-2) (eta(10)). This high activity is attributed to the ability of the COF to confine the Ni3N nanoparticles to size regimes otherwise difficult to obtain and to its low band gap character (1.49 eV) arising from the synergy between the conducting Ni3N nanoparticles and the pi-conjugated COF. The COF itself, as a metalfree self-standing framework, has an oxygen evolution reaction activity with 10 of 400 mV. The periodic structure of the COF makes it serve as a matrix to disperse the catalytically active Ni3N nanoparticles favoring their high accessibility and thereby good charge-transport within the composite. This is evident from the amount of O-2 evolved (230 mmol h(-1) g(-1)), which, to the best of our knowledge, is the highest reported. The work reveals the emergence of COF as supports for electrocatalysts.

Low-overpotential electrocatalytic water splitting with noble-metal-free nanoparticles supported in a sp(3) n-rich flexible COF - Mullangi, Dinesh; Dhavale, Vishal M.; Shalini, Sorout; Nandi, Shyamapada; Collins, Sean; Woo, Tom; Kurungot, Sreekumar; Vaidhyanathan, Ramanathan (Advanced Energy Materials, 2016)
Covalent organic frameworks (COFs) are crystalline organic polymers with tunable structures. Here, a COF is prepared using building units with highly flexible tetrahedral sp(3) nitrogens. This flexibility gives rise to structural changes which generate mesopores capable of confining very small (<2 nm sized) non-noble-metal-based nanoparticles (NPs). This nanocomposite shows exceptional activity toward the oxygen-evolution reaction from alkaline water with an overpotential of 258 mV at a current density of 10 mA cm(-2). The overpotential observed in the COF-nanoparticle system is the best in class, and is close to the current record of approximate to 200 mV for any noble-metalfree electrocatalytic water splitting system-the Fe-Co-Ni metal-oxide-film system. Also, it possesses outstanding kinetics (Tafel slope of 38.9 mV dec(-1)) for the reaction. The COF is able to stabilize such small-sized NP in the absence of any capping agent because of the COF-Ni(OH)(2) interactions arising from the N-rich backbone of the COF. Density-functional-theory modeling of the interaction between the hexagonal Ni(OH)(2) nanosheets and the COF shows that in the most favorable configuration the Ni(OH)(2) nanosheets are sandwiched between the sp(3) nitrogens of the adjacent COF layers and this can be crucial to maximizing their synergistic interactions.

Molecular cloning and in silico studies of physiologically significant trehalase from drosophila melanogaster - Shukla, Ekta; Thorat, Leena; Bhavnani, Varsha; Bendre, Ameya D.; Pal, J. K.; Nath, B. B.; Gaikwad, Sushama M. (International Journal of Biological Macromolecules, 2016)
Trehalase, a physiologically important glycosidase is known for its crucial role in insect glycometabolism and stress recovery. The present study describes the molecular cloning of a gene fragment, encoding the catalytically active trehalase from Drosophila melanogaster (DmTre) and its heterologous expression in Escherichia coli. The 1275 bp gene was overexpressed in two different vectors viz., pET28a and pCOLD TF and investigated for variable soluble expression, purification and activity of the recombinant enzyme with optimum pH and temperature of enzyme as 6 and 55 degrees C, respectively. The sequence was characterized in silico by subjecting it to homology search, multiple sequence alignment and phylogenetic tree construction revealing its identity to other trehalases which belong to glycoside hydrolase family 37. The deduced amino acid sequence and modeled 3D structure of DmTre possessed all features of trehalase superfamily, including signature motifs and catalytic domain. The active site pocket of recombinant DmTre was compared with the crystal structure of E. coli trehalase identifying Glu424 and Asp226 as the putative catalytic residues. Additionally, enzyme-substrate docking suggests possible involvement of other residues in the catalysis along with Asp226. The present study holds significance in understanding the structural aspects of Drosophila trehalase in spite of unavailabilty of eukaryotic trehalase crystal structure. (C) 2016 Elsevier B.V. All rights reserved.

New analytical method for rapid analysis and speciation of arsenic in rice - Nambiar, O. G. B. (Arsenic Research and Global Sustainability - Proceedings of the 6th International Congress on Arsenic in the Environment, AS 2016, 2016)
A new analytical method for the direct quantitative determination of arsenic (As) in rice is presented in this paper. This procedure is capable of performing speciation of As (III) and As (V). Thiamine present in the sample can also be measured by this procedure. Filter-plug inserted inside the reactor cap fixes the hydrogen sulfide gas generated in the reactor vessel. Arsenic along with the hydrogen sulfide is measured by substituting the filter plug with cotton plug without the sulfide absorbent. The hydrogen sulfide also produces pink stain in the detector tube. Arsenic and thiamine are found to be in the molar ratio of 1:1. For determining total As, the arsenate is converted to arsenite by a catalyst incorporated in the reagent, which is converted to arsine by sodium borohydride. The main As species detected in rice samples was inorganic As (III), which is consistent with the reported results. It takes only about 20 minutes to analyze one sample of rice. The present procedure can also analyze biological samples like urine, hair etc.

Nitrogen doping in oxygen-deficient Ca2Fe2O5: a strategy for efficient oxygen reduction oxide catalysts - Jijil, Chamundi P.; Lokanathan, Moorthi; Chithiravel, Sundaresan; Nayak, Chandrani; Bhattacharyya, Dibyendu; Jha, Shambhu Nath; Babu, P. D.; Kakade, Bhalchandra A.; Devi, R. Nandini (ACS Applied Materials and Interfaces, 2016)

No promoter left behind (NPLB): learn de novo promoter architectures from genome-wide transcription start sites - Mitra, Sneha; Narlikar, Leelavati (Bioinformatics, 2016)
Promoters have diverse regulatory architectures and thus activate genes differently. For example, some have a TATA-box, many others do not. Even the ones with it can differ in its position relative to the transcription start site (TSS). No Promoter Left Behind (NPLB) is an efficient, organism-independent method for characterizing such diverse architectures directly from experimentally identified genome-wide TSSs, without relying on known promoter elements. As a test case, we show its application in identifying novel architectures in the fly genome.

Novel tetrazoloquinoline-rhodanine conjugates: highly efficient synthesis and biological evaluation - Subhedar, Dnyaneshwar D.; Shaikh, Mubarak H.; Nawale, Laxman; Yeware, Amar; Sarkar, Dhiman; Khan, Firoz A. Kalam; Sangshetti, Jaiprakash N.; Shingate, Bapurao B. (Bioorganic & Medicinal Chemistry Letters, 2016)
In search of new active molecules against Mycobacterium tuberculosis (MTB) H37Ra and Mycobacterium bovis BCG, a small focused library of rhodanine incorporated tetrazoloquinoline has been efficiently synthesized by using [HDBU][HSO4] acidic ionic liquid. The compound 3c found to be promising inhibitor of MTB H37Ra and M. bovis BCG characterized by lower MIC values 4.5 and 2.0 mu g/mL, respectively. The active compounds were further tested for cytotoxicity against HeLa, THP-1, A549 and PANC-1 cell lines using MTT assay and showed no significant cytotoxic activity at the maximum concentration evaluated. Again, the synthesized compounds were found to have potential antifungal activity. Furthermore, to rationalize the observed biological activity data, the molecular docking study also been carried out against a potential target Zmp1 enzyme of MTB H37Ra, which revealed a significant correlation between the binding score and biological activity for these compounds. The results of in vitro and in silico study suggest that these compounds possess ideal structural requirement for the further development of novel therapeutic agents. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: antifungal; Antitubercular; Cytotoxicity; Docking study; Rhodanine derivatives

Novel tetrazoloquinoline-thiazolidinone conjugates as possible antitubercular agents: synthesis and molecular docking - Subhedar, Dnyaneshwar D.; Shaikh, Mubarak H.; Shingate, Bapurao B.; Nawale, Laxman; Sarkar, Dhiman; Khedkar, Vijay M. (Medchemcomm, 2016)
A novel approach for the synthesis of a new 4-thiazolidinone scaffold was developed by a one-pot three-component cyclocondensation of various tetrazolo quinoline aldehydes 1a-f, acid hydrazide 2a-c, and thioglycolic acid 3 in the presence of [DBUH].OAc] as a catalyst in high yields. All the conjugates were screened for their antimycobacterial activity against MTB H37Ra and M. bovis BCG strains, with the MIC values ranging from 0.99-13.55 mu mol mL(-1) and 0.14-20.11 mu mol mL(-1), respectively. The 4-thiazolidinone-incorporated tetrazoloquinoline derivatives 4a, 4d, 4g, 4j, 4m, and 4p were highly potent against MTB H37Ra and M. bovis BCG strains. The most active compounds were also evaluated for their cytotoxicity against MCF-7, A549, and HCT 116 cell lines and were found to be non-cytotoxic. Further, molecular docking studies into the active site of the InhA enzyme revealed a similar binding mode to the native ligand in the crystal structure, thereby helping us to understand the ligand-protein binding interaction and establish a structural basis for the inhibition of mycobacterium tuberculosis. The results suggest that the tetrazoloquinoline-thiazolidinone conjugates 4a, 4d, 4g, 4j, 4m, and 4p are promising antitubercular agents.

Optimization by box-behnken experimental design fur synthesis of n-hexyl levulinate biolubricant over hierarchical H-ZSM-5: an effort towards agricultural waste minimization - Nandiwale, Kakasaheb Y.; Bokade, Vijay V. (Process Safety and Environmental Protection, 2016)
The present study is devoted to develop efficient catalytic process for conversion of agricultural waste feedstock to value added chemicals. In this context, the n-hexyl levulinate, a renewable biolubricant was synthesized by esterification of biomass derived levulinic acid (LA) with n-hexanol in a closed batch system. Hierarchical-HZ-5 (modified H-ZSM-5) was used as a heterogeneous acid catalyst. There are no reports available on the synthesis of n-hexyl levulinate biolubricant using renewable levulinic acid. The process variables such as catalyst to LA ratio (X-1), n-hexanol to LA molar ratio (X-2), reaction time (X-3) and reaction temperature (X-4) were optimized by response surface methodology (RSM), using the Box-Behnken model. Analysis of variance was done to check the suitability and significance of the quadratic model. The yield of n-hexyl levulinate obtained was 97% with 100% selectivity at optimum process parameters. The RSM analysis predicted that catalyst to LA ratio is most significant (value of p < 0.0001) and n-hexanol to LA molar ratio is least significant (value of p = 0.0064) process parameter in esterification. The quadratic model established was revealed to be suitable and statistically precise with correlation value (R-2) of 0.9837 to predict the yield of n-hexyl levulinate. (C) 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Agricultural waste feedstock; Esterification; Hierarchical-HZ-5; n-Hexyl levulinate; Optimization; Response surface methodology

Orientation effect induced selective chelation of Fe2+ to a glutamic acid appended conjugated polymer for sensing and live cell imaging - Senthilkumar, T.; Parekh, Nimisha; Nikama, Shrikant B.; Asha, S. K. (Journal of Materials Chemistry B, 2016)
Intracellular detection and imaging of labile iron(II) pools is very important in tracking physiological processes that demand new and rapid sensing probes. In this report, we present a water soluble polymer based probe for the fluorescence sensing and live cell imaging of labile Fe2+ ions with high selectivity for the first time. The polymer probe was based on conjugated polyfluorene which was appended with amino acid (L-glutamic acid). The biocompatibility of the polymer was confirmed from an MTT assay which demonstrated >90% cell viability even at 300 mu g ml(-1) loading of polymers. Simple glutamic acid did not show selectivity towards any of the divalent ions. However, glutamic acid appended polyfluorene exhibited selective chelation to Fe2+ ions resulting in immediate sensing activity for Fe2+ ions in water and living cells with fluorescence turn-off response. The limit of detection of the PF-Ph-GA polymer probe was 46 (+/- 2) nM which indicated high sensitivity for Fe2+ over other ions reported in the literature. The polymer also exhibited improved sensing activity in the range of intracellular pH (5-9) which is advantageous in differentiating endogenous changes. The probe was successfully applied for the fluorescence imaging of intracellular and supplemented labile iron(II) pools in living HeLa cells.

Oxidation of linezolid by permanganate in acidic medium: Pd(II) catalysis, kinetics and pathways - Kulkarni, Raviraj M.; Hanagadakar, Manjunath S.; Malladi, Ramesh S.; Santhakumari, B.; Nandibewoor, Sharanappa T. (Progress in Reaction Kinetics and Mechanism, 2016)
The uncatalysed and Pd(II)-catalysed oxidation of linezolid (LNZ) by permanganate (PMGT) in acidic medium was carried out in the pH range from 3.0 to 6.0. The second order rate constants were found to decrease with increase in pH. The apparent second order rate constants for the uncatalysed reaction were, for example, k `'(app)= 6.32 dm(3) mol(-1) at pH 3.0 and k `'(app). = 2.64 dm(3) mol(-1) s(-1) at pH 6.0 and at 25 +/- 0.2 degrees C and for the Pd(II)-catalysed reaction the total apparent second order rate constants were k `'(app) = 75.5 dm(3) mol(-1) s(-1) at pH 3.0 and k `'(app). = 45.66 dm(3) mol(-1) s(-1) at pH 6.0 and at 25 +/- 0.2 degrees C. The rate constant of the Pd(II)-catalysed reaction was thus ten times higher than for the uncatalysed reaction. The oxidation products of the reaction were identified using high resolution LC-MS. The reaction progresses via formation of a Pd-LNZ complex, which reacts with acidic PMGT to form an intermediate compound, which then decomposes to give oxidised products. The dependence of the rate of reaction on various parameters, such as pH, temperature, [LNZ], [PMGT], [Pd(II)], dielectric constant and ionic strength were studied and activation parameters for the reaction were evaluated and discussed.

Palladium-catalyzed internal nucleophile-assisted hydration-olefin insertion cascade: diastereoselective synthesis of 2,3-dihydro-1H-inden-1-ones - Vinoth, Perumal; Nagarajan, Subbiah; Maheswari, C. Uma; Sudalai, Arumugam; Pace, Vittorio; Sridharan, Vellaisamy (Organic Letters, 2016)
A novel palladium-catalyzed hydration-olefin insertion cascade assisted by internal nucleophiles was developed for the synthesis of biologically significant 2,3-dihydro-1H-inden-1-ones under mild conditions. A detailed mechanistic study revealed that the assistance of the internal nucleophiles is crucial to trigger the cascade reaction via nucleopalladation of the alkyne moiety. The overall reaction is equivalent to regioselective hydration of alkynes followed by intramolecular Michael addition. This highly efficient and 100% atom-economical domino sequence afforded cis-2,3-disubstituted 2,3-dihydro-1H-inden-1-ones in excellent yields (up to 99%) with complete diastereoselectivity.

Peeping into genomic architecture by re-sequencing of Ochrobactrum intermedium M86 strain during laboratory adapted conditions - Gohil, K. N.; Neurgaonkar, P. S.; Paranjpe, A.; Dastager, S. G.; Dharne, M. S. (Genomics Data, 2016)
Advances in de novo sequencing technologies allow us to track deeper insights into microbial genomes for restructuring events during the course of their evolution inside and outside the host. Bacterial species belonging to Ochrobactrum genus are being reported as emerging, and opportunistic pathogens in this technology driven era probably due to insertion and deletion of genes. The Ochrobactrum intermedium M86 was isolated in 2005 from a case of non-ulcer dyspeptic human stomach followed by its first draft genome sequence in 2009. Here we report re-sequencing of O. intermedium M86 laboratory adapted strain in terms of gain and loss of genes. We also attempted for finer scale genome sequence with 10 times more genome coverage than earlier one followed by comparative evaluation on Ion PGM and Illumina MiSeq. Despite their similarities at genomic level, lab-adapted strain mainly lacked genes encoding for transposase protein, insertion elements family, phage tail-proteins that were not detected in original strain on both chromosomes. Interestingly, a 5 kb indel was detected in chromosome 2 that was absent in original strain mapped with phage integrase gene of Rhizobium spp. and may be acquired and integrated through horizontal gene transfer indicating the gene loss and gene gain phenomenon in this genus. Majority of indel fragments did not match with known genes indicating more bioinformatic dissection of this fragment. Additionally we report genes related to antibiotic resistance, heavy metal tolerance in earlier and re-sequenced strain. Though SNPs detected, there did not span urease and flagellar genes. We also conclude that third generation sequencing technologies might be useful for understanding genomic architecture and re-arrangement of genes in the genome due to their ability of larger coverage that can be used to trace evolutionary aspects in microbial system.

Pharmaceutical cocrystals: walking the talk - Bolla, Geetha; Nangia, Ashwini (Chemical Communications, 2016)
Pharmaceutical cocrystals belong to a sub-class of cocrystals wherein one of the components is a drug molecule (or an active pharmaceutical ingredient, API) and the second is a benign food or drug grade additive (generally regarded as safe, GRAS). The two components are hydrogen-bonded in a fixed stoichiometric ratio in the crystal lattice. In the past decade, pharmaceutical cocrystals have demonstrated significant promise in their ability to modify the physicochemical and pharmacokinetic properties of drug substances, such as the solubility and dissolution rate, bioavailability, particle morphology and size, tableting and compaction, melting point, physical form, biochemical and hydration stability, and permeability. In this feature review, we highlight some prominent examples of drug cocrystals which exhibit variable hardness/softness and elasticity/plasticity depending on coformer selection, improvement of solubility and permeability in the same cocrystal, increase of the melting point for solid formulation, enhanced color performance, photostability and hydration stability, and a longer half-life. Cocrystals of flavanoids and polyphenols can make improved pharmaceuticals and also extend to the larger class of nutraceuticals. The application of crystal engineering to assemble ternary cocrystals expands this field to drug-drug cocrystals which may be useful in multi-drug resistance, mitigating side effects of drugs, or attenuating/enhancing drug action synergistically by rational selection. The advent of new techniques for structural characterization beyond the standard X-ray diffraction will provide a better understanding of drug phases which are at the borderline of crystalline-amorphous nature and even newer opportunities in the future.

Photocatalytic H-2 evolution from water-methanol mixtures on InGaO3(ZnO)(m) with an anisotropic layered structure modified with CuO and NiO cocatalysts - Narendranath, Soumya B.; Thekkeparambil, Saranya V.; George, Leena; Thundiyil, Shibin; Devi, R. Nandini (Journal of Molecular Catalysis A-Chemical, 2016)
InGaO3(ZnO)(m) series of oxides is found to be active for photocatalytic H-2 evolution from water-methanol mixtures. The structure of this series is highly anisotropic with InO6 octahedral layers sandwiching Ga/ZnOn polyhedra. The structural anisotropy in which the conducting layer is spatially separated from the charge generation sites may help in suppressing charge recombination and consequently enhance catalytic activity. The band gaps of the series obtained from absorption spectra are above 3.6 eV and hence they are not active under visible light irradiation. H-2 evolution is considerably enhanced under UV light on employing NiO as cocatalyst due to facile electron transfer from InGaO3(ZnO)(m). to NiO. However, when CuO is used as cocatalyst, visible light activity could be brought out. Due to the very low band gap of CuO, it can act as a sensitizer absorbing in visible light. The band positions become conducive for H-2 evolution due to band alignments consequent to electron accumulation in CuO conduction band. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: InGaO3(ZnO)(m); photocatalytic water splitting; visible light; XPS; XRD

Physicochemical and antimicrobial photodynamic chemotherapy of unsymmetrical indium phthalocyanines alone or in the presence of magnetic nanoparticles - Osifeko, Olawale L.; Uddin, Imran; Mashazi, Philani N.; Nyokong, Tebello (New Journal of Chemistry, 2016)
An AB(3) type photosensitiser, consisting of 4-pyridylsulfanyl units (denoted as B-3) and one aminophenoxy (denoted as A) group (complex 3) was synthesized. Complex 3 was then quaternized to form complex 4. The aminophenoxy substituent of complex 3 was used for the formation of the amide linkage with the carboxylic functionalised magnetic nanoparticles. Complexes 3 and 4 and their conjugates with magnetic nanoparticles were then used for photodynamic antimicrobial chemotherapy on E. coli. The cationic photosensitiser 4 showed a high efficiency for photodynamic antimicrobial chemotherapy at a very low concentration compared to its conjugate on E. coli.

Phytogenic silver, gold, and bimetallic nanoparticles as novel antitubercular agents - Singh, Richa; Nawale, Laxman; Arkile, Manisha A.; Wadhwani, Sweety; Shedbalkar, Utkarsha; Chopade, Snehal; Sarkar, Dhiman; Chopade, Balu Ananda (International Journal of Nanomedicine, 2016)
Purpose: Multi- and extensively drug-resistant tuberculosis (TB) is a global threat to human health. It requires immediate action to seek new antitubercular compounds and devise alternate strategies. Nanomaterials, in the present scenario, have opened new avenues in medicine, diagnosis, and therapeutics. In view of this, the current study aims to determine the efficacy of phytogenic metal nanoparticles to inhibit mycobacteria. Methods: Silver (AgNPs), gold (AuNPs), and gold-silver bimetallic (Au-AgNPs) nanoparticles synthesized from medicinal plants, such as Barleria prionitis, Plumbago zeylanica, and Syzygium cumini, were tested against Mycobacterium tuberculosis and M. bovis BCG. In vitro and ex vivo macrophage infection model assays were designed to determine minimum inhibitory concentration (MIC) and half maximal inhibitory concentration of nanoparticles. Microscopic analyses were carried out to demonstrate intracellular uptake of nanoparticles in macrophages. Besides this, biocompatibility, specificity, and selectivity of nanoparticles were also established with respect to human cell lines. Results: Au-AgNPs exhibited highest antitubercular activity, with MIC of <2.56 mu g/mL, followed by AgNPs. AuNPs did not show such activity at concentrations of up to 100 mu g/mL. In vitro and ex vivo macrophage infection model assays revealed the inhibition of both active and dormant stage mycobacteria on exposure to Au-AgNPs. These nanoparticles were capable of entering macrophage cells and exhibited up to 45% cytotoxicity at 30 mu g/mL (ten times MIC concentration) after 48 hours. Among these, Au-AgNPs synthesized from S. cumini were found to be more specific toward mycobacteria, with their selectivity index in the range of 94-108. Conclusion: This is the first study to report the antimycobacterial activity of AuNPs, AgNPs, and Au-AgNPs synthesized from medicinal plants. Among these, Au-AgNPs from S. cumini showed profound efficiency, specificity, and selectivity to kill mycobacteria. These should be investigated further to develop novel TB nanoantibiotics.
Keywords: Antimycobacterial agent; Cytotoxicity; drug resistance; Mycobacteria; Nanoparticles; tuberculosis

PolyHIPE derived freestanding 3D carbon foam for cobalt hydroxide nanorods based highperformance supercapacitor - Patil, Umakant M.; Ghorpade, Ravindra V.; Nam, Min Sik; Nalawade, Archana C.; Lee, Sangrae; Han, Haksoo; Jun, Seong Chan (Scientific Reports, 2016)
The current paper describes enhanced electrochemical capacitive performance of chemically grown Cobalt hydroxide (Co(OH)(2)) nanorods (NRs) decorated porous three dimensional graphitic carbon foam (Co(OH)(2)/3D GCF) as a supercapacitor electrode. Freestanding 3D porous GCF is prepared by carbonizing, high internal phase emulsion (HIPE) polymerized styrene and divinylbenzene. The PolyHIPE was sulfonated and carbonized at temperature up to 850 degrees C to obtain graphitic 3D carbon foam with high surface area (389 m(2) g(-1)) having open voids (14 mu m) interconnected by windows (4 mu m) in monolithic form. Moreover, entangled Co(OH)(2) NRs are anchored on 3D GCF electrodes by using a facile chemical bath deposition (CBD) method. The wide porous structure with high specific surface area (520 m(2) g(-1)) access offered by the interconnected 3D GCF along with Co(OH)(2) NRs morphology, displays ultrahigh specific capacitance, specific energy and power. The Co(OH)(2)/3D GCF electrode exhibits maximum specific capacitance about similar to 1235 F g(-1) at similar to 1 Ag-1 charge-discharge current density, in 1 M aqueous KOH solution. These results endorse potential applicability of Co(OH)(2)/3D GCF electrode in supercapacitors and signifies that, the porous GCF is a proficient 3D freestanding framework for loading pseudocapacitive nanostructured materials.

Promotional effect of Fe on the performance of supported Cu catalyst for ambient pressure hydrogenation of furfural - Manikandan, Marimuthu; Venugopal, Ashok Kumar; Nagpure, Atul S.; Chilukuri, Satyanarayana V.; Raja, Thirumalaiswamy (RSC Advances, 2016)
A noble-metal free FeCu based bimetallic catalyst system prepared by facile co-impregnation method was found to be highly admirable for vapour phase selective hydrogenation of furfural to furfuryl alcohol at ambient pressure. Monometallic Cu/gamma-Al2O3, Fe/gamma-Al2O3 and bimetallic FeCu/gamma-Al2O3 catalysts with different Fe loadings were prepared. Structural and morphological features of the catalysts were thoroughly investigated by several physico-chemical characterization techniques. The influence of various reaction parameters, such as Fe loading, reaction temperature and flow of reactants was examined with respect to furfural conversion and furfuryl alcohol yield. The results clearly showed that an optimum amount of Fe is necessary to enhance the catalytic activity of monometallic Cu/gamma-Al2O3 for the selective hydrogenation of furfural. The catalyst FC-10 with 10 wt% Fe exhibited excellent activity which led to high furfural conversion (>93%) and furfuryl alcohol selectivity (>98%) under mild reaction conditions. The higher activity of bimetallic FeCu/gamma-Al2O3 compared to monometallic Cu/gamma-Al2O3 is ascribed to the formation of FeCu bimetallic particles and the existence of oxygen vacancies in the Fe oxide system. The superior activity after Fe loading on the Cu-based catalyst was attributed to the synergy between Cu and Fe. A plausible mechanism is proposed to explain the promoting effect of Fe, which involves synergism between Fe sites with strong oxophilic nature and Cu sites with a high ability for hydrogen activation. Based on the activity results, prolonged catalytic activity and spent catalyst analysis, the developed FeCu/gamma-Al2O3 catalyst is inexpensive, eco-benign and robust, which makes it a promising candidate for the efficient conversion of biomass-derived substrates to fine chemicals and drop-in biofuels.

Recent advances in N-heterocyclic carbene (NHC)-catalysed benzoin reactions (vol 12, pg 444, 2016) - Menon, Rajeev S.; Biju, Akkattu T.; Nair, Vijay (Beilstein Journal of Organic Chemistry, 2016)
Keywords: acyloin reaction; benzoin reaction; N-heterocyclic carbenes; organocatalysis; umpolung

Recent advances in N-heterocyclic carbene (NHC)-catalysed benzoin reactions - Menon, Rajeev S.; Biju, Akkattu T.; Nair, Vijay (Beilstein Journal of Organic Chemistry, 2016)
N-Heterocyclic carbenes (NHCs) have emerged as a powerful class of organocatalysts that mediate a variety of organic transformations. The Benzoin reaction constitutes one of the earliest known carbon-carbon bond-forming reactions catalysed by NHCs. The rapid growth of NHC catalysis in general has resulted in the development of a variety of benzoin and benzoin-type reactions. An overview of such NHC-catalysed benzoin reactions is presented.
Keywords: acyloin reaction; benzoin reaction; N-heterocyclic carbenes; organocatalysis; umpolung

Relativistic coupled-cluster study of RaF as a candidate for the parity- and time-reversal-violating interaction - Sasmal, Sudip; Pathak, Himadri; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Physical Review A, 2016)
We have employed both the Z-vector method and the expectation-value approach in the relativistic coupled-cluster framework to calculate the scalar-pseudoscalar (S-PS) P, T-odd interaction constant W-s and the effective electric field E-eff experienced by the unpaired electron in the ground electronic state of RaF. Further, the magnetic hyperfine structure constants of Ra-223 in RaF and Ra-223(+) are also calculated and compared with the experimental values wherever available to judge the extent of the accuracy obtained with the employed methods. The outcome of our study reveals that the Z-vector method is superior to the expectation-value approach in terms of accuracy obtained for the calculation of ground-state property. The Z-vector calculation shows that RaF has a high Eeff (52.5 GV/cm) and W-s (141.2 kHz), which makes it a potential candidate for the electric dipole moment of the electron (eEDM) experiment. An estimation of uncertainty associated with our final results is made, and it is found that it lies below 10%.

Relativistic equation-of-motion coupled-cluster method for the electron attachment problem - Pathak, Himadri; Sasmal, Sudip; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Computational and Theoretical Chemistry, 2016)
The article considers the successful implementation of relativistic equation-of-motion coupled cluster method for the electron attachment problem (EA-EOMCC) at the level of single- and double- excitation approximation. The implemented relativistic EA-EOMCC method is employed to calculate ionization potential values of alkali metal atoms (Li, Na, K, Rb, Cs, Fr) and the vertical electron affinity values of LiX (X = H, F, Cl, Br), NaY (Y = H, F, Cl) starting from their closed-shell configuration. Both four component and exact two-component calculations are done for all the opted systems. Further, we have shown the effect of spin-orbit interaction considering the atomic systems. The results of our atomic calculations are compared with the values from the NIST database and the results are found to be very accurate (<1%). (C) 2015 Elsevier B.V. All rights reserved.

Relativistic equation-of-motion coupled-cluster method using open-shell reference wavefunction: application to ionization potential - Pathak, H.; Sasmal, S.; Nayak, M. K.; Vaval, N.; Pal, S. (Journal of Chemical Physics, 2016)
The open-shell reference relativistic equation-of-motion coupled-cluster method within its four-component description is successfully implemented with the consideration of single- and double- excitation approximations using the Dirac-Coulomb Hamiltonian. At the first attempt, the implemented method is employed to calculate ionization potential value of heavy atomic (Ag, Cs, Au, Fr, and Lr) and molecular (HgH and PbF) systems, where the effect of relativity does really matter to obtain highly accurate results. Not only the relativistic effect but also the effect of electron correlation is crucial in these heavy atomic and molecular systems. To justify the fact, we have taken two further approximations in the four-component relativistic equation-of-motion framework to quantify how the effect of electron correlation plays a role in the calculated values at different levels of theory. All these calculated results are compared with the available experimental data as well as with other theoretically calculated values to judge the extent of accuracy obtained in our calculations.

Remediation of domestic and industrial effluents using algae - Nene, S. N.; Gera, G.; Yewalkar, S. N. (Algal Biorefinery: An Integrated Approach, 2016)
In the environment, microbial activity is considered as one of the most important mechanisms for the abatement of water-borne pollutants. In the natural and anthropogenic environment the wide range of contaminates are not eliminated by single specie but by the complex interaction of a mixed microbial population performing complementary reactions. This principle is very much applicable for the treatment of the industrial and domestic wastewater, which has excess of nitrogenous compounds (N) and phosphates (P). N and P along with various organic pollutants, if not properly treated, would create a devastating impact on natural aquatic ecosystems. Among the many other disturbing impacts, most prevalent is the phenomenon of eutrophication, which is the accumulation of high levels of organic matter and the decomposing organisms, which deplete the oxygen in water, and causing the death of other organisms, such as fish. The excess nutrients in the aquatic ecosystem support the growth of various phytoplanktons. It not only spoils the water quality but also adversely affects the whole aquatic ecosystem. This chapter will address the possibility of effectively utilizing a natural microbial flora/consortium, enriched with the rapidly growing algae for the remediation of polluted water bodies.

Reporter nanoparticle that monitors its anticancer efficacy in real time - Kulkarni, Ashish; Rao, Poornima; Natarajan, Siva; Goldman, Aaron; Sabbisetti, Venkata S.; Khater, Yashika; Korimerla, Navya; Chandrasekar, Vineethkrishna; Mashelkar, Raghunath Anant; Sengupta, Shiladitya (Proceedings of the National Academy of Sciences of the United States of America, 2016)
The ability to monitor the efficacy of an anticancer treatment in real time can have a critical effect on the outcome. Currently, clinical readouts of efficacy rely on indirect or anatomic measurements, which occur over prolonged time scales postchemotherapy or postimmunotherapy and may not be concordant with the actual effect. Here we describe the biology-inspired engineering of a simple 2-in-1 reporter nanoparticle that not only delivers a cytotoxic or an immunotherapy payload to the tumor but also reports back on the efficacy in real time. The reporter nanoparticles are engineered from a novel two-staged stimuli-responsive polymeric material with an optimal ratio of an enzyme-cleavable drug or immunotherapy (effector elements) and a drug function-activatable reporter element. The spatiotemporally constrained delivery of the effector and the reporter elements in a single nanoparticle produces maximum signal enhancement due to the availability of the reporter element in the same cell as the drug, thereby effectively capturing the temporal apoptosis process. Using chemotherapy-sensitive and chemotherapy-resistant tumors in vivo, we show that the reporter nanoparticles can provide a real-time noninvasive readout of tumor response to chemotherapy. The reporter nanoparticle can also monitor the efficacy of immune checkpoint inhibition in melanoma. The self-reporting capability, for the first time to our knowledge, captures an anticancer nanoparticle in action in vivo.
Keywords: chemotherapy; immunotherapy; monitoring; nanoparticle; reporter

Search for parity and time reversal violating effects in HgH: relativistic coupled-cluster study - Sasmal, Sudip; Pathak, Himadri; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Journal of Chemical Physics, 2016)
The high effective electric field (E-eff) experienced by the unpaired electron in an atom or a molecule is one of the key ingredients in the success of electron electric dipole moment (eEDM) experiment and its precise calculation requires a very accurate theory. We, therefore, employed the Z-vector method in the relativistic coupled-cluster framework and found that HgH has a very large E-eff value (123.2 GV/cm) which makes it a potential candidate for the next generation eEDM experiment. Our study also reveals that it has a large scalar-pseudoscalar (S-PS) P, T-violating interaction constant, W-s = 284.2 kHz. To judge the accuracy of the obtained results, we have calculated parallel and perpendicular magnetic hyperfine structure (HFS) constants and compared with the available experimental values. The results of our calculation are found to be in nice agreement with the experimental values. Therefore, by looking at the HFS results, we can say that both E-eff and W-s values are also very accurate. Further, We have derived the relationship between these quantities and the ratio which will help to get model independent value of eEDM and S-PS interaction constant. (C) 2016 AIP Publishing LLC.

Self-assembly of biohybrid polymers - Kedracki, Dawid; Abraham, Jancy Nixon; Prado, Enora; Nardin, Corinne (Macromolecular self-assembly, 2016)
Self-assembly is considered to be the process through which building blocks spontaneously organize into well-defined frequently functional structures. The tailoring of properties of such structures has drawn attention in various fields, in particular, in enzymatic cascade reactions, drug delivery, amphiphilic copolymer nanocontainers, and nanoreactors. Polymer-DNA hybrid self-assemblies, in addition to responsiveness to ionic strength, are sensitive to hybridization, which renders the establishment of a theoretical framework challenging when both specific hydrogen bonding between complementary sequences and association are to be taken into consideration. Numerous various highly characterized self-assemblies are recognized to organize through nucleation dependent polymerization, including microtubule formation, sickle-cell fibril formation, flagellum assembly, among others. Interpolyelectrolyte complexes (IPECs) have attracted attention due to the large number of emerging and potential applications. Environmental factors such as the medium also play a role in the complex formation process, especially pH and ionic strength.

Silk fibroin-sophorolipid gelation: deciphering the underlying mechanism - Dubey, Parul; Kumar, Sugam; Aswal, Vinod K.; Ravindranathan, Sapna; Rajamohanan, Pattuparambil R.; Prabhune, Asmita; Nisal, Anuya (Biomacromolecules, 2016)
Silk fibroin (SF) protein, produced by silkworm Bombyx mori, is a promising biomaterial, while sophorolipid (SL) is an amphiphilic functional biosurfactant synthesized by nonpathogenic yeast Candida bombicola. SL is a mixture of two forms, acidic (ASL) and lactonic (LSL), which when added to SF results in accelerated gelation of silk fibroin. LSL is known to have multiple biological functionalities and hence hydrogels of these green molecules have promising applications in the biomedical sector. In this work, SANS, NMR, and rheology are employed to examine the assembling properties of individual and mixed SLs and their interactions with SF to understand the mechanism that leads to rapid gelation. SANS and NMR studies show that ASL assembles to form charged micelles, while LSL forms micellar assemblies and aggregates of a mass fractal nature. ASL and LSL together form larger mixed micelles, all of which interact differently with SF. It is shown that preferential binding of LSL to SF causes rapid unfolding of the SF chain leading to the formation of intermolecular beta sheets, which trigger fast gelation. Based on the observations, a mechanism for gelation of SF in the presence of different sophorolipids is proposed.

Silver nanoparticles: a new perspective in endodontic therapy - Jadhav, Rajashree; Bhide, Shrinivas; Bhagavatula L. V. Prasad; Kunchiraman, Bipinraj; Shimpi, Jayesh; Nandhini, Usha (OAB Journal, 2016)
Silver has been in use in medicine since time immemorial because of its antimicrobial properties. But due to the emergence of antibiotics the use of silver has been declined. Several pathogenic bacteria have developed resistance against various antibiotics. This has led to reemergence of silver. Recently nano science and nanotechnology are gaining tremendous popularity. The small size of nanoparticles provides larger surface area and hence increases the effectiveness of nanoparticles. Silver nanoparticles are used in medical and dental applications ranging from silver based wound dressings, silver coated medicinal devices like catheters, endotrachial tubes, bone cements, in gels, lotions, cosmetics, in dental restorative materials, endodontic cements, dental implants caries inhibitory agents, and in prosthesis. The purpose of this article is to discuss briefly the potential role of silver nano particles in endodontic therapy.

Spectroscopy and catalytic activity study of gold supported on barium titanate nanotubes for styrene epoxidation - Nepak, Devadutta; Srinivas, Darbha (Applied Catalysis A-General, 2016)
Gold (0.5-5 wt.%) supported on barium titanate nanotubes (Au/BaTNT) were prepared, characterized and for the first time, investigated as catalysts for selective oxidation of styrene with oxygen (O-2 or H-2 + O-2) and peroxides (H2O2 or TBHP). Conversion of styrene enhanced when H-2 was co-added to O-2 in the reactions. Au/BaTNT activated O-2 and H-2 and produced H2O2 in situ for use in oxidations. Peroxides were found better oxidants than O-2. At optimized conditions, styrene oxide selectivity of 80.1 wt.% at styrene conversion of 60.5 wt.% was achieved over Au(1 wt.%)/BaTNT using TBHP. Au particles (5.0-7.4 nm) were dispersed and decorated on the walls of BaTNT. They exhibited superior performance to the known Au catalysts in styrene oxidation. Reactive oxygen species formed during oxidation reactions were followed with in situ spectral characterizations (diffuse reflectance UV-vis and FT -Raman). Au/BaTNT was reusable in four recycles with little loss in catalytic activity. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Au Nanoparticles; reactive oxygen species; spectroscopy; Styrene Oxidation; Titanate nanotubes

Stereoselective quenching of cedryl carbocation in epicedrol biosynthesis - Shinde, Sandip S.; Navale, Govinda R.; Said, Madhukar S.; Thulasiram, Hirekodathakallu V. (Tetrahedron Letters, 2016)
Epicedrol synthase catalyzes the cyclization of achiral diphosphate substrate, (E,E)-farnesyldiphosphate (FPP) into epicedrol. GC-MS analysis of assay extracts obtained by incubating FPP with epicedrol synthase in 21.6 at % H2(18)O buffer showed the molecular ion of 224 for epicedrol. The labeled oxygen study presented here unambiguously demonstrates that the hydroxyl group of the epicedrol synthase enzymatic product, epicedrol, is derived from a water molecule, not from the phosphate moiety of the FPP. (C) 2016 Elsevier Ltd. All rights reserved.

Surface tailored PS/TiO2 composite nanofiber membrane for copper removal from water - Wanjale, Santosh; Birajdar, Mallinath S.; Jog, Jyoti Prakash; Neppalli, Ramesh; Causin, Valerio; Karger-Kocsis, Jozsef; Lee, Jonghwi; Panzade, Prasad (Journal of Colloid and Interface Science, 2016)
Polystyrene (PS)/TiO2 composite nanofiber membranes have been fabricated by electrospinning process for Cu2+ ions removal from water. The surface properties of the polystyrene nanofibers were modulated by introducing TiO2 nanoparticles. The contact angle of the PS nanofiber membrane was found to be decreased with increasing concentration of TiO2, depicted enhanced hydrophilicity. These membranes were highly effective in adsorbing Cu2+ ions from water. The adsorption capacity of these membranes was found to be 522 mg/g, which is significantly higher than the results reported by other researchers. This was attributed to enhanced hydrophilicity of the PS/TiO2 composite nanofiber membranes and effective adsorption property of TiO2 nanoparticles. (C) 2016 Elsevier Inc. All rights reserved.
Keywords: electrospinning; Metal ion adsorption; Nanofiber; TiO2; Water treatment/purification

Sustainable catalytic process for synthesis of triethyl citrate plasticizer over phosphonated USY zeolite - Nandiwaleand, Kakasaheb Y.; Bokade, Vijay V. (Bulletin of Chemical Reaction Engineering and Catalysis, 2016)
Fruits wastage is harmful to health and environment concerning spreading diseases and soil pollution, respectively. To avoid this issue, use of citrus fruit waste for the production of citric acid (CA) is one of viable mean to obtain value added chemicals. Moreover, synthesis of triethyl citrate (TEC), a non-toxic plasticizer by esterification of CA with ethanol over heterogeneous catalyst would be renewable and sustainable catalytic process. In this context, parent Ultrastable Y (USY) and different percentage phosphonated USY (P-USY) zeolites were used for the synthesis of TEC in a closed batch reactor, for the first time. The synthesized catalysts were characterized by N2-adsorption desorption isotherm, powder X-ray diffraction (XRD) and NH3 temperature programmed desorption (TPD. Effect of reaction conditions, such as the molar ratio of ethanol to CA (5:1 - 20:1), the catalyst to CA ratio (0.05-0.25) and reaction temperature (363-403 K), were studied in view to maximizing CA conversion and TEC yield. Phosphonated USY catalysts were found to be superior in activity (CA conversion and TEC yield) than parent USY, which is attributed to the increased in total acidity with phosphonation. Among the studied catalysts, the P2USY (2% phosphorous loaded on USY) was found to be an optimum catalyst with 99% CA conversion and 82% TEC yield, which is higher than the reported values. This study opens new avenues of research demonstrating principles of green chemistry such as easy separable and reusable catalyst, non-toxic product, bio-renewable synthetic route, milder operating parameters and waste minimization.

Synthesis and antitubercular activity of new 1,3,4-oxadiazoles bearing pyridyl and thiazolyl scaffolds - Dhumal, Sambhaji T.; Deshmukh, Amarsinh R.; Bhosle, Manisha R.; Khedkar, Vijay M.; Nawale, Laxman U.; Sarkar, Dhiman; Mane, Ramrao A. (Bioorganic & Medicinal Chemistry Letters, 2016)
In search of more potent and safe new antitubercular agents, here new 2-pyridinyl substituted thiazolyl-5-aryl-1,3,4-oxadiazoles (6a-o), have been designed and synthesized using thionicotinamide as a starting, following novel multistep synthetic route. An intermediate, pyridinyl substituted thiazolyl acid hydrazide (4) when condensed with benzoic acids/nicotinic acids (5a-o) in the presence of silica supported POCl3 yielded better to excellent yields of the title compounds. All the synthesized compounds (6a-o) and intermediate acid hydrazide (4) have been screened for their in vitro antitubercular activity against Mycobacterium tuberculosis H37Ra (MTB) and Mycobacterium bovis BCG. Amongst them, 6f, 6j, 6l and 6o have revealed promising activity against M. bovis BCG at concentrations less than 3 mu g/mL. These compounds have shown low cytotoxicity (CC50: > 100 mu g/mL) towards four human cancer cell lines. Molecular docking study has also been performed against mycobacterial enoyl reductase (InhA) enzyme to gain an insight into the binding modes of these molecules and recorded good binding affinity. The ADME properties the title products have also been analyzed. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: 1; 3; 4-Oxadiazole; Antitubercular activity; Cytotoxicity; Molecular docking; Pyridine; Thiazole

Synthesis and antitubercular activity of new benzo[b]thiophenes - Mahajan, Pravin S.; Nikam, Mukesh D.; Nawale, Laxman U.; Khedkar, Vijay M.; Sarkar, Dhiman; Gill, Charansingh H. (ACS Medicinal Chemistry Letters, 2016)
In vitro and ex vivo efficacies of four series of benzo[b]thiophene-2-carboxylic acid derivatives were studied against Mycobacterium tuberculosis H37Ra (MTB). Benzo[b]thiophenes were also tested in vitro against multidrug resistant Mycobacterium tuberculosis H37Ra (MDR-MTB), and 7b was found to be highly active against A- and DMDR-MTB/MTB (MIC ranges 2.73-22.86 mu g/mL). The activity of all benzo[b]-thiophenes against M. bovis BCG (BCG) was also assessed grown under aerobic and under conditions of oxygen depletion. Compounds 8c and 8g showed significant activity with MICs of 0.60 and 0.61 mu g/mL against dormant BCG. The low cytotoxicity and high selectivity index data against human cancer cell lines, HeLa, Panc-1, and THP-1 indicate the potential importance of the development of benzo[b]thiophene-based 1,3-diketones and flavones as lead candidates to treat mycobacterial infections. Molecular docking studies into the active site of DprE1 (Decaprenylphosphoryl-beta-n-ribose-2'-epimerase) enzyme revealed a similar binding mode to native ligand in the crystal structure thereby helping to understand the ligand protein interactions and establish a structural basis for inhibition of MTB. In summary, its good activity in in vitro and ex vivo model, as well as its activity against multidrug-resistant M. tuberculosis H37Ra in a potentially latent state, makes 7b an attractive drug candidate for the therapy of tuberculosis.
Keywords: Benzo[b]thiophene; Cytotoxicity; M. Bovis BCG; MDR-MTB; Molecular docking

Synthesis and evaluation of thieno[2,3-d]pyrimidin-4(3H)-ones as potential antitubercular agents (vol 6, pg 2209, 2015) - Borate, Hanumant B.; Annadate, Ritesh A.; Vagh, Sandip S.; Pisal, Mahesh M.; Deokate, Sagar B.; Arkile, Manisha A.; Jadhav, Nandadeep J.; Nawale, Laxman U.; Sarkar, Dhiman (Medchemcomm, 2016)

Synthesis, biological evaluation and molecular docking of novel coumarin incorporated triazoles as antitubercular, antioxidant and antimicrobial agents - Shaikh, Mubarak H.; Subhedar, Dnyaneshwar D.; Shingate, Bapurao B.; Khan, Firoz A. Kalam; Sangshetti, Jaiprakash N.; Khedkar, Vijay M.; Nawale, Laxman; Sarkar, Dhiman; Navale, Govinda R.; Shinde, Sandip S. (Medicinal Chemistry Research, 2016)
A series of new coumarin-based 1,2,3-triazole derivatives were designed, synthesized and evaluated for their antitubercular activity in vitro against Mycobacterium tuberculosis H37Ra, antioxidant activity by DPPH radical scavenging assay, antimicrobial activity in vitro against three gram-positive bacteria (Staphylococcus aureus, Micrococcus luteus and Bacillus cereus) and three gram-negative bacteria (Escherichia coli, Pseudomonas fluorescens and Flavobacterium devorans as well as three fungi (Aspergillus niger, Penicillium chrysogenum and Curvularia lunata). The bioactive assay showed that some synthesized coumarin triazoles displayed comparable or even better antitubercular, antioxidant, antibacterial and antifungal efficacy in comparison with reference drugs. Furthermore, docking study has been performed against DprE1 enzyme of M. tuberculosis that showed good binding interactions. Moreover, the synthesized compounds were also analyzed for ADME properties and showed potential to build up as good oral drug candidates. New coumarin-based 1,2,3-triazole derivatives were designed, synthesized and evaluated for their antitubercular, antioxidant, antibacterial and antifungal activity. Some of the coumarin-based triazole derivatives displayed comparable or even better efficacy in comparison with reference drugs. Molecular docking study has been performed against DprE1 enzyme of Mycobacterium tuberculosis showed good binding interactions. [GRAPHICS] .
Keywords: 1; 2; 3-Triazole; ADME prediction; Antimicrobial; Antioxidant; Antitubercular; Click chemistry; Docking study

Synthesis, biological evaluation and molecular docking studies of N-acylheteroaryl hydrazone derivatives as antioxidant and anti-inflammatory agents - Mahajan, Pravin S.; Nikam, Mukesh D.; Khedkar, Vijay M.; Jha, Prakash C.; Sarkar, Dhiman; Gill, Charansingh H. (Research on Chemical Intermediates, 2016)
In search of new therapeutics with greater potency, three new series of 3-methyl-1-phenyl-1H-thieno[2,3-c]pyrazole-5-carbohydrazide derivatives have been synthesized and evaluated for their in vitro antioxidant and anti-inflammatory activities. The hydrazones bearing a core pyrazole, chromone and tetrazolo[1,5-a]quinoline scaffold showed promising activities. Interestingly, compounds 3a (EC50 = 06.00 +/- A 2.36) and 5c (EC50 = 07.21 +/- A 0.67) showed the most potent antioxidant activity, while compounds 3a (EC50 = 10.25 +/- A 1.08), 7b (EC50 = 10.50 +/- A 0.99) and 7c (EC50 = 11.18 +/- A 0.15) showed significant anti-inflammatory activity. Furthermore, molecular docking studies also revealed a significant correlation between the binding score and biological activity for these compounds to describe the molecular basis for the structure activity relationship (SAR) results. As these compounds are good cyclooxygenase inhibitors, isoenzyme inhibitory potency studies are warranted.
Keywords: Anti-inflammatory; Antioxidant; Docking study; N-Acylhydrazones; Structure-activity relationship

Synthesis, biological evaluation and molecular docking study of some novel indole and pyridine based 1,3,4-oxadiazole derivatives as potential antitubercular agents - Desai, N. C.; Somani, Hardik; Trivedi, Amit; Bhatt, Kandarp; Nawale, Laxman; Khedkar, Vijay M.; Jha, Prakash C.; Sarkar, Dhiman (Bioorganic & Medicinal Chemistry Letters, 2016)
A series of indole and pyridine based 1,3,4-oxadiazole derivatives 5a-t were synthesized and evaluated for their in vitro antitubercular activity against Mycobacterium tuberculosis H37Ra (MTB) and Mycobacterium bovis BCG both in active and dormant state. Compounds 5b, 5e, 5g and 5q exhibited very good antitubercular activity. All the newly synthesized compounds 5a-t were further evaluated for antiproliferative activity against HeLa, A549 and PANC-1 cell lines using modified MTT assay and found to be noncytotoxic. On the basis of cytotoxicity and MIC values against Mycobacterium bovis BCG, selectivity index (SI) of most active compounds 5b, 5e, 5g and 5q was calculated (SI = GI(50)/MIC) in active and dormant state. Compounds 5b, 5e and 5g demonstrated SI values >= 10 against all three cell lines and were found to safe for advance screening. Compounds 5a-t were further screened for their antibacterial activity against four bacteria strains to assess their selectivity towards MTB. In addition, the molecular docking studies revealed the binding modes of these compounds in active site of enoyl reductase (InhA), which in turn helped to establish a structural basis of inhibition of mycobacteria. The potency, low cytotoxicity and selectivity of these compounds make them valid lead compounds for further optimization. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: 1; 3; 4-Oxadiazole; Antitubercular activity; Cytotoxicity; Indole; Molecular docking; Pyridine

Synthesis, microstructure, optical and field emission studies of iron vanadium oxide nanosheets - Badadhe, Satish S.; Suryawanshi, Sachin R.; Naphade, Rounak A.; Chaudhary, Minakshi V.; More, Mahendra A.; Shelke, Manjusha V.; Ogale, Satishchandra B. (Journal of Physics D-Applied Physics, 2016)
We report a single step growth of thin graphene-like, densely packed FeV3O8 (FVO) nanosheets on silicon substrates via facile hydrothermal synthesis. These nanosheets have dimensions of a few microns with thin edges, offering very high aspect ratio. These FVO nanosheets exhibit excellent field emission behaviour with low turn on and threshold voltages of 1.3 V mu m(-1) and 1.7 V mu m(-1), respectively. The corresponding emitter delivers high emission current density of (similar to 1.650 mA cm(-2)) at fairly low applied field (similar to 4.00 V mu m(-1)).
Keywords: FeV3O8; field emission; nanosheets

Synthesis of fuel intermediates from HMF/fructose - Nale, S. D.; Jadhav, V. H. (Catalysis Letters, 2016)
Alkylation of toluene, anisole and mesitylene with HMF and fructose is reported using Glu–Fe3O4–SO3H solid acid catalyst. HMF was found to alkylate toluene, anisole and mesitylene in high yields and high selectivity under solvent free conditions. Polyalkylation and self etherification of HMF was not observed. The alkylated product on hydrodeoxygenation forms liquid alkanes of different chain lengths which have properties of transportation fuels or diesel fuels. The catalyst was easily recoverable and reusable minimum 5 times to achieve good yields and high selectivity of alkylated product.

Synthesis of Sn-containing anatase (TiO2) by sol-gel method and their performance in catalytic water splitting under visible light as a function of tin content - Tangale, N. P.; Niphadkar, P. S.; Samuel, V.; Deshpande, Suvarna S.; Joshi, P. N.; Awate, S. V. (Materials Letters, 2016)
Sol-gel route was employed to prepare a series of Sn-containing anatase with different molar (Ti/Sn) ratios ranging from 49 to 1. Samples were characterized by powder XRD, UV-vis, XPS, SEM, EDAX, low temperature N-2 sorption technique and Raman Spectroscopy. Except anatase phase, no other crystalline phase was observed when Ti/Sn molar ratio was varied from 49 to 9 and for Sn free sample. However, further decrease in the ratio lead to the appearance of additional SnO2 phase whose peak intensities were increased with the increase in the tin content. Irrespective of tin content, all samples showed red-shift in UV-vis spectra. Moreover, samples showed Raman shift to higher vibration side from 143 cm(-1) to 147 cm(-1) indicating the doping of Sn2+ into TiO2. By virtue of low band gap, anatase crystallite size and an absence of XRD visible SnO2, ST (19) has shown maximum photocatalytic activity upon 1 wt% Pt loading. It has exhibited the highest rate (0.1264 mmole/g/h) for visible light induced hydrogen evolution by water splitting. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Semiconductors; Sn2+ doped titania; SnO2/TiO2; Sol-gel preparation; visible light; water splitting

Synthesis of tyrosyl-DNA phosphodiesterase i inhibitors - Nale, S. D.; Jadhav, V. H. (Tetrahedron Letters, 2016)
The first report for the synthesis of tyrosyl-DNA phosphodiesterase I inhibitors 3,4-dimethoxyphenol-1-β-d-(6′-O-galloyl)glucopyranoside 3 and 3-(4-hydroxy-3-methoxyphenyl)propane-1,2-diol 2-β-d-(6′-O-galloyl) glucopyranoside 5 has been accomplished starting from readily available d-glucose as a starting material. An efficient and general approach has been reported for the synthesis of compounds 3 and 5 with an overall yield of 26% and 27%, respectively.

Syringic acid: structural elucidation and co-crystallization - Thipparaboina, Rajesh; Mittapalli, Sudhir; Thatikonda, Sowjanya; Nangia, Ashwini; Naidu, V. G. M.; Shastri, Nalini R. (Crystal Growth & Design, 2016)
Syringic acid (SYRA) is a potential antioxidant used in traditional Chinese medicine and is an emerging nutraceutical. Current reports claim its potential anti-angiogenic, anti-glycating, anti-hyperglycaemic, neuroprotective, and memory-enhancing properties in various animal models. To date, SYRA crystal structure has not been elucidated, and no crystal engineering studies have been reported. This study reports the crystal structure of SYRA for the first time along with its nicotinamide (SNCT-E) and urea (SU-EA-M) co-crystals. All forms were successfully characterized using single crystal X-ray diffraction (XRD), powder XRD, and differential scanning calorimetry. Single crystal analysis revealed that SYRA crystallized in the C2/c space group, whereas SNCT-E (2:1) and SU-EA-M (1:2) crystallized in the P21/n and Cmca space group, respectively. Novel co-crystals have shown improved solubility, modified dissolution profiles, and improved flow and compressibility. Cytotoxic effects were explored in DU145 prostate cancer cell lines for the first time, and significant enhancement in cytotoxicity by the co-crystals was observed compared to plain components. A two-fold increase in % cytotoxicity of SNCT-E was observed when compared to the corresponding physical mixture. These studies shed light on potential utility of SYRA as a coformer for various pharmaceutical applications to design synergistic and organ-protective co-crystals.

Systematic evaluation of biophysical and functional characteristics of selenomethylene-locked nucleic acid-mediated inhibition of miR-21 - Nahar, Smita; Singh, Amrita; Morihiro, Kunihiko; Moai, Yoshihiro; Kodama, Tetsuya; Obika, Satoshi; Maiti, Souvik (Biochemistry, 2016)
miRNAs constitute an important layer of gene regulation mediated by sequence-specific targeting of mRNAs. Aberrant expression of miRNAs contributes to a host of pathological states. Promoting cancer, miR-21 is upregulated in variety of cancers and promotes tumor progresion by suppressing a network of tumor suppressor genes. Here we describe a novel class of bicyclic RNA analogues, selenomethylene-locked nucleic acid (SeLNA), that display high affinity, improved metabolic stability, and increased potency for miR-21 inhibition. The thermal stability (T-m) for duplexes was increased significantly with incorporation of SeLNA monomers as compared to that of the unmodified DNA RNA hybrid. A comprehensive thermodynamic profile obtained by isothermal titration calorimetry revealed a favorable increase in the enthalpy of hybridization for SeLNA containing DNA and target RNA heteroduplexes. SeLNA modifications displayed remarkable binding affinity for miR-21 target RNA with a K-a of <= 1.05 x 10(8) M-1. We also observed enhanced serum stability for SeLNA RNA duplexes with a half-life of <= 36 h. These in vitro results were well correlated with the antisense activity in cancer cells imparting up to similar to 91% inhibition of miR-21. The functional impact of SeLNA modifications on miR-21 inhibition was further gauged by investigating the migration and invasion characterisitics of cancer cells, which were drastically reduced to similar to 49 and similar to 55%, respectively, with SeLNA having four such modifications. Our findings demonstrate SeLNA as a promising candidate for therapeutics for disease associated miRNAs.

Thickness tunable transport in alloyed WSSe field effect transistors - Karande, Shruti D.; Kaushik, Naveen; Narang, Deepa S.; Late, Dattatray; Lodha, Saurabh (Applied Physics Letters, 2016)
We report the field effect transistor characteristics of exfoliated transition metal dichalcogenide alloy tungsten sulphoselenide. WSSe is a layered material of strongly bonded S-W-Se atoms having weak interlayer van der Waals forces with a significant potential for spintronic and valleytronic applications due to its polar nature. The X-ray photoelectron spectroscopy measurements on crystals grown by the chemical vapor transport method indicate a stoichiometry of the form WSSe. We report flake thickness tunable transport mechanism with n-type behavior in thin flakes (<= 11 nm) and ambipolarity in thicker flakes. The devices with flake thicknesses of 2.4 nm-54.8nm exhibit a maximum electron mobility of similar to 50 cm(2)/V s along with an I-ON/I-OFF ratio > 10(6). The electron Schottky barrier height values of 35 meV and 52meV extracted from low temperature I-V measurements for 3.9 nm and 25.5 nm thick flakes, respectively, indicate that an increase in hole current with thickness is likely due to lowering of the bandgap through an increase in energy of the valence band maximum. Published by AIP Publishing.

Tracing the architecture of caffeic acid phenethyl ester cocrystals: studies on crystal structure, solubility, and bioavailability implications - Ketkar, Sameer; Pagire, Sudhir K.; Goud, N. Rajesh; Mahadik, Kakasaheb R.; Nangia, Ashwini; Paradkar, Anant (Crystal Growth & Design, 2016)
Caffeic acid phenethyl ester (CAPE) is a polyphenolic active compound present in popular apiproduct, "propolis", obtained from beehives, Though it has broad therapeutic capability, the bioavailability of CAPE is limited due to poor solubility. In this study, we report novel cocrystals of CAPE engineered using coformers such as caffeine (CAP), isonicotinamide (INIC), and nicotinamide (NIC) with enhanced solubility and bioavailability of CAPE. The cocrystals were prepared by microwave-assisted cocrystallization and characterized using PXRD, DSC, and Raman spectroscopy. PXRD and DSC confirm the successful formation and phase purity of CAPE-CAF, CAPE-INIC, and CAPE-NIC cocrystals. Raman spectra of CAPE cocrystals complement these results in confirming the formation of novel crystalline phases. CAPE-NIC cocrystal was further subjected X-ray crystallography to understand its molecular arrangement and hydrogen bonding in the crystal structure. The CAPE-NIC cocrystal structure is found to be stabilized by a rare 1,2-benzenediol-amide heterosynthon. Cocrystallization of CAPE with NIC improved its aqueous solubility and pharmacokinetic profile, thereby demonstrating a 2.76-fold escalation in bioavailability.

Two chitotriose-specific lectins show anti-angiogenesis, induces caspase-9-mediated apoptosis and early arrest of pancreatic tumor cell cycle - Singh, Ruby; Nawale, Laxman; Sarkar, Dhiman; Suresh, C. G. (Plos One, 2016)
The antiproliferative activity of two chito-specific agglutinins purified from Benincasa hispida (BhL) and Datura innoxia (DiL9) of different plant family origin was investigated on various cancer cell lines. Both lectins showed chitotriose specificity, by inhibiting lectin hemagglutinating activity. On further studies, it was revealed that these agglutinins caused remarkable concentration-dependent antiproliferative effect on human pancreatic cancerous cells but not on the normal human umbilical vein endothelial cells even at higher doses determined using MTT assay. The GI(50) values were approximately 8.4 mu g ml(-1) (0.247 mu M) and 142 mu g ml(-1) (14.8 mu M) for BhL and DiL9, respectively, against PANC-1 cells. The growth inhibitory effect of these lectins on pancreatic cancer cells were shown to be a consequence of lectin cell surface binding and triggering G(0)/G(1) arrest, mitochondrial membrane depolarization, sustained increase of the intracellular calcium release and the apoptotic signal is amplified by activation of caspases executing cell death. Interestingly, these lectins also showed anti-angiogenic activity by disrupting the endothelial tubulogenesis. Therefore, we report for the first time two chito-specific lectins specifically binding to tumor glycans; they can be considered to be a class of molecules with antitumor activity against pancreatic cancer cells mediated through caspase dependent mitochondrial apoptotic pathway.

Ultrasound- and molecular sieves-assisted synthesis, molecular docking and antifungal evaluation of 5-(4-(benzyloxy)-substituted phenyl)-3-((phenylamino)methyl)-1,3,4-oxadiazole-2(3H)-thiones - Nimbalkar, Urja D.; Tupe, Santosh G.; Seijas Vazquez, Julio A.; Khan, Firoz A. Kalam; Sangshetti, Jaiprakash N.; Nikalje, Anna Pratima G. (Molecules, 2016)
A novel series of 5-(4-(benzyloxy) substituted phenyl)-3-((phenyl amino) methyl)-1,3,4-oxadiazole-2(3H)-thione Mannich bases 6a-o were synthesized in good yield from the key compound 5-(4-(benzyloxy) phenyl)-1,3,4-oxadiazole-2(3H)-thione by aminomethylation with paraformaldehyde and substituted amines using molecular sieves and sonication as green chemistry tools. The antifungal activity of the new products was evaluated against seven human pathogenic fungal strains, namely, Candida albicans ATCC 24433, Candida albicans ATCC 10231, Candida glabrata NCYC 388, Cryptococcus neoformans ATCC 34664, Cryptococcus neoformans PRL 518, Aspergillus fumigatus NCIM 902 and Aspergillus niger ATCC 10578. The synthesized compounds 6d, 6f, 6g, 6h and 6j exhibited promising antifungal activity against the tested fungal pathogens. In molecular docking studies, derivatives 6c, 6f and 6i showed good binding at the active site of C. albicans cytochrome P450 enzyme lanosterol 14 alpha-demethylase. The in vitro antifungal activity results and docking studies indicated that the synthesized compounds have potential antifungal activity and can be further optimized as privileged scaffolds to design and develop potent antifungal drugs.
Keywords: 1; 3; 4-oxadiazoles; Antifungal activity; Mannich reaction; Molecular docking; Molecular sieves; Ultrasound

Use of the term "crystal engineering" in the regulatory and patent literature of pharmaceutical solid forms. some comments - Desiraju, Gautam R.; Nangia, Ashwini (Crystal Growth & Design, 2016)

Versatile Cu-II metal-organic framework exhibiting high gas storage capacity with selectivity for CO2: conversion of CO2 to cyclic carbonate and other catalytic abilities - De, Dinesh; Pal, Tapan K.; Neogi, Subhadip; Senthilkumar, S.; Das, Debasree; Sen Gupta, Sayam; Bharadwaj, Parimal K. (Chemistry-A European Journal, 2016)
A linear tetracarboxylic acid ligand, H4L, with a pendent amine moiety solvothermally forms two isostructural metal-organic frameworks (MOFs) L-M (M=Zn-II, Cu-II). Framework L-Cu can also be obtained from L-Zn by post- synthetic metathesis without losing crystallinity. Compared with L-Zn, the L-Cu framework exhibits high thermal stability and allows removal of guest solvent and metal-bound water molecules to afford the highly porous, L-Cu. At 77K, L-Cu absorbs 2.57wt% of H-2 at 1bar, which increases significantly to 4.67wt% at 36bar. The framework absorbs substantially high amounts of methane (238.38cm(3)g(-1), 17.03wt%) at 303K and 60bar. The CH4 absorption at 303K gives a total volumetric capacity of 166cm(3)(STP)cm(-3) at 35bar (223.25cm(3)g(-1), 15.95wt%). Interestingly, the NH2 groups in the linker, which decorate the channel surface, allow a remarkable 39.0wt% of CO2 to be absorbed at 1bar and 273K, which comes within the dominion of the most famous MOFs for CO2 absorption. Also, L-Cu shows pronounced selectivity for CO2 absorption over CH4, N-2, and H-2 at 273K. The absorbed CO2 can be converted to value-added cyclic carbonates under relatively mild reaction conditions (20bar, 120 degrees C). Finally, L-Cu is found to be an excellent heterogeneous catalyst in regioselective 1,3-dipolar cycloaddition reactions (click reactions) and provides an efficient, economic route for the one-pot synthesis of structurally divergent propargylamines through three-component coupling of alkynes, amines, and aldehydes.
Keywords: click reactions; CO2 absorption; cyclic carbonate; heterogeneous catalysis; metal-organic frameworks

Acemetacin cocrystal structures by powder X-ray diffraction - Bolla, Geetha; Chernyshev, Vladimir; Nangia, Ashwini (Iucrj, 2017)
Cocrystals of acemetacin drug (ACM) with nicotinamide (NAM), p-aminobenzoic acid (PABA), valerolactam (VLM) and 2-pyridone (2HP) were prepared by melt crystallization and their X-ray crystal structures determined by high-resolution powder X-ray diffraction. The powerful technique of structure determination from powder data (SDPD) provided details of molecular packing and hydrogen bonding in pharmaceutical cocrystals of acemetacin. ACM-NAM occurs in anhydrate and hydrate forms, whereas the other structures crystallized in a single crystalline form. The carboxylic acid group of ACM forms theacid-amide dimer three-point synthon R-3(2)(9) R-2(2)(8) R-3(2)(9) with three different syn amides (VLM, 2HP and caprolactam). The conformations of the ACM molecule observed in the crystal structures differ mainly in the mutual orientation of chlorobenzene fragment and the neighboring methyl group, being anti (type I) or syn (type II). ACM hydrate, ACM-NAM, ACM-NAM-hydrate and the piperazine salt of ACM exhibit the type I conformation, whereas ACM polymorphs and other cocrystals adopt the ACM type II conformation. Hydrogen-bond interactions in all the crystal structures were quantified by calculating their molecular electrostatic potential (MEP) surfaces. Hirshfeld surface analysis of the cocrystal surfaces shows that about 50% of the contribution is due to a combination of strong and weak O center dot center dot center dot H, N center dot center dot center dot H, Cl center dot center dot center dot H and C center dot center dot center dot H interactions. The physicochemical properties of these cocrystals are under study.

All-solid-state-supercapacitor possessing a non-aqueous gel polymer electrolyte prepared using a UV-assisted in situ polymerization strategy - Vijayakumar, V.; Anothumakkool, B.; Torris, A. T. A.; Nair, S. B.; Badiger, M. V.; Kurungot, S. (Journal of Materials Chemistry A, 2017)
In this work, we report the synthesis of a high ionic conducting and mechanically stable non-aqueous gel polymer electrolyte (GPE) in which a liquid electrolyte (LiClO4/propylene carbonate) is entrapped in a poly(2-hydroxy-3-phenoxy propyl acrylate) matrix by a UV assisted in situ polymerisation strategy. Unlike conventional dry and quasi-solid non-aqueous GPEs, our system (H-P-L-3M-80%) shows an excellent ionic conductivity of 4.7 x 10(-3) S cm(-1), a value which is comparable to those of non-aqueous liquid electrolytes. The high mechanical stability of GPE arises due to the covalent cross-links present in the polymer matrix as well as the reversible non-covalent cross-links between the solvent and the polymer matrix through the Li+ cations. Subsequently, the GPE has been prepared in situ on the inner and the outer surface of the electrode material to fabricate a 2.0 V supercapacitor device with a high mass loading (3.8 mg cm(-2)) of the active material (YP-80F, a high surface area porous carbon). The device shows an equivalent series resistance (ESR) as low as 2.2 Omega, which is close to that of the device fabricated from the corresponding liquid electrolyte and is far better than those of the devices evolved from conventional GPEs and dry polymer electrolytes. The mass specific capacitance of 113 F g(-1) obtained at a current density of 2 mA cm(-2) shows 81% retention even at a high current density of 20 mA cm(-2). The scalability of the strategy is demonstrated by fabricating a large area (area = 16 cm(2), loading = 4.0 mg cm(-2)) all-solid-state flexible-supercapacitor (H-P-L-3M-S-4.0) device which can be operated at a potential window of 2.5 V. The device was found to show a mass specific capacitance of 111 F g(-1) at a current density of 1 mA cm(-2) (0.25 A g(-1)), all the while, retaining a very low ESR of 2.2 Omega. The potential of the strategy to mimic the liquid-like electrode-electrolyte interface, augmented with the ability to tune further, opens up new horizons for energy storage devices.

Anti-proliferative effect of novel primary cetyl alcohol derived sophorolipids against human cervical cancer cells HeLa - Nawale, Laxman; Dubey, Parul; Chaudhari, Bhushan; Sarkar, Dhiman; Prabhune, Asmita (Plos One, 2017)
Sophorolipids (SLs) are glycolipid biosurfactants that have been shown to display anticancer activity. In the present study, we report anti-proliferative studies on purified forms of novel SLs synthesized using cetyl alcohol as the substrate (referred as SLCA) and their anticancer mechanism in human cervical cancer cells. Antiproliferative effect of column purified SLCA fractions (A, B, C, D, E and F) was examined in panel of human cancer cell lines as well as primary cells. Among these fractions, SLCA B and C significantly inhibited the survival of HeLa and HCT 116 cells without affecting the viability of normal human umbilical vein endothelial cells (HUVEC). The two fractions were identified as cetyl alcohol sophorolipids with non-hydroxylated tail differing in the degree of acetylation on sophorose head group. At an IC50 concentration SLCA B (16.32 mu g ml(-1)) and SLCA C (14.14 mu g ml(-1)) blocked the cell cycle progression of HeLa cells at G1/S phase in time-dependent manner. Moreover, SLCA B and SLCA C induced apoptosis in HeLa cells through an increase in intracellular Ca2+ leading to depolarization of mitochondrial membrane potential and increase in the caspase-3, -8 and -9 activity. All these findings suggest that these SLCAs could be explored for their chemopreventive potential in cervical cancer.

Assessing therapeutic potential of molecules: molecular property diagnostic suite for tuberculosis - Gaur, A. S.; Bhardwaj, A.; Sharma, A.; John, L.; Vivek, M. R.; Tripathi, N.; Bharatam, P. V.; Kumar, R.; Janardhan, S.; Mori, A.; Banerji, A.; Lynn, A. M.; et al. (Journal of Chemical Sciences, 2017)
Abstract: Molecular Property Diagnostic Suite (MPDS TB) is a web tool (http://mpds.osdd.net) designed to assist the in silico drug discovery attempts towards Mycobacterium tuberculosis (Mtb). MPDS TB tool has nine modules which are classified into data library (1–3), data processing (4–5) and data analysis (6–9). Module 1 is a repository of literature and related information available on the Mtb. Module 2 deals with the protein target analysis of the chosen disease area. Module 3 is the compound library consisting of 110.31 million unique molecules generated from public domain databases and custom designed search tools. Module 4 contains tools for chemical file format conversions and 2D to 3D coordinate conversions. Module 5 helps in calculating the molecular descriptors. Module 6 specifically handles QSAR model development tools using descriptors generated in the Module 5. Module 7 integrates the AutoDock Vina algorithm for docking, while module 8 provides screening filters. Module 9 provides the necessary visualization tools for both small and large molecules. The workflow-based open source web portal, MPDS TB 1.0.1 can be a potential enabler for scientists engaged in drug discovery in general and in anti-TB research in particular. Graphical Abstract: SYNOPSIS: A web-based MPDS TB Galaxy tool is developed for assessing therapeutic potential of molecules. MPDS TB is categorized into Data Library, Data Processing and Data Analysis. It can be a potential enabler for scientists engaged in drug discovery in general and in anti-TB research in particular. [Figure not available: see fulltext.] © 2017, Indian Academy of Sciences.
Keywords: chemical analysis; Chemoinformatics; computational chemistry; Diagnosis; Drug discovery portal; Information analysis; Libraries; Molecular graphics; Molecules; Neglected diseases; Open science; Portals; tuberculosis; Web-based technology; Websites

Band alignment and charge transfer pathway in three phase anatase-rutile-brookite TiO2 nanotubes: an efficient photocatalyst for water splitting - Preethi, L. K.; Mathews, Tom; Nand, Mangla; Jha, S. N.; Chinnakonda, Gopinath S.; Dash, Sitaram (Applied Catalysis B-Environmental, 2017)
The study reports electrochemical synthesis, phase evolution and hydrogen generation efficiency of anatase, anatase-rutile and anatase-rutile-brookite (ARB) TiO2 nanotubes for the first time. The SEM and TEM micrographs confirm the tubular morphology of the samples. The presence of anatase, rutile and brookite phases in a single nanotube is confirmed from high resolution TEM analysis. The water splitting efficiency of the three systems are studied under one sun illumination. It is observed that the anatase-rutile-brookite TiO2 nanotubes are highly efficient compared to anatase-rutile or anatase TiO2 nanotubes. The hydrogen generated by ARB composites, after four hours of one sun illumination, is found to be nearly twice that of anatase TiO2 nanotubes and 1.6 times that of anatase-rutile TiO2 nanotubes. The results suggest that the ARB in single nanotube having two junction interfaces, highly facilitate interparticle charge transfer compared to single junction anatase-rutile or bare anatase TiO2 nanotubes. From the deconvolution of PL spectra and the synchrotron radiation assisted valence band edge analysis, the band diagram for the anatase-rutile-brookite phase is constructed. The charge separation and its transfer pathway for efficient photo-assisted water splitting are delineated. This opens a new route for the simple synthesis and study of tri-phase TiO2 for efficient photocatalytic water splitting compared to the widely studied two phase TiO2. (C) 2017 Published by Elsevier B.V.
Keywords: Anatase-Rutile-Brookite; Hydrogen generation; nanotubes; Photocatalysis; photoluminescence; Valence band edge

Binding selectivity of vitamin K3 based chemosensors towards nickel(II) and copper(II) metal ions - Patil, Amit; Lande, Dipali N.; Nalkar, Archana; (Gejji, Shridhar P.; Chakrovorty, Debamitra; Gonnade, Rajesh; Moniz, Tania; Rangel, Maria; Pereira, Eulalia; Salunke-Gawali, Sunita (Journal of molecular Structure, 2017)
The vitamin K3 derivatives 2-methyl-3-[(pyridin-2-ylmethyl)-amino]-1,4-naphthoquinone (M-1), 2-methyl-3-[(pyridin-2-ylethyl)-amino]-1,4-naphthoquinone (M-2), 2-methyl-3-((2-(thiophen-2-yl) methyl)amino)naphthalene-1,4-dione (M-3) and 2-methyl-3-((2-(thiophen-2-yl)ethyl)amino)naphthalene-1,4-dione (M-4) have been synthesized, characterized and studied for their chemosensor abilities towards transition metal ions. Crystal structures of M-1 to M-4 revealed a variety of N-H center dot center dot O, C-H center dot center dot center dot O, C-H center dot center dot center dot pi and pi center dot center dot center dot pi interactions. Minor variations in such interactions by chemical stimuli such as metal ions, results in change in color that can be visualized by naked eyes. It has been shown that electronic structure and H-1 NMR, vibrational as well as electronic spectra from the density functional theory agree well with the experiments. The metal ion binding in ethanol, ethanol-water and in mild base triethylamine brings forth recognizing ability of M-1 toward Ni2+ whereas M-2 exhibits large sensing ability for Cu2+ ion. Interestingly M-1 display varying metal ion binding specificity in different solvents with the association constant in ethanol being 11,786 M-1 for Ni2+ compared to 9462 M-1 for the Cu2+. A reversal in preferential binding of M-2 with the respective association constants being 4190 M-1 and 6370 M-1 is discernible. (C) 2017 Elsevier B.V. All rights reserved.
Keywords: Aminonaphthoquinone Molecular-structures; Anthraquinone; Aqueous-solution; Chemosensor; Crystal-structures; Cu(II); Derivatives; DFT; Fluorometric Chemosensors; hydrogen bonding; Naphthoquinone; pi-pi stacking; Recognition; sensors

Biosurfactant surfactin as a kinetic promoter for methane hydrate formation - Bhattacharjee, Gaurav; Barmecha, Vivek; Pradhan, Darshan; Naik, Rajesh; Zare, Kirti; Mawlankar, Rahul R.; Dastager, Syed Gulam; Kushwaha, Omkar Singh; Kumar, Rajnish (Energy Procedia, 2017)
In the present study, the effect of the biosurfactant Surfactin on methane hydrate formation kinetics was studied. Initially, several marine derived species were screened for the presence of Surfactin. The polymerase chain reaction technique was used as the preliminary screening step for Surfactin which was then followed up by a couple of different assays to provide conclusive evidence of the same. Based on these tests, the D-9 bacterial strain was identified as a producer of Surfactin. Once the presence of Surfactin had been proven, its effect on methane hydrate formation kinetics was investigated upon by carrying out hydrate formation experiments in a stirred tank reactor. The cell free supernatant containing Surfactin was itself used as the hydrate forming solution without any further processing. It was found that the presence of Surfactin in the system greatly enhances hydrate formation kinetics as compared to pure water. In fact the kinetics in presence of Surfactin also surpassed that obtained with 1 wt% SDS, the most commonly used synthetic kinetic hydrate promoter. This basic study can pave the way for more sophisticated research on the use of biosurfactants as kinetic promoters with a view on rapid methane hydrate formation kinetics for applications such as methane separation, storage and transport.

Camptothecin-producing endophytic bacteria from pyrenacantha volubilis hook. (Icacinaceae): a possible role of a plasmid in the production of camptothecin - Soujanya, K. N.; Siva, R.; Kumara, P. Mohana; Srimany, Amitava; Ravikanth, G.; Mulani, F. A.; Aarthy, T.; Thulasiram, H. V.; Santhoshkumar, T. R.; Nataraja, Karaba N.; Shaanker, R. Uma (Phytomedicine, 2017)
Background: Camptothecin (CPT), a quinoline alkaloid, is a potent inhibitor of eukaryotic topoisomerase I. Because of this property, several derivatives of CPT are used as chemotherapeutic agents. CPT is produced by several plant species belonging to the Asterid clade as well as by a number of endophytic fungal associates of these plants. In this study, we report the production of CPT by four bacterial endophytes and show the possible role of a plasmid in the biosynthesis of CPT. Methods: Endophytic bacteria were isolated from leaves, stems and fruits of Pyrenacantha volubilis Hook. (Icacinanceae). The bacterial isolates were purified and analyzed for production of CPT by ESI-MS/MS and NMR analysis. Bacterial identity was established based on the morphology and 16s rRNA sequence analysis. Crude extracts of the bacterial endophytes were evaluated for their cytotoxicity using colon cancer cell lines. The role of plasmid in the production of CPT was studied by purging the plasmid, using acriflavine, as well as reconstituting the bacteria with the plasmid. Results: Four bacterial isolates, Bacillus sp. (KP125955 and KP125956), Bacillus subtilis (KY741853) and Bacillus amyloliquefaciens (KY741854) were found to produce CPT in culture. Both based on ESI-MS/MS and NMR analysis, the identity of CPT was found to be similar to that produced by the host plant. The CPT was biologically active as evident by its cytotoxicity against colon cancer cell line. The production of CPT by the endophyte (Bacillus subtilis, KY741853) attenuated with sub-culture. A likely role of a plasmid in the production of CPT was established. A 5 kbp plasmid was recovered from the bacteria. Bacterial isolate cured of plasmid failed to produce CPT. Conclusion: Our study implies a possible role of a plasmid in the production of CPT by the endophytic bacteria and opens up further work to unravel the exact mechanisms that might be involved.

Carboxymethyl cellulose-grafted mesoporous silica hybrid nanogels for enhanced cellular uptake and release of curcumin - Tiwari, Neha; Nawale, Laxman U.; Sarkar, Dhiman; Badiger, Manohar V. (Gels, 2017)
Mesoporous silica nanoparticles (MSNs) with ordered pore structure have beensynthesized and used as carriers for the anticancer drug curcumin. MSNs were functionalizedwith amine groups and further attached with carboxymethyl cellulose (CMC) using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) coupling chemistry, which increased the hydrophilicityand biocompatibility of MSNs. The functionalized MSNs (MSN-NH2and MSN-CMC) werecharacterized using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM),Dynamic Light Scattering (DLS), N2adsorption, X-Ray Diffraction (XRD), Thermo GravimetricAnalysis (TGA) and Fourier Transform Infrared Spectroscopy (FT-IR). Thein vitrorelease of curcuminfrom the –NH2and CMC functionalized MSNs (MSN-cur-NH2and MSN-cur-CMC) was performedin 0.5% aqueous solution of sodium lauryl sulphate (SLS). The effect of CMC functionalization ofMSNs towards cellular uptake was studied in the human breast cancer cell line MDA-MB-231 andwas compared with that of MSN-NH2and free curcumin (cur). Both MSN-NH2and MSN-CMCshowed good biocompatibility with the breast cancer cell line. The MTT assay study revealedthat curcumin-loaded MSN-cur-CMC showed better uptake as compared to curcumin-loadedMSN-cur-NH2. Free curcumin was used as a control and was shown to have much less internalizationas compared to the curcumin-loaded functionalized MSNs due to poor bioavailability. Fluorescencemicroscopy was used to localize the ﬂuorescent drug curcumin inside the cells. The workdemonstrates that CMC-functionalized MSNs can be used as potential carriers for loading and releaseof hydrophobic drugs that otherwise cannot be used effectively in their free form for cancer therapy.

CH3NH3PbI3 based solar cell: modified by antisolvent treatment - Nandi, P.; Giri, C.; Bansode, U.; Topwal, D. (AIP Conference Proceedings, 2017)
Solar cells based on new class of organic inorganic hybrid perovskite CH3NH3PbI3 were prepared by Ethyl acetate (EA); antisolvent treatment for the first time. This treatment results in new morphology for CH3NH3PbI3 thin film. FESEM image shows microrod type structures of CH3NH3PbI3 after EA antisolvent treatment. Energy band diagram was constructed using photoluminescence and photoemission studies. A better power conversion efficiency was achieved in EA treated film compare to without EA treated film.
Keywords: CH3NH3PbI3; Perovskite solar cell

Chitosan intercalated metal organic gel as a green precursor of fe entrenched and fe distributed N-doped mesoporous graphitic carbon for oxygen reduction reaction - Shijina, Kottarathil; Illathvalappil, Rajith; Kurungot, Sreekumar; Nair, Balagopal N.; Mohamed, A. Peer; Yamaguchi, Takeo; Anilkumar, Gopinathan M.; Hareesh, U. S.; Sailaja, G. S. (Chemistryselect, 2017)
Herein, we present Metal-Organic Gel intercalated with chitosan, a `green'' precursor for the synthesis of intrinsic N-doped Fe entrenched (CHI-TMA-Fe-CW) and Fe distributed mesoporous graphitic carbon structures (CHI-TMA-Fe-CW-M1) with appreciable Oxygen Reduction Reaction (ORR) activity in alkaline medium. Modulation of the synthetic protocol as a function of reaction kinetics and gelation time while maintaining identical pyrolysis conditions (900 degrees C, flowing N-2 atmosphere) improves the microstructure, surface area and Fe distribution of the graphitic structures (CHI-TMA-Fe-CW-M1). CHI-TMA-Fe-CW has a Fe entrenched graphitic nanocapsule like morphology while Fe distributed mesoporous graphitic carbon sheets, with a specific surface area value of 565 m(2) g(-1) obtained by modulating the synthesis chemistry in CHI-TMA-Fe-CW-M1. The higher percentage of graphitic N in CHI-TMA-Fe-CW-M1 apparent from the XPS data validate that the modified synthetic method favours creation of more graphitic N sites contributing for better catalytic performance. CHI-TMA-Fe-CW-M1 catalyst exhibited comparable electrocatalytic activity with that of the commercially available Pt/C via an efficient four-electron-dominant ORR pathway with a positive onset potential value of 0.925 V vs RHE. Good durability of CHI-TMA-Fe-CW-M1 after 5000 cycles further confirm the prospects of MOG-chitosan and the feasibility to be used as a potential catalyst for ORR.
Keywords: electrocatalyst; fuel cell; Metal-Organic-Gel; oxygen reduction reaction

Cisplatin-induced self-assembly of graphene oxide sheets into spherical nanoparticles for damaging sub-cellular DNA - Nandi, Aditi; Mallick, Abhik; More, Piyush; Sengupta, Poulomi; Ballav, Nirmalya; Basu, Sudipta (Chemical Communications, 2017)
This report describes the hitherto unobserved cisplatin induced self-assembly of 2D-graphene oxide sheets into 3D-spherical nano-scale particles. These nanoparticles can encompass dual DNA damaging drugs simultaneously. A combination of confocal microscopy, gel electrophoresis and flow cytometry studies clearly demonstrated that these novel nanoparticles can internalize into cancer cells by endocytosis, localize into lysosomes, and damage DNA, leading to apoptosis. Cell viability assays indicated that these nanoparticles were more cytotoxic towards cancer cells compared to healthy cells.

Click-chemistry-based multicomponent condensation approach for design and synthesis of spirochromene-tethered 1,2,3-triazoles as potential antitubercular agents - Chavan, Pramod V.; Pandit, Kapil S.; Desai, Uday V.; Wadgaonkar, Prakash P.; Nawale, Laxman; Bhansali, Sujit; Sarkar, Dhiman (Research on Chemical Intermediates, 2017)

Colloidal nanocomposite of TiN and N-doped few-layer graphene for plasmonics and electrocatalysis - Shanker, G. Shiva; Markad, Ganesh B.; Jagadeeswararao, Metikoti; Bansode, Umesh; Nag, Angshuman (ACS Energy Letters, 2017)
A combination of high carrier density, high surface area, solution processability, and low cost is desired in a material for electrocatalytic applications, including H-2 evolution and a counter electrode of a solar cell. Also, plasmonic-based applications in biological systems can be derived from such material. In this regard, a colloidal nanocomposite of TiN and N-doped few-layer graphene (TiN NFG) is synthesized from molecular precursors. TiN nano crystals (NCs) provide free electrons for electrical conductivity and plasmonics, whereas NFG is responsible for charge transport, high surface area, and colloidal stability. Colloidal TiN NFG nano composites exhibit a localized surface plasmon resonance band at around 700 nm. Coatings of the nanocomposite form a counter electrode for efficient (8.9%) dye-sensitized solar cells. Furthermore, the nanocomposite acts as an efficient electrocatalyst for hydrogen evolution reaction, exhibiting an overpotential similar to 161 mV at a current density of 10 mA/cm(2).

Control of polymerization reactors - Schurk, F. J; Deshpande, P. B; Leffew, K. W.; Nadkarni, V. M. (CRC Press, 2017)
This reference and text provides an in-depth description of developments in control techniques and their application to polymerization reactors and offers important introductory background information on polymerization reaction engineering.;Discussing modelling, identification, linear, nonlinear and multivariable schemes, Control of Polymerization Reactors: presents all available techniques that can be used to control reactors properly for optimal performance; shows how to manipulate pivotal variables that affect reactor control; examines methods for deriving dynamic process models to improve reactor efficiency; reviews reactor control problems and points out end-use properties; supplies methods for measuring process variables, and ways to estimate variables that can’t be measured; and explains how single-input, single-output (SISO) strategies can be effectively used for control.;Filled with illustrative examples to clarify concepts, including more than 730 figures, tables and equations, Control of Polymerization Reactors is intended for use as a reference for chemical, process development, process design, research and development, control systems, and polymer engineers; and polymer chemists and physicists; as well as a text for upper-level undergraduate and graduate students in polymerization reactor control courses.

Convenient new and efficient commercial synthetic route for dasatinib (sprycel®) - Suresh, Garbapu; Nadh, Ratnakaram Venkata; Srinivasu, Navuluri; Yennity, Durgaprasad (Synthetic Communications, 2017)
A new and efficient synthetic route for dual Src/Abl kinase inhibitor Dasatinib (Sprycel®), an anticancer drug, is described. This commercially viable process yields Dasatinib monohydrate free of potential impurities with consistent yield of 68% in route A and 61% in route B with HPLC purity >99.80% over 4 stages.

Convenient route for Au@Ti-SiO2 nanocatalyst synthesis and its application for room temperature CO oxidation - Soni, Yogita; Kumar, Anumol Erumpukuthical Ashok; Nayak, Chandrani; Deepak, Francis Leonard; Vinod, C. P. (Journal of Physical Chemistry C, 2017)
Small gold nanoparticles.of size less than 5 nm encapsulated inside titanium modified silica shell have been reported. Here, a modified sol-gel method, which is a one-step process, produces Au@Ti-SiO2 nanocatalyst with a good control of titanium loading. With a titanium loading of 0.9 and 2.2 wt % in silica, unprecedented low temperature activity (full conversion) is observed for this catalyst for CO oxidation reaction compared to Au@SiO2 catalyst. A combination of optimum sized gold nanoparticles with a large amount of oxygen vacancies created due to Ti incorporation in silica matrix is considered to be the reason for this enhanced catalytic activity. The size of.gold nanoparticles is maintained even after high temperature pretreatments, which show the benefit of encapsulation. The effect of the various pretreatments on the catalytic activity has also been reported.