Olfactory stimulation of apis cerana indica towards different doses of volatile constituents: SEM and EAG approaches - Bhowmik, Biswanath; Lakare, Sachin; Sen, Ayalokiteswar; Bhadra, Kakali (Journal of Asia-Pacific Entomology, 2016)
Morphological and peripheral olfactory responses of antennal chemosensilla of Apis cerana indica, worker honeybee, to commonly occurring plant volatiles were recorded using SEM and EAG techniques, respectively. The antennae of A. cerana indica reveal the predominance of olfactory sensilla besides gustatory and mechanoreceptor cells. Ten different types of olfactory sensilla including sensilla basiconica, placodea type A and B, chaetica, coeloconica, coelocapitula, trichodea type A, B, C and D were reported. Of these, trichodea B and placodea A types were reported to be maximum. Responses to 47 commonly occurring plant volatiles (including 10 aromatic, 12 aliphatic, 04 green leaf volatile, 10 hydrocarbon monoterpene, 08 oxygenated monoterpenes and 03 sesquiterpenes compounds) were shown to elicit the response. Normalized EAG response, relative to the standard 1-hexanol, reveal significant differences between the chemicals and were concentration dependent. At 0.1 mg/mL dose, the largest amplitude was obtained with p-cymene (119.74 +/- 6.94) followed by cinnamaldehyde (97.07 +/- 4.94) and veratrol (92.99 +/- 7.82). Furthermore, at 1.0 mg/mL, maximum stimulation was reported with cinnamaldehyde (92.02 +/- 4.26) followed by phenethyl alcohol (86.02 +/- 2.63), benzyl alcohol (70.53 +/- 2.47), 2-heptanone (67.71 +/- 5.02) and 1-heptanol (67.56 +/- 2.8). Again, amplitude of the response was found to be maximum with cinnamaldehyde (115.59 +/- 6.73) followed by 1-heptanol (105.69 +/- 2.45) and citral (100.78 +/- 4.93) at 5.0 mg/mL, whereas, at 10.0 mg/mL, phenethyl alcohol (93.45 +/- 1.87) and 2-heptanone (93.14 +/- 1.85) showed highest stimulation followed by 2-pentanone (92.22 +/- 0.43). These documentations provide valuable information regarding how diversity in chemoreceptive antennal sensilla reveals better ability to sense a diversity of odors that are important cues to help honeybee distinguish among species of various flowering plants. (C) 2016 Korean Society of Applied Entomology, Taiwan Entomological Society and Malaysian Plant Protection Society. Published by Elsevier B.V. All rights reserved.

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

Oxidative transformation of antiretroviral drug zidovudine during water treatment with permanganate: reaction kinetics and pathways - Kulkarni, Raviraj M.; Bhamare, Vijaykumar S.; Santhakumari, B. (Desalination and Water Treatment, 2016)
The presence of the pharmaceutical substances in the water has been reported by many studies and has attracted attention across the world. The mechanistic insight into oxidation of antiretroviral drug zidovudine (ZDV) by potassium permanganate was investigated between the pH values 3.0 and 9.0. The pH-dependent second-order rate constants were determined and rate constants decreased with an increase in pH. The products of the reaction were identified by high-resolution mass spectrometry. A probable mechanism is proposed which involves the formation of an intermediate complex between permanganate and ZDV, which further undergoes degradation in subsequent fast steps to form various oxidized products. The different parameters like effect of initially added products, solvent polarity, ionic strength, temperature, and pH on the rate of the oxidative degradation of ZDV by permanganate were systematically studied. The various activation parameters were determined from the effect of variation in temperature on the oxidative degradation of ZDV by permanganate in acidic medium and discussed in detail.
Keywords: Degradation; kinetics; Mechanism; Permanganate; Zidovudine

Palladium supported on fluorite structured redox CeZrO4-δ for heterogeneous suzuki coupling in water: a green protocol - Burange, Anand S.; Shukla, Rakesh; Tyagi, Avesh Kumar; Gopinath, Chinnakonda S. (Chemistry Select, 2016)
Pd on redox CeZrO4-δ catalysts was prepared, characterized and their activity was evaluated for Suzuki coupling reaction in water under reflux condition. Fresh and reduced form of 5 % Pd (R−Pd5) on CeZrO4-δ catalyst exhibited 100 % conversion in 2.5 and 1 h, respectively. R−Pd5 shows significant activity for wide range of substrate compatibility and for less reactive aryl bromides too. The mechanistic investigations proved the important role of redox CeZrO4-δ support on the catalytic activity. It was observed that the presence of oxygen vacancy along with Ce3+ enhances the activity. 1 wt % Pd photodeposited on pre-reduced CeZrO4-δ support requires a mere 20 min. for 100 % conversion of Suzuki coupling. Effect of metal dispersion and particle size on catalytic activity is also discussed. High Pd dispersion with small particle size (4±1 nm), particle size preservation after reaction, strong metal-support interaction and no leaching fully suggest the heterogeneous mechanism is operative for Suzuki coupling on 1 wt % Pd photodeposited on reduced CeZrO4-δ support. Present work hints the possibility of achieving high conversion for Suzuki reaction with very small amount of Pd through better dispersion by taking advantage of redox support and in water.

Pb2+-N bonding chemistry: recycling of polyaniline-pb nanocrystals waste for generating high-performance supercapacitor electrodes - Jha, Plawan Kumar; Singh, Santosh K.; Gatla, Suresh; Mathon, Olivier; Kurungot, Sreekumar; Ballav, Nirmalya (Journal of Physical Chemistry C, 2016)
Understanding of Pb-N bonding chemistry is not only fundamentally important in the view of relativistic inert-pair effect but also is important for therapeutic as well as environmental applications. In the present study, an unusual reactivity of N-containing pi-conjugated polyaniline emeraldine base (EB) toward aqueous Pb2+ ions has been identified. In the course of sequestering Pb2+ ions by EB, cuboid-shaped nanocrystals were isolated. Synchrotron-based X-ray absorption near-edge structure and extended X-ray absorption fine structure techniques were employed to understand Pb-N bonding chemistry in EB-Pb nanocrystals. The adopted methodology of slow exposure of HCl vapor to EB-Pb nanomaterial facilitated the isolation of polyaniline emeraldine-salt (ES) with unique morphological patterns, porosity and electrical conductivity. The electrochemical device based on recycled ES showed high-capacitance value (similar to 606 F/g @1 A/g and similar to 663 F/g @10 mV/s), high-energy density (similar to 14.8 Wh/kg at power density of similar to 663 W/kg) and excellent-cycling stability (only similar to 15% degradation after 1100 continued cycles at current density of 5 A/g). Notably, ES materials prepared directly from EB and upon exposing HNO3 vapor exhibited greatly inferior device performance.

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 degradation of methylene blue on Sn-doped titania nanoparticles synthesized by solution combustion route - Bhange, P. D.; Awate, S. V.; Gholap, Ramkrishna S.; Gokavi, G. S.; Bhange, Deu S. (Materials Research Bulletin, 2016)
Series of tin-doped titania nanoparticles with varying tin content in the range 0-20 mol% have been prepared by solution combustion synthesis route using urea as a fuel. The structure, surface morphology and optical activity of Sn-doped TiO2 nanoparticles were investigated by various analytical techniques such as powder XRD, SEM, TEM, UV-vis and N-2 adsorption study. The crystalline structures of the various phases were studied by rietveld refinement of the XRD data. The photocatalytic performance of Sn-doped titania nanoparticles were tested for degradation of MB under UV and visible light irradiation. The results reveal that the photocatalytic activity increases with increase in tin content which may be due to decrease in crystallite size with increase in surface area. The doping of Sn into TiO2 lattice hinders the recombination of electrons and holes thus enhance the quantum efficiency of photocatalytic reaction. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Catalytic properties; composites; Nanostructures; X-ray diffraction

Photochromic metal-organic frameworks for inkless and erasable printing - Garai, Bikash; Mallick, Arijit; Banerjee, Rahul (Chemical Science, 2016)
Inkless and erasable printing is the key solution towards a more sustainable paper industry, in terms of reducing paper wastages and the associated environmental hazards from waste paper processing. However, only a few cases have been reported in the literature where inkless printing has been tested in some practical systems. In an attempt to address this solution, we used photochromic metal-organic frameworks (MOFs) and tested their capability as inkless and erasable printing media. The printing was performed using sunlight as the light source on MOF-coated papers. The resulting printing had good resolution and stability, and was capable of being read both by the human eye and smart electronic devices; furthermore, the paper could be reused for several cycles without any significant loss in intensity. Interestingly, different coloured printing with a similar efficiency was achieved by varying the structure of the MOF.

Photoluminescent tetrahedral d(10)-metal Schiff base complexes exhibiting highly ordered mesomorphism - Chakraborty, Sutapa; Purkayastha, Debraj Dhar; Das, Gobinda; Bhattacharjee, Chira R.; Mondal, Paritosh; Prasad, S. Krishna; Rao, D. S. Shankar (Polyhedron, 2016)
A series of four-coordinate d(10)-metal complexes of the type [ML2] {M = Zn, Cd, Hg; L = 4-nitro-2-((octadecylimino)methyl)phenol}, incorporating a new N-alkylated bidentate [N,O]-donor salicylaldimine Schiff base ligand, has been synthesized and characterized by elemental analyses, FT-IR, UV-Vis, H-1 NMR and FAB-mass spectroscopies. The ligand is non-mesomorphic and devoid of any photoluminescence. The zinc(II) and cadmium(II) complexes displayed highly ordered mesophases reminiscent of soft crystals. The phases have been characterized by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD) studies. The complex of mercury(II) decomposed prior to melting. An orthogonal symmetry with a `herringbone' array for the zinc complex and a primitive triclinic symmetry (p(1)) for the cadmium complex, respectively, has been proposed. The complexes exhibited fluorescence at room temperature, both in the solution and in the solid state, with emission maxima in the blue region. Density functional theory (DFT) calculations carried out using the GAUSSIAN 09 program at the B3LYP level revealed a distorted tetrahedral geometry around the metal center in all the complexes. Natural bond orbital (NBO) analysis suggested appreciable charge transfer from the ligand to the metal center in the complexes. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Density functional theory; Luminescence; Mesophase; Schiff base; X-ray diffraction

Photoresponsive assemblies of linear-dendritic copolymers containing azobenzene in the dendron interior: the effect of the dendron structure on dye encapsulation and release - Kalva, Nagendra; Basutkar, Nitin B.; Ambade, Ashootosh V. (RSC Advances, 2016)
Hydrophobic dendrons with different numbers and positions of azobenzenes as well as different groups benzyl and dodecyl, on the periphery were synthesised and attached to poly(ethylene glycol) using copper-catalysed azide-alkyne cycloaddition to obtain linear-dendritic copolymers. Self-assembly of the polymers in aqueous solution was characterised using dynamic light scattering (DLS), transmission electron microscopy (TEM) and critical micelle concentration (cmc). Formation of H-aggregates during micellisation was shown for polymers with a higher number of azobenzene units. Photoisomerisation of azobenzene in the assemblies was studied and the rate constant of thermal photoisomerisation was calculated. Release of hydrophobic dye Nile red upon photoisomerisation of azobenzene occurred without disruption of micellar aggregates. Dye release varied with the pathway - thermal or visible light irradiation, followed for cis-trans isomerisation. The encapsulation capacity of the micelles and extent of dye release in either pathway were found to be influenced by the dendron structure. A polymer with a lower number of azobenzenes and aliphatic periphery on the dendron showed significantly different behaviour than polymers with a larger number of aromatic units.

Phytase production by solid-state fermentation of groundnut oil cake by Aspergillus niger: A bioprocess optimization study for animal feedstock applications - Buddhiwant, Priyanka; Bhavsar, Kavita; Kumar, V. Ravi; Khire, Jayant M. (Preparative Biochemistry & Biotechnology, 2016)
This investigation deals with the use of agro-industrial waste, namely groundnut oil cake (GOC), for phytase production by the fungi Aspergillus niger NCIM 563. Plackett-Burman design (PBD) was used to evaluate the effect of 11 process variables and studies here showed that phytase production was significantly influenced by glucose, dextrin, distilled water, and MgSO4 center dot 7H(2)O. The use of response surface methodology (RSM) by Box-Behnken design (BBD) of experiments further enhanced the production by a remarkable 36.67-fold from the original finding of 15 IU/gds (grams of dry substrate) to 550 IU/gds. This is the highest solid-state fermentation (SSF) phytase production reported when compared to other microorganisms and in fact betters the best known by a factor of 2. Experiments carried out using dried fermented koji for phosphorus and mineral release and also thermal stability have shown the phytase to be as efficient as the liquid enzyme extract. Also, the enzyme, while exhibiting optimal activity under acidic conditions, was found to have significant activity in a broad range of pH values (1.5-6.5). The studies suggest the suitability of the koji supplemented with phytase produced in an SSF process by the "generally regarded as safe" (GRAS) microorganism A. niger as a cost-effective value-added livestock feed when compared to that obtained by submerged fermentation (SmF).

Pick and choose the spectroscopic method to calibrate the local electric field inside proteins - Haldar, Tapas; Kashid, Somnath M.; Deb, Pranab; Kesh, Sandeep; Bagchi, Sayan (Journal of Physical Chemistry Letters, 2016)
Electrostatic interactions in proteins play a crucial role in determining the structure function relation in biomolecules. In recent years, fluorescent probes have been extensively employed to interrogate the polarity in biological cavities through dielectric constants or semiempirical polarity scales. A choice of multiple spectroscopic methods, not limited by fluorophores, along with a molecular level description of electrostatics involving solute-solvent interactions, would allow more flexibility to pick and choose the experimental technique to determine the local electrostatics within protein interiors. In this work we report that ultraviolet/visible-absorption, infrared-absorption, or C-13 NMR can be used to calibrate the local electric field in both hydrogen bonded and non-hydrogen bonded protein environments. The local electric field at the binding site of a serum protein has been determined using the absorption wavelength as well as the carbonyl stretching frequency of its natural steroid substrate, testosterone. Excellent agreement is observed in the results obtained from two independent spectroscopic techniques.

Potential dual role of eugenol in inhibiting advanced glycation end products in diabetes: proteomic and mechanistic insights - Singh, Priyanka; Jayaramaiah, Ramesha H.; Agawane, Sachin B.; Vannuruswamy, Garikapati; Korwar, Arvind M.; Anand, Atul; Dhaygude, Vitthal S.; Shaikh, Mahemud L.; Joshi, Rakesh S.; Boppana, Ramanamurthy; Kulkarni, Mahesh J.; Thulasiram, Hirekodathakallu V.; et al. (Scientific Reports, 2016)
Medicinally important genus Ocimum harbors a vast pool of chemically diverse metabolites. Current study aims at identifying anti-diabetic candidate compounds from Ocimum species. Major metabolites in O. kilimandscharicum, O. tenuiflorum, O. gratissimum were purified, characterized and evaluated for anti-glycation activity. In vitro inhibition of advanced glycation end products (AGEs) by eugenol was found to be highest. Preliminary biophysical analysis and blind docking studies to understand eugenol-albumin interaction indicated eugenol to possess strong binding affinity for surface exposed lysines. However, binding of eugenol to bovine serum albumin (BSA) did not result in significant change in secondary structure of protein. In vivo diabetic mice model studies with eugenol showed reduction in blood glucose levels by 38% likely due to inhibition of alpha-glucosidase while insulin and glycated hemoglobin levels remain unchanged. Western blotting using anti-AGE antibody and mass spectrometry detected notably fewer AGE modified peptides upon eugenol treatment both in vivo and in vitro. Histopathological examination revealed comparatively lesser lesions in eugenol-treated mice. Thus, we propose eugenol has dual mode of action in combating diabetes; it lowers blood glucose by inhibiting a-glucosidase and prevents AGE formation by binding to epsilon-amine group on lysine, protecting it from glycation, offering potential use in diabetic management.

Preparation and characterization of microcapsules containing industrially important reactive water-soluble polyamine - Shukla, Parshuram G.; Jagtap, Siddheshwar B.; Biradar, Satish C.; Charpe, Vaibhav P.; Jadhav, Arun S. (Colloid and Polymer Science, 2016)
Polyurea microcapsules containing water-soluble reactive polyamine, namely, polyaziridine (A33), were prepared by interfacial polymerization technique in non-aqueous medium, wherein (i) A33 was encapsulated for the first time as a neat amine without forming its salt or adduct and (ii) microcapsules formed were without any deleterious effect on A33. A systematic study was conducted by preparing microcapsules with different polyurea wall architectures. Fourier transform infrared (FTIR) and proton nuclear magnetic resonance (H-1 NMR) spectroscopic analysis of extracted A33 from microcapsules do not show any structural changes during microencapsulation. A titration method was developed to analyze the amount of encapsulated A33 quantitatively. Polyurea microcapsules obtained from reaction of ethylene diamine (E) and isophorone diisocyanate (I) monomers have shown better properties such as encapsulation efficiency and extent of agglomeration. Significant reduction in the size was observed when microcapsules of EI wall material were prepared by homogenizing the initial emulsion of A33 in paraffin oil. The process described in this paper for the preparation of microcapsules is cost-effective and industrially viable, which can find applications in agrochemicals, coatings, self-healing composites, etc.

Product distribution in hydrogenation of styrene oxide over Pd/chitosan catalyst - Viswanadhan, Maya; Potdar, Aparna; Divakaran, Anumon V.; Badiger, Manohar V.; Rode, Chandrashekhar (Research on Chemical Intermediates, 2016)
Palladium-decorated chitosan catalyst was synthesized by an impregnation method by varying the Pd loading in the range of 1-6 %, and was evaluated for the regioselective hydrogenation of styrene oxide. In order to correlate the chemical and textural properties with the catalytic activity, all the prepared catalysts were characterized by techniques such as Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron spectroscopy, thermo-gravimetric analysis, temperature-programmed desorption of NH3, and CO2 and N-2 physisorption. The synthesized catalysts were utilized for the efficient and regioselective ring opening of styrene oxide by hydrogenation under different conditions. The complete conversion of styrene oxide with 65 % selectivity for 2-phenyl ethanol and 33 % for 1-phenyl ethanol were obtained using 4 % Pd/CS catalyst at 70 degrees C temperature and 3 MPa pressure. The mechanism for the regio selective ring opening of styrene oxide to 1- and 2-phenyl ethanol was also proposed on the basis of properties of the catalyst support, catalytic activity and selectivity. These results indicated that the catalytic activity and selectivity of the catalysts were affected by the nature of support. Further, the basic properties of the support play an important role in the selectivity of the styrene oxide hydrogenation reaction.

Proteomic insight reveals elevated levels of albumin in circulating immunecomplexes in diabetic plasma - Bhat, Shweta; Jagadeeshaprasad, Mashanipalya G.; Patil, Yugendra R.; Shaikh, Mahemud L.; Regin, Bhaskaran S.; Mohan, Viswanathan; Giri, Ashok P.; Balasubramanyam, Muthuswamy; Boppana, Ramanamurthy; Kulkarni, Mahesh J. (Molecular & Cellular Proteomics, 2016)
A Hyperglycemic condition in diabetes promotes formation of advanced glycation end products, which are known to elicit immune response and form complexes with immunoglobulins called circulating immune complexes. To investigate the involvement of advanced glycation end product (AGE)-modified proteins in the elicitation of an immune response, circulating immune complexes were isolated and proteins associated were identified and characterized. Label-free-based mass spectrometric analysis of circulating immune complexes in clinical plasma of prediabetic, newly diagnosed diabetes, and diabetic microalbuminurea revealed elevated levels of serum albumin in the circulating immune complexes, which were also observed to be AGE modified. Further, to examine the role of glycation, circulating immune complexeswere analyzed in the streptozotocin-induced diabetic mice treated with or without aminoguanidine, a prototype glycation inhibitor. Mass spectrometric analysis of circulating immune complexes showed elevated levels of serum albumin in plasma from diabetic mice over that of control animals. Aminoguanidine-treated diabetic mice displayed decreased AGE modification of plasma albumin, accompanied by a reduced level of albumin in the circulating immune complexes. In addition, elevated levels of proinflammatory cytokines such as IL-1b, IL-2, and TNF-alpha were observed in diabetes, which were reduced with aminoguanidine treatment, suggesting the involvement of glycation in the immune response.

Pt- and TCO-free flexible cathode for DSSC from highly conducting and flexible PEDOT paper prepared via in situ interfacial polymerization - Anothumakkool, Bihag; Agrawal, Ishita; Bhange, Siddheshwar N.; Soni, Roby; Game, Onkar S.; Ogale, Satishchandra B.; Kurungot, Sreekumar (ACS Applied Materials & Interfaces, 2016)
Here, we report the preparation of a flexible, free-standing, Pt- and TCO-free counter electrode in dye-sensitized solar cell (DSSC)-derived from polyethylenedioxythiophene (PEDOT)-impregnated cellulose paper. The synthetic strategy of making the thin flexible PEDOT paper is simple and scalable, which can be achieved via in situ polymerization all through a roll coating technique. The very low sheet resistance (4 Omega/square) obtained from a film of 40 mu m thick PEDOT paper (PEDOT-p-5) is found to be superior to the conventional fluorine-doped tin oxide (FTO) substrate. The high conductivity (357 S/cm) displayed by PEDOT-p-5 is observed to be stable under ambient conditions as well as flexible and bending conditions. With all of these features in place, we could develop an efficient Pt- and TCO-free flexible counter electrode from PEDOT-p-5 for DSSC applications. The catalytic activity toward the tri-iodide reduction of the flexible electrode is analyzed by adopting various electrochemical methodologies. PEDOT-p-5 is found to display higher exchange current density (7.12 mA/cm(2)) and low charge transfer resistance (4.6 Omega) compared to the benchmark Pt-coated FTO glass (2.40 mA/cm(2) and 9.4 Omega, respectively). Further, a DSSC fabricated using PEDOT-p-5 as the counter electrode displays a comparable efficiency of 6.1% relative to 6.9% delivered by a system based on Pt/FTO as the counter electrode.
Keywords: counter electrode; dye-sensitized solar cell; flexible and thin devices; impedance analysis; interfacial polymerization; polyethylenedioxythiophene

Pyramiding PvPGIP2 and TAXI-III but not PvPGIP2 and PMEI enhances resistance against fusarium graminearum - Tundo, Silvio; Kalunke, Raviraj; Janni, Michela; Volpi, Chiara; Lionetti, Vincenzo; Bellincampi, Daniela; Favaron, Francesco; D'Ovidio, Renato (Molecular Plant-Microbe Interactions, 2016)
Plant protein inhibitors counteract the activity of cell wall degrading enzymes (CWDEs) secreted by pathogens to breach the plant cell-wall barrier. Transgenic plants expressing a single protein inhibitor restrict pathogen infections. However, since pathogens secrete a number of CWDEs at the onset of infection, we combined more inhibitors in a single wheat genotype to reinforce further the cell-wall barrier. We combined polygalacturonase (PG) inhibiting protein (PGIP) and pectin methyl esterase inhibitor (PMEI), both controlling the activity of PG, one of the first CWDEs secreted during infection. We also pyramided PGIP and TAXI-M, a xylanase inhibitor that controls the activity of xylanases, key factors for the degradation of xylan, a main component of cereal cell wall. We demonstrated that the pyramiding of PGIP and PMEI did not contribute to any further improvement of disease resistance. However, the presence of both pectinase inhibitors ensured a broader spectrum of disease resistance. Conversely, the PGIP and TAXI-HI combination contributed to further improvement of Fusarium head blight (FHB) resistance, probably because these inhibitors target the activity of different types of CWDEs, i.e., PGs and xylanases. Worth mentioning, the reduction of FHB symptoms is accompanied by a reduction of deoxynivalenol accumulation with a foreseen great benefit to human and animal health.

Radio-frequency triggered heating and drug release using doxorubicin-loaded LSMO nanoparticles for bimodal treatment of breast cancer - Kulkarni, Vaishnavi M.; Bodas, Dhananjay; Dhoble, Deepa; Ghormade, Vandana; Paknikar, Kishore (Colloids and Surfaces B-Biointerfaces, 2016)
Radio-frequency responsive nanomaterials combined with drugs for simultaneous hyperthermia and drug delivery are potential anti-cancer agents. In this study, chitosan coated La0.7Sr0.3MnO3 nanoparticles (C-LSMO NPs) were synthesized and characterized by X-ray diffraction, dynamic light scattering, Fourier transform infra red spectroscopy, vibrating sample magnetometer, scanning electron and atomic force microscopy, Under low radio-frequency (365 kHz, RF), C-LSMO NPs (90 nm) showed good colloidal stability (+22 mV), superparamagnetic nature (15.4 emu/g) and heating capacity (57.4W/g SAR value). Chitosan facilitated doxorubicin entrapment (76%) resulted in DC-LSMO NPs that showed drug release upon a 5 min RF exposure. MCF-7 and MDA-MB-231 cancer cells responded to a 5 min RF exposure in the presence of bimodal DC-LSMO NPs with a significant decrease in viability to 73% and 88% (Pearson correlation, r = 1, P<0.01) respectively, as compared to hyperthermia alone. Internalization of DC-LSMO NPs via the endosomal pathway led to an efficient localization of doxorubicin within the cell nucleus. The ensuing DNA damage, heat shock protein induction, and caspase production triggered apoptotic cell death. Moreover, DC-LSMO NPs successfully restricted the migration of metastatic MDA-MB-231 cancer cells. These data suggest that DC-LSMO NPs are potential bimodal therapeutic agents for cancer treatment and hold promise against disease recurrence and drug resistance. (C) 2016 Elsevier B.V. All rights reserved.

Rapid methane hydrate formation to develop a cost effective large scale energy storage system - Veluswamy, Hari Prakash; Wong, Alison Jia Hui; Babu, Ponnivalavan; Kumar, Rajnish; Kulprathipanja, Santi; Rangsunvigit, Pramoch; Linga, Praveen (Chemical Engineering Journal, 2016)
Natural gas (NG) is the cleanest burning fossil fuel and its usage can significantly reduce CO2 emissions from power plants. With its widespread use, there is an ever increasing need to develop technologies to store NG on a large scale. NG storage via clathrate hydrates is the best option for a large scale storage system because of its non-explosive nature, mild storage conditions, high volumetric capacity and being an environmentally benign process. In this work, we demonstrate a new method to achieve rapid methane hydrate formation in an unstirred tank reactor configuration (UTR) at moderate temperature and pressure conditions employing tetrahydrofuran (THF) as a promoter. For the first time, THF is reported to act both as a thermodynamic and an excellent kinetic promoter for methane hydrate formation. We demonstrate a multi-scale experimental validation of our method to a volumetric sample scale-up factor of 120 and internal reactor diameter scale-up factor of 10. Further, new insights on the dissociation behavior of the hydrates are reported. There is a competitive edge for storing NG via clathrate hydrates compared to compressed natural gas storage both in terms of cost and safety. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Energy storage; Enhanced kinetics; Gas hydrates; Natural gas storage; Tetrahydrofuran; Unstirred tank reactor

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

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

Reduced graphene oxide modified electrodes for sensitive sensing of gliadin in food samples - Chekin, Fereshteh; Singh, Santosh K.; Vasilescu, Alina; Dhavale, Vishal M.; Kurungot, Sreekumar; Boukherroub, Rabah; Szunerits, Sabine (ACS Sensors, 2016)
Incidences of food allergies are on the rise, which can greatly affect the well-being of children as well as adults. Intolerance to gluten, a protein composite of gliadin and glutenin, present in wheat, barley, and rye and several cereals, can be the causative agent of celiac disease (CD) and other allergic reactions. A gluten-free diet has become essential for people affected by CD, and consequently, the amount of gluten in food products needs to be strictly controlled. In this paper, we report an electrochemical label-free immunosensor for ultrasensitive and specific detection of gliadin. The sensor takes advantage of the specific properties of porous reduced graphene oxide (prGO) covalently functionalized with anti-gliadin antibodies using 1-pyrenecarboxylic acid as linker molecule. Using differential pulse voltammetry (DPV) and [Fe(CN)6](3-/4-) as a redox probe, a decrease of current is linked to the presence of gliadin. The sensor achieved a detection limit of 1.2 ng mL(-1) over a 1.2-34 ng mL(-1) linear range with high selectivity. The advantages offered by this sensor are the possibility to regenerate the surface of the immunosensor, its rapid and ease of production, as well as applicability for the screening of gliadin concentrations in real food samples, as shown here.
Keywords: anti-gliadin antibody; food samples; gliadin; Immunosensor; Porous reduced graphene oxide

Reductive cyclization of levulinic acid to gamma-valerolactone over non-noble bimetallic nanocomposite - Kadu, Brijesh S.; Hengne, Amol M.; Biradar, Narayan S.; Rode, Chandrashekhar V.; Chikate, Rajeev C. (Industrial & Engineering Chemistry Research, 2016)
Bimetallic nanoparticles have diverse applications in catalytic processes owing to the differences in individual properties that contribute to their increased catalytic activity. To further improve the efficiency, they are dispersed in an inert support that enhances the catalytic activity toward organic transformations. In this study, we report simple, facile, and cost-effective chemical route for the fabrication of nanocomposites with Fe-Ni bimetallic nanoparticles supported on montmorillonite (MMT) possessing variation in the Fe and Ni content. These composites are characterized with X-ray diffraction, transmission electron microscopy surface area, and NH3-TPD. Fe Ni bimetallic nanoparticles are well-dispersed within MMT structure having particle sizes of about 30-40 nm. Among various compositions of Fe-Ni/MMT catalysts, composite with 25% Fe and 25% Ni exhibits >99% LA conversion with 98% selectivity to GVL within 1 h. IPA is found to be better solvent for levulinic acid (LA) to gamma-valerolactone (GVL) conversion, while substantial leaching of iron takes place when water is used as a solvent. It is observed that bimetallic sites are responsible for reduction of LA, while strong acidic sites of MMT are favoring subsequent cyclization to GVL. XPS analysis of fresh and reused Fe-Ni/MMT composites suggest that the catalyst surface does not undergo any chemical change during successive cycles, and the catalytic activity is retained up to six cycles. The plausible mechanism for LA to GVL conversion involves reductive cyclization processes through formation of levulinate ester that undergoes lactonization due to synergism in bimetallic nanoparticles and MMT clay.

Relevance of small laboratory animals as models in translational research: challenges and road ahead - Siddiqui, E. A.; Jagdale, P.; Ahire, K.; Jadhav, S.; Khan, S. A.; Bhosle, S.; Pal, A.; Jamdagni, P.; Chaudhari, B. (Journal of Applied Pharmaceutical Science, 2016)
Translational research using small laboratory animals is being done to demonstrate proof of concept, to study pharmacokinetics as well as to understand efficacy and safety of new drug molecules. During the evaluation of a drug candidate, the assessment of efficacy and safety is normally performed in different experiments using various animal models. In such experiments, efficacy is assessed by mimicking the disease state in animal model while safety is investigated in healthy animals. Inventing new drugs using biotechnological and nanotechnological approaches is becoming a major thrust area in drug research. Apart from this, the development of medicine from traditional knowledge like Ayurveda has emerged as major area for drug industry. Use of conventional in-vivo approaches may not prove useful to answer many questions. Transgenic/knock-out/knock-in animals are now getting space in pharmaceutical research for target identification and validation. Predictability of in-vivo research depends on scientific protocols and methods adopted for model selection and development. Various alternative approaches for in-vivo research are being followed. It is a fact that no animal model is 100 % capable of mimicking the complex human body but still, researchers have not yet found any alternative model which can completely replace in-vivo models. This review is a holistic approach explaining the various animal models being used for translational research, animal ethical issues, alternative approaches available and provides a critical analysis of major issues/challenges faced in translational research using in-vivo approaches.

Restricted diet breadth of the larvae of antheraea assamensis and the role of the labrum-epipharynx and galeal sensilla - Bora, Dipsikha S.; Deka, Bhabesh; Sen, Avolikiteswar (Entomological Research, 2016)
The silkworm, Antheraea assamensisHelfer (Lepidoptera: Saturniidae), grows primarily on Persea bombycina and Litsea polyantha. To understand if the restricted diet breadth is due to the specific role of gustatory sensilla of the larvae of A.assamensis, the same fifth instar larvae retaining only labrum-epipharynx or galeal sensilla were subjected to food choice tests. The foods used were leaves of two host-plant and two non-host-plant species. Mean per cent consumption and per cent of choosing larvae were used as parameters for drawing conclusions. The finding indicated involvement of the labrum-epipharynx for acceptance and galeal sensilla for rejection of a non-host-plant species. Scanning electron microscope studies revealed the presence of two sensilla on the galea, one lateral and one medial sensilla styloconicum and two gustatory sensilla in the epipharynx of A.assamensis. The study revealed the key role of galeal sensilla in the restrictive diet-breadth of A.assamensis.
Keywords: food choice; galea; gustatory organs; labrum

RNAi of selected candidate genes interrupts growth and development of Helicoverpa armigera - Chikate, Yojana R.; Dawkar, Vishal V.; Barbole, Ranjit S.; Tilak, Priyadarshini V.; Gupta, Vidya S.; Giri, Ashok P. (Pesticide Biochemistry and Physiology, 2016)
Helicoverpa armigera is one of the major crop pests and is less amenable to current pest control approaches. RNA interference (RNAi) is emerging as a potent arsenal for the insect pest control over current methods. Here, we examined the effect on growth and development in H. armigera by targeting various enzymes/proteins such as proteases like trypsins (HaTry2, 3, 4 and 6), chymotrypsin (HaChy4) and cysteine protease like cathepsin (HaCATHL); glutathione S-transferases (HaGST1a, 6 and 8); esterases (HaAce4, HaJHE); catalase (HaCAT); super-oxide-dismutase (HaCu/ZnSOD); fatty acid binding protein (HaFabp) and chitin deacetylase (HaCda5b) through dsRNA approach. Significant downregulation of cognate mRNA expression and reduced activity of trypsin and GST-like enzyme were evident upon feeding candidate dsRNAs to the larvae. Among these, the highest mortality was observed in HaAce4 dsRNA fed larvae followed by HaJHE; HaCAT; HaCuZnSOD; HaFabp and HaTry3 whereas remaining ones showed relatively lower mortality. Furthermore, the dsRNA fed larvae showed significant reduction in the larval mass and abnormalities at the different stages of H. armigera development compared to their control diets. For example, malformed larvae, pupae and moth at a dose of 60 pg/day were evident in high number of individual insects fed on dsRNA containing diets. Moreover, the growth and development of insects and moths were retarded in dsRNA fed larvae. These findings might provide potential new candidates for designing effective dsRNA as pesticide in crop protection. (C) 2016 Elsevier Inc. All rights reserved.

Robust highly flexible all-solid-state micro pseudocapacitor based on ternary oxide CuCo2O4 having ultrathin porous nanowall type morphology blended with CNT - Basu, Aniruddha; Bhardwaj, Monika; Gawli, Yogesh; Rode, Chandrasekhar V.; Ogale, Satishchandra B. (Chemistryselect, 2016)
In this work we demonstrate a facile approach to the fabrication of all solid state flexible interdigitated micro pseudocapacitor device using pre-synthesized CuCo2O4 (CCO) ternary metal oxide as the electrode material. The hydrothermally synthesized CCO exhibits a peculiar 3D interconnected aligned porous nanowall type morphology which is highly desirable for storage as well as charge transfer. The device is fabricated using CO2 laser scribing technique and the PVA-H3PO4 gel electrolyte is used as the electrolyte. The as-synthesized CCO as well as its blend with 10 wt.% CNT are examined for the electrochemical performance. CNT blending is shown to reduce the charge transfer resistance dramatically, thereby enhancing the pseudo capacitance. The areal capacitance of 2.29 mF cm(-2) is obtained from the solid state device. Moreover, the CCO-CNT electrode also shows a high stability upto 9000 cycles without a sign of further decay. Importantly, the devices also retain over 65% of their initial capacitance after 1000 large angle (608) bending cycles and 93% of the initial capacitance under 1208 bending condition, thanks to the mechanical flexibility afforded by CNTs without disrupting conducting paths.

Role of acceptor strength on OFET properties of small molecular organic semiconducting materials with D-A-D architecture - Sasikumar, M.; Bharath, D.; Kumar, G. Siva; Chereddy, Narendra Reddy; Chithiravel, S.; Krishnamoorthy, K.; Shanigaram, Balaiah; Bhanuprakash, K.; Rao, V. Jayathirtha (Synthetic Metals, 2016)
Two organic semiconducting materials 2,5-didodecyl-3,6-bis(4-(11-dodecyl-11H-benzo[a]carbazol-8yl)phenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione. (BCDPP) and 1,5-didodecyl-3,7-bis(4-(11-dodecyl-11H-benzo[a]carbazol-8-yl)phenyl)dipyrrolo[3,2-b:3',2'-e]pyrazine-2,6(1H,5H)-dione (BCPzDP) with D-A-D architecture have been designed, synthesized and well characterized. Both the materials have benzocarbazole donor end-capping units. While BCDPP contains well explored diketopyrrolopyrrole (DPP), BCPzDP possesses electron deficient dipyrrolopyrazinedione (PzDP) as acceptor moiety. The importance of the nature of acceptor moiety in tuning the charge transport properties of the synthesized materials is explored. Thermal, photo-physical and electrochemical properties of these materials are measured and solution processed OFETs are fabricated. OFETs with BCDPP show unipolar p-type semiconducting properties with hole mobility of 1.02 x 10(-4) cm(2) V-1 s(-1) and OFETs of BCPzDP exhibit ambipolar charge transport behaviour with optimal saturation hole and electron mobilities of 0.0054 and 0.0013 cm(2) V-1 s(-1), respectively. (C) 2016 Elsevier B.V. All rights reserved.

Role of aliphatic hydrocarbon content in non-solvating porogens toward porosity of cross-linked microbeads - Mane, Sachin; Badiger, Manohar V.; Rajan, C. R.; Ponrathnam, Surendra; Chavan, Nayaku (Polymer, 2016)
Megaporous spherical acrylate copolymer beads were synthesized by suspension polymerization using non-solvating porogens. Non-solvating porogens with higher aliphatic hydrocarbon content generated megaporous morphology with lower surface area. Surface area increased and inversely megaporosity was decreased with decrease in the aliphatic hydrocarbon content of porogen. Megaporosity (5.47 mu m) and pore volume of 5.52 cm(3)/g was obtained with n-decanol. Thermal property of copolymer is a function of type (rigidity/flexibility/elemental composition) and concentration (cross-link density) of monomer and cross-linker. Copolymer containing rigid cross-linker (divinylbenzene) had better thermal stability over copolymer with flexible cross-linker (ethylene dimethacrylate). Further, higher concentration of rigid cross-linker or lower concentration of flexible cross-linker enhanced the thermal stability. Porous polymers are potentially recognized as a solid support for solid-phase synthesis. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: Cross-linked microbeads; Interfacial tension; Megaporosity; Non-solvating porogens; Thermal properties

Role of Rhamnolipid: A biosurfactant in methane gas hydrate formation kinetics - Arora, Amit; Cameotra, Swaranjit Singh; Kumar, Rajnish; Singh, Anil Kumar; Kumar, Pushpendra; Balomajumder, Chandrajit; Laik, Sukumar (Proceedings of The First International Conference on Recent Advances in Bioenergy Research, 2016)
Naturally occurring methane gas hydrate is a vast source of methane gas which is trapped in crystalline ice-like structure present in permafrost regions and under the sea in outer continental margins. It is purposed that total amount of carbon in the form of methane hydrates is almost twice the carbon content in all the fossil fuel reserves put together, and hence these are supposed to be the future potential energy resource. This paper investigates the laboratory investigations on effect of a biosurfactant rhamnolipid on methane hydrate formation kinetics. Rhamnolipid was produced by Pseudomonas aeruginosa strain A11. The presence of P. aeruginosa has been reported in Gulf of Mexico gas hydrate samples. Biosurfactant reduced the surface tension of water from 72 to 36 mN/m with CMC of 70 mg/L. The biosurfactant dose is studied at two different concentrations in the solution at 100 and 1000 ppm. Kinetic of hydrate formation and growth is compared at 0, 100, and 1000 ppm of rhamnolipid showing that rhamnolipid acts as a hydrate promoter at these concentrations. Thus, small dosages of rhamnolipids produced by P. aeruginosa strain A11 must clearly affect the gas hydrate formation kinetics in natural sites (as in Gulf of Mexico).
Keywords: Induction time; methane hydrate; Potential energy resource; Pseudomonas aeruginosa; Rhamnolipid

Scandium triflate catalyzed unexpected cleavage of C-C bonds in ynones - Kavthe, Rahul D.; Bansode, Avinash H.; Patil, Nitin T. (Arkivoc, 2016)
An unexpected C-C bond cleavage in ynones in the presence of catalytic amounts of Sc(OTf)(3) in methanol under microwave irradiation has been discussed. The effect of substituent on the regioselectivity of C-C bond cleavage has carefully been addressed by employing various ynones derivatives. The mechanism has been proposed for the observed regioselectivity.
Keywords: C-C bond cleavage; Esters; Ketones; scandium triflate; ynones

Seeding of Au on CdSe/CdS nanoplates using Langmuir-Blodgett technique - Das, Subhasis; Satpati, Biswarup; Chauhan, Himani; Deka, Sasanka; Ghosalya, Manoj Kumar; Gopinath, Chinnakonda S.; Bala, Tanushree (RSC Advances, 2016)
Oleyl amine capped CdSe/CdS nanoplates were synthesized by hot injection technique which formed a stable monolayer over both a water subphase and an aqueous HAuCl4 subphase using a Langmuir-Blodgett trough. Au islands were generated at the edge as well as on one specific surface of the flat nanoplates by exploiting the reducing capacity of oleyl amine to form Au nanoseeds from AuCl4- ions. The initial Au nanoseeds changed to a shell surrounding these nanoplates on prolonged exposure to the subphase containing the Au precursor. Monolayer of the hybrid structures was deposited onto suitable substrates for characterization by a number of different techniques and to study the photocatalytic activity. The same substrate with the monolayers could be re-used in several cycles of photocatalysis.

Selective synthesis of N-unsubstituted and N-arylindoles by the reaction of arynes with azirines - Thangaraj, Manikandan; Bhojgude, Sachin Suresh; "Jain, Shailja"; Gonnade, Rajesh G.; Biju, Akkattu T. (Journal of Organic Chemistry, 2016)
The transition-metal-free and temperature-dependent highly selective reaction of arynes with 2H-azirines allowing the synthesis of either N-unsubstituted or N-arylindoles has been developed. At 60 degrees C, arynes generated from 2-(trimethylsilyl)aryl triflates smoothly insert into 2H-azirines to form 2,3-diarylindoles with high selectivity. Interestingly, when the reaction was performed at -10 degrees C, the selectivity was switched to the formation of 1,2,3-triarylindoles in good yields.

Selenium-containing fused bicyclic heterocycle diselenolodiselenole: field effect transistorstudy and structure property relationship - Debnath, Sashi; Chithiravel, Sundaresan; Sharma, Sagar; Bedi, Anjan; Krishnamoorthy, Kothandam; Zade, Sanjio S. (ACS Applied Materials & Interfaces, 2016)
The first application of the diselenolodiselenole (C4Se4) heterocycle as an active organic field effect transistor materials is demonstrated here. C4Se4 derivatives (2a-2d) were obtained by using a newly developed straightforward diselenocyclization protocol, which includes the reaction of diynes with selenium powder at elevated temperature. C4Se4 derivatives exhibit strong donor characteristics and planar structure (except 2d). The atomic force microscopic analysis and thin-film X-ray diffraction pattern of compounds 2a-2d indicated the formation of distinct crystalline films that contain large domains. A scanning electron microscopy study of compound 2b showed development of symmetrical grains with an average diameter of 150 nm. Interestingly, 2b exhibited superior hole mobility, approaching 0.027 cm(2) V-1 s(-1) with a transconductance of 9.2 mu S. This study correlate the effect of p-stacking, Se center dot center dot center dot Se intermolecular interaction, and planarity with the charge transport properties and performance in the field effect transistor devices. We have shown that the planarity in C4Se4 derivatives was achieved by varying the end groups attached to the C4Se4 core. In turn, optoelectronic properties can also be tuned for all these derivatives by end-group variation.

Self-exfoliated metal-organic nanosheets through hydrolytic unfolding of metal-organic polyhedra - Garai, Bikash; Mallick, Arijit; Das, Anuja; Mukherjee, Rabibrata; Banerjee, Rahul (Chemistry-A European Journal, 2016)
Few-layers thick metal-organic nanosheets have been synthesized using water-assisted solid-state transformation through a combined top-down and bottom-up approach. The metal-organic polyhedra (MOPs) convert into metal-organic frameworks (MOFs) which subsequently selfexfoliate into few-layered metal-organic nanosheets. These MOP crystals experience a hydrophobicity gradient with the inner surface during contact with water because of the existence of hydrophobic spikes on their outer surface. When the amount of water available for interaction is higher, the resultant layers are not stacked to form bulk materials; instead few-layered nanosheets with high uniformity were obtained in high yield. The phenomenon has resulted high yield production of uniformly distributed layered metal-organic nanosheets from three different MOPs, showing its general adaptability.

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.

Single pot transfer hydrogenation and aldolization of furfural over metal oxide catalysts - Biradar, Narayan S.; Hengne, Amol M.; Sakate, S. S.; Swami, R. K.; Rode, Chandrashekhar V. (Catalysis Letters, 2016)
One pot catalytic transfer hydrogenation (CTH) of furfural to furfuryl alcohol (FAL) by using hydrogen producing alcohols and simultaneous aldolization of carbonyl compounds produced during CTH, with furfural was achieved over non-noble metal oxides with bifunctional sites. Basic sites of MgO responsible for abstraction of proton showed complete conversion of furfural to give FAL and C8 monomer in a ratio of 3:1, respectively, the later altered to 1:1 by incorporating Al into MgO. Catalyst stability was established by its four cycles study. [GRAPHICS]
Keywords: Aldol; furfural; Furfuryl alcohol; Metal oxides; transfer hydrogenation

Site-selective synthesis and characterization of BODIPY-acetylene copolymers and their transistor properties - Debnath, Sashi; Singh, Saumya; Bedi, Anjan; Krishnamoorthy, Kothandam; Zade, Sanjio S. (Journal of Polymer Science Part A-Polymer Chemistry, 2016)
To study the effect of site-selective copolymerization of borondipyrromethene (BODIPY) with acetylene on the structural and optoelectronic properties, three copolymers P1-P3 were synthesized by the Sonogashira cross-coupling of BODIPY units with diacetylene and bromine capping through all the possible linkages: alpha-alpha (P1), alpha-beta (P2), and beta-beta (P3). The optoelectronic properties of the polymers were investigated systematically to understand the effect of site-selective polymerization. The HOMO levels of the polymers were significantly tuned from P1 to P3 with negligible change in the LUMO levels. Broadening of absorption spectra from P3 to P1 was observed because of increase in the extent of conjugation. Additionally, the charge transport properties of these polymers in organic thin-film transistors (OTFTs) revealed that P1 and P3 exhibited only p-type mobility, whereas P2 exhibited electron mobility. Notably, the further investigations of the surface morphology of polymer films by atomic force microscopy (AFM) unveiled that comb like nanostructural arrangements in P3 was beneficial for the charge-carrier mobility over the circular arrangements in P1 and P2. (C) 2016 Wiley Periodicals, Inc.
Keywords: acetylene; BODIPY; DFT; low-band gap

Situ fabrication of highly crystalline CdS decorated Bi2S3 nanowires (nano-heterostructure) for visible light photocatalyst application - Panmand, Rajendra P.; Sethi, Yogesh A.; Deokar, Rajashree S.; Late, Dattatray J.; Gholap, Haribhau M.; Baeg, Jin-Ook; Kale, Bharat B. (RSC Advances, 2016)
In situ synthesis of the orthorhombic Bi2S3 nanowires decorated with hexagonal CdS nanoparticles (nano-heterostructure) has been demonstrated by a facile solvothermal method. The tiny 5-7 nm CdS spherical nanoparticles are decorated on the surfaces of 30-40 nm Bi2S3 nanowires, successfully. Structural, morphological and optical studies clearly show the existence of CdS on the nanowires. A possible sequential deposition growth mechanism is proposed on the basis of experimental results to reveal the formation of the nano heterostructure. The heterostructures have been used as a photocatalyst for hydrogen production as well as degradation of methylene blue under solar light. The maximum hydrogen evolution i.e. 4560 and 2340 mu mol h(-1) 0.5 g was obtained from H2S splitting and glycerol degradation for Bi2S3 NWs decorated with CdS nanoparticles (nano-heterostructure) which is higher than that of the Bi2S3 NWs (3000 and 1170 mu mol h(-1) 0.5 g, respectively). The enhanced photocatalytical hydrogen evolution efficiency of the heterostructures is mainly attributed to its nanostructure. In the nano heterostructure, the CdS nanoparticles control the charge carrier transition, recombination, and separation, while the Bi2S3 nanowire serves as a support for the CdS nanoparticles. The photogenerated electron's migration is faster than the holes from the inside of a CdS nanoparticle to its surface or to the phase interface, resulting in a relatively higher hole density inside the CdS nanoparticle leaving electron density at surface of the Bi2S3 NWs. This influences the photocatalytic activity under solar light. Such nano-heterostructures may have potential in other photocatalytic reactions.

SnS2 nanoflakes for efficient humidity and alcohol sensing at room temperature - Bharatula, Lakshmi Deepika; Erande, Manisha B.; Mulla, Imtiaz S.; Rout, Chandra Sekhar; Late, Dattatray J. (RSC Advances, 2016)
We report a one step facile hydrothermal synthesis of layered SnS2 nanoflakes. The as-synthesized nanosheets are characterized using X-ray diffraction, Raman spectroscopy and Transmission Electron Microscopy (TEM). The humidity sensing behavior of SnS2 nanoflake sensor device were investigated in the range of 11-97% of relative humidity (RH) at room temperature. The response time of similar to 85 s and recovery time of similar to 6 s were observed for the SnS2 nanoflake based humidity sensor. A maximum sensitivity of 11.300% is recorded. We also investigate the SnS2 nanoflake based alcohol sensing properties towards methanol, ethanol and iso-propyl alcohol. An exclusive selectivity towards methanol with a response of 1580 is shown as compared to other analytes. The response time of similar to 67 s and recovery time of just 5 s were observed for the SnS2 nanoflake based methanol sensor.

Solid acid catalyzed synthesis of furans from carbohydrates - Bhaumik, Prasenjit; Dhepe, Paresh Laxmikant (Catalysis Reviews-Science and Engineering, 2016)
The alternative feedstock, biomass (particularly lignocelluloses), having the profuse availability, is promising for the synthesis of several value-added chemicals which are currently obtained from fossil feedstock. In this article, the synthesis of two extremely significant furan chemicals viz. furfural and 5-hydroxymethylfurfural (HMF) are discussed. In the synthesis of furans from biomass, numerous challenges, i.e., use of edible sugars as substrates, selectivity to furans, their isolation in pure form, reuse of catalyst, environmental issues, etc., are perceived and in the recent past researchers tried to resolve those by developing advance methodologies. This article comprehensively summarizes the latest progress made in the above-mentioned areas and also provides commentary on the analyses of results, rationale for observed activity and mechanisms, etc. It also discusses future aspects of this work.
Keywords: Biomass conversion; carbohydrates; cellulose; furans; furfural; hemicelluloses; HMF; solid acid catalyst

Solution chemistry-based nano-structuring of copper dendrites for efficient use in catalysis and superhydrophobic surfaces - Bakthavatsalam, Rangarajan; Ghosh, Subrata; Biswas, Ratul Kumar; Saxena, Aayushi; Raja, Alagar; Thotiyl, Musthafa Ottakam; Wadhai, Sandip; Banpurkar, Arun G.; Kundu, Janardan (RSC Advances, 2016)
Despite their performance and economic advantages over Ag and Au, there have been no focused research efforts on the nano-structuring of Cu dendrites with respect to fine-tuning their structure/morphology towards the efficiency enhancement of suitable applications. Reported here is a simple, versatile, environmentally-friendly and galvanic replacement reaction-based solution chemistry methodology to synthesize highly nano-structured copper dendrites targeted towards the efficiency enhancement of desired applications. Herein, copper is deposited galvanically on an Al foil in the presence of NaCl/HCl, wherein the chloride anions augment an uninterrupted replacement reaction. The growth process of Cu dendrites has been probed in detail. The presence of acid, the type of Cu2+ precursor salt, the Cu2+ ion concentration, the surfactant concentration and the reaction temperature are all demonstrated to provide useful means of modulating the surface structure/morphology of the dendrites. Notably, dendrites formed in the presence of acid are found to be highly nano-structured. Moreover, it is also found that the morphology/structure of the obtained Cu deposit depends considerably upon the choice of the Cu2+ precursor salt, a parameter that has been completely overlooked in the past. The acid-induced nano-structuring of the dendrites is exploited for enhancing their efficiency in the catalytic reduction of para-nitrophenol and for fabricating self-cleaning superhydrophobic surfaces. These nano-structured dendrites are demonstrated to have the highest ever normalized rate constant for the catalytic reduction reaction. Superhydrophobic surfaces fabricated using these dendrites demonstrate excellent self-cleaning abilities, showing a high contact angle (159 degrees) with low contact angle hysteresis (2 degrees). This facile synthetic strategy for the fabrication of highly nano-structured Cu dendrites is expected to open up avenues for the production of Cu-based low-cost functional nano/micro-materials.

Spatially branched CdS-Bi2S3 heteroarchitecture: single step hydrothermal synthesis approach with enhanced field emission performance and highly responsive broadband photodetection - Bankar, Prashant K.; Pawar, Mahendra S.; Pawbake, Amit S.; Warule, Sambhaji S.; Late, Dattatray J.; More, Mahendra A. (RSC Advances, 2016)
This report explores the controlled hierarchical synthesis of CdS nanostructure branches on Bi2S3 nanorod cores via a facile single step hydrothermal route. Morphological and structural studies reveal the formation of CdS-Bi2S3 heteroarchitecture with excellent stoichiometry between the constituent elements. The growth of CdS over Bi2S3 strongly depends on optimization of the reaction conditions, especially low PVP concentration. Furthermore, the as-synthesized CdS-Bi2S3 heteroarchitecture demonstrates multifunctionality in field emission and photoresponse. Interestingly, the CdS-Bi2S3 heteroarchitecture shows enhanced field emission properties such as low turn-on field (similar to 1.8 V mu m(-1) for 10 mu A cm(2)), high emission current density and better current stability in comparison to Bi2S3 and other nanostructures. The as-synthesized CdS-Bi2S3 heteroarchitecture exhibits considerable response and recovery times, similar to 207 ms and 315 ms, respectively in comparison to bare Bi2S3 nanostructures (similar to 655 ms and 678 ms). The present results demonstrate CdS-Bi2S3 heteroarchitecture as a potential candidate for future optoelectronic device applications.

Spectacular rate enhancement of the diels-alder reaction at the ionic liquid/n-hexane interface - Beniwal, Vijay; Manna, Arpan; Kumar, Anil (Chemphyschem, 2016)
The use of the ionic liquid/n-hexane interface as a new class of reaction medium for the Diels-Alder reaction gives large rate enhancements of the order of 10(6) to 10(8) times and high stereoselectivity, as compared to homogeneous media. The rate enhancement is attributed to the H-bonding abilities and polarities of the ionic liquids, whereas the hydrophobicity of ionic liquids was considered to be the factor in controlling stereoselectivity.
Keywords: Diels-Alder reaction; Interfaces; ionic liquids; kinetics; stereoselectivity

State-of-the-art catechol porphyrin COF catalyst for chemical fixation of carbon dioxide via cyclic carbonates and oxazolidinones - Saptal, Vitthal; Shinde, Digambar Balaji; Banerjee, Rahul; Bhanage, Bhalchandra M. (Catalysis Science & Technology, 2016)
A highly porous, crystalline catechol porphyrin COF was synthesized and applied as an organocatalyst for the chemical fixation of carbon dioxide to synthesize value-added chemicals such as cyclic carbonates and oxazolidinones under solvent-free and transition-metal-free conditions. The high surface area and the functionalities of the COF catalyst act synergistically to activate the starting material. The 2,3-DhaTph shows excellent activity towards cyclic carbonates at the atmospheric pressure of carbon dioxide. Additionally, this catalytic system is recyclable in nature and provides a higher turnover number than previously reported organocatalysts.

Studies of synergy between metal-support interfaces and selective hydrogenation of HMF to DMF in water - Goyal, Reena; Sarkar, Bipul; Bag, Arijit; Siddiqui, Nazia; Dumbre, Deepa K.; Lucas, Nishita; Bhargava, Suresh Kumar; Bordoloi, Ankur (Journal of Catalysis, 2016)
Metal-support interfaces play a very important role in heterogeneous catalysis. The interfacial interactions not only are responsible for stabilizing the necessary oxidation state to facilitate the reaction but also enhance the stability of the catalyst system. Nano dispersion of Ni on mesoporous nitrogen-rich carbon material has been achieved using two different synthesis methods. It was observed that nickel (0) gets stabilized by strong interfacial interaction with the nitrogen atoms of the support material, and the material was found to be very economic and efficient for the conversion of HMF to DMF in aqueous medium. The material shows >= 99% conversion to 5-(hydroxymethyl) furfural (HMF) within 6 h of reaction with 98.7% DMF selectivity. A unique correlation between synthesis methods and particle sizes with catalytic performance has been observed for these newly developed materials. Furthermore, a DFT calculation has been performed to predict the reaction mechanism. (C) 2016 Elsevier Inc. All rights reserved.
Keywords: biofuels; Biomass; Hydrogenation; mesoporous carbon; Ni-CNx

Study of magnetic entropy and heat capacity in ferrimagnetic Fe3Se4 nanorods - Sen Bishwas, Mousumi; Poddar, Pankaj (Journal Of Physics D-Applied Physics, 2016)
Change in the magnetic entropy and specific heat capacity in Fe3Se4 nanorods synthesized by a wet-chemical method in a broad temperature (215-340 K) and magnetic field range (0-60 k Oe) was studied. The isothermal magnetic entropy change (Delta S-M) is estimated by an indirect method from the isothermal magnetization curves measured in this temperature range. S-M(max) of -46 x 10(-2) J kg(-1).K-1 was obtained at similar to 317 K when the field was changed from 0 to 60 kOe. The maximum in the isothermal magnetic entropy change (Delta S-M) is observed in close proximity to TC (similar to 323 K), which is linked to the order-disorder transition. The nature of this transition was analyzed by universal curve behavior. The temperature and magnetic field dependence of specific heat capacity was studied and analyzed to estimate the adiabatic temperature change (Delta T-ad). The magnetic entropy change of Fe3Se4 nanoparticles is found to be comparable with similar ferrite and manganite nanoparticle systems and a broad operating temperature window of similar to 30 K was observed around room temperature.
Keywords: heat capacity; iron selenide; Magnetic anisotropy; magnetic entropy; order-disorder phase transition

Substrate-controlled selectivity switch in the three-component coupling involving arynes, aromatic tertiary amines, and CO2 - Bhojgude, Sachin Suresh; Roy, Tony; Gonnade, Rajesh G.; Biju, Akkattu T. (Organic Letters, 2016)
The transition-metal-free multicomponent coupling involving arynes, aromatic tertiary amines, and CO2 is reported. The reaction exhibits switchable selectivity depending on the electronic nature of the aromatic amines used. With amines bearing electron-releasing/neutral groups as the nucleophilic trigger, the reaction afforded 2-arylamino benzoates via a nitrogen to oxygen alkyl group migration. Employing electron-deficient amines in the reaction furnished 2-aminoaryl benzoates proceeding via the aryl to aryl amino group migration resembling a Smiles rearrangement.

Sunlight assisted degradation of dye molecules and reduction of toxic Cr(VI) in aqueous medium using magnetically recoverable Fe3O4/reduced graphene oxide nanocomposite - Boruah, Purna K.; Borthakur, Priyakshree; Darabdhara, Gitashree; Kamaja, Chaitanya Krishna; Karbhal, Indrapal; Shelke, Manjusha V.; Phukan, Pallabi; Saikia, Dulen; Das, Manash R. (RSC Advances, 2016)
In view of the significant impact of magnetically recoverable catalysts in photocatalytic applications, Fe3O4/reduced graphene oxide (rGO) nanocomposite photocatalyst was synthesized by adopting an eco-friendly solution chemistry approach and has been characterized by high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and photoluminescence (PL) spectroscopy. Fe3O4/rGO nanocomposite is efficiently utilized towards photocatalytic degradation of carcinogenic and mutagenic cationic as well as anionic dye molecules namely methyl green (MG), methyl blue (MB) and rhodamine B (RhB) under direct sunlight irradiation. The Fe3O4/rGO nanocomposite also demonstrated excellent photocatalytic reduction of aqueous Cr(VI) solution to nontoxic aqueous Cr(III) solution of more than 96% within 25 min under sunlight irradiation. Moreover, reusability of the magnetically recovered photocatalyst was studied efficiently up to 10 cycles in the degradation process. The catalyst was also characterized after the degradation of the dye molecule and the particle size of the Fe3O4 nanoparticles on the rGO sheets remained unchanged. The present investigation focuses on the importance of the use of Fe3O4/rGO nanocomposite towards photocatalytic degradation of waste water containing organic dye pollutants and toxic Cr(VI), as an easily recoverable and reusable photocatalyst with potential for many environmental remediation applications.

Supramolecular metallogel that imparts self-healing properties to other gel networks - Feldner, Tobias; Haering, Marleen; Saha, Subhadeep; Esquena, Jordi; Banerjee, Rahul; Diaz, David Diaz (Chemistry of Materials, 2016)
A unique proton conductive and moldable supramolecular metallogel (CuA-Ox-gel) made upon mixing at room temperature well-defined stock solutions of Cu(OAc)(2). H2O and oxalic acid dehydrate was found to have self-healing properties. Remarkably, the system also displayed an unprecedented ability to impart self-healing properties to other gel networks lacking this capacity. A self-healed CuA-Ox metallogel was found to have essentially the same nanofibrillar morphology, thermal stability, rheological properties, and conductivity as the freshly prepared sample. The discovery also allowed the fabrication of self-healing conductive composites containing conductive carbonaceous materials. Overall, this work serves as a proof of concept for the transfer of self-healing properties between completely different gel networks.

Surface chemical bonds, surface-enhanced Raman scattering, and dielectric constant of SiO2 nanospheres in-situ decorated with Ag-nanoparticles by electron-irradiation - Phatangare, A. B.; Dhole, S. D.; Dahiwale, S. S.; Mathe, V. L.; Bhoraskar, S. V.; Late, Dattatray J.; Bhoraskar, V. N. (Journal of Applied Physics, 2016)
Nanostructures of dielectric materials decorated with metal nanoparticles are of great scientific interest; however, the involved synthesis methods are complicated and require multistep chemical processing, including functionalization of the dielectric surfaces. In the present work, without chemical processes, silver nanoparticles of average sizes in the range of 11 to 15 nm were in-situ synthesized and decorated on SiO2 nanospheres in a single step process by irradiating a solution (AgNO3-polyvinylpyrrolidone (PVP)-SiO2 nanospheres) with 6 MeV electrons at 1.5 x 10(15) e(-)/cm(2), 3.0 x 10(15) e(-)/cm(2), and 4.5 x 10(15) e(-)/cm(2) fluences. The electron irradiated solutions were characterized with different surface and other techniques. The results revealed that the SiO2 nanospheres were uniformly decorated with Ag nanoparticles, and the prominent chemical bonds involved were Ag-O, Si-O-Ag, and Si-Ag. Moreover, the sizes and the decoration density of Ag nanoparticles could be tailored by varying electron fluence. The Surface-enhanced Raman scattering (SERS) of 4-aminothiophenol (4-ATP) solutions was studied using substrates in the form of thin coatings of the solutions of Ag-decorated SiO2 nanospheres. The appearance of the characteristic SERS peaks of both 4-ATP and 4, 4'-dimercaptoazobenzene (4, 4'-DMAB) in Raman spectra confirmed the conversion of a fraction of 4-ATP into 4, 4'-DMAB in the presence of Ag nanoparticles. Composites in the form of thin films were synthesized from the mixture solutions of PVP and Ag-decorated SiO2 nanospheres. The dielectric constant of each thin film was higher as compared to polymers, and could be tailored by varying electron fluence used for decorating Ag nanoparticles. Published by AIP Publishing.

Surface modification of aligned CdO nanosheets and their enhanced field emission properties - Bagal, Vivekanand S.; Patil, Girish P.; Deore, Amol B.; Suryawanshi, Sachin R.; Late, Dattatray J.; More, Mahendra A.; Chavan, Padmakar G. (RSC Advances, 2016)
Porous aligned CdO nanosheets were grown on a cadmium (Cd) substrate by the simple and cost effective method of thermal annealing. Further, decoration of gold (Au) nanoparticles on the porous aligned CdO nanosheets (specimen A) was achieved by coating with a Au thin film and subsequent annealing treatment. The average diameters of decorated Au nanoparticles were found to be 15 nm, 21 nm and 28 nm for the Au thin films with 20 s, 40 s and 60 s (specimens B, C, and D) coating times. Detailed characterizations, such as structural and morphological analysis of porous CdO nanosheets and Au/CdO nanocomposite (Au decorated porous CdO nanosheets), have been carried out using a Field Emission Scanning Electron Microscope (FESEM), X-ray diffraction (XRD) and a Transmission Electron Microscope (TEM). Field emission studies of specimens A, B, C and D were carried out in the planar diode configuration. Turn-on fields of 1.9 V mu m(-1), 1.1 V mu m(-1), 2.4 V mu m(-1) and 2.8 V mu m(-1) have been found for the emission current density of 10 RA cm(-2) for specimens A, B, C and D, respectively. The observed low turn -on field of specimen B (Au diameter of 15 nm) was found to be superior to other semiconducting nanostructures reported in the literature. The field emission current stability over a period of 3 h at the preset current density of 1 RA cm(-2) is found to be excellent for all specimens. To the best of our knowledge, field emission studies along with surface modification of porous aligned CdO nanosheets have not been reported in the literature. The simple synthesis route, facile surface modification and the superior field emission results make the present emitter very suitable for micro/nano electronic devices.

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.

Sustainable Iron-catalyzed direct imine formation by acceptorless dehydrogenative coupling of alcohols with amines - Jaiswal, Garima; Landge, Vinod Gokulkrishna; Jagadeesan, Dinesh; Balaraman, Ekambaram (Green Chemistry, 2016)
The Acceptorless Dehydrogenative Coupling (ADC) of alcohols with amines is reported using a heterogeneous Fe-catalyst. The reaction operates under mild conditions with the liberation of dihydrogen and water as the byproducts. The developed ADC strategy is simple, efficient, exhibits wide functional group tolerance and can be scaled up. The present catalytic approach possesses a dual role; acting as a catalyst as well as being magnetically separable. The sustainable reuse of a heterogeneous iron catalyst is also shown.

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 characterization of novel polymer-hybrid silver nanoparticles and its biomedical study - Verma, Suresh Kumar; Jha, Ealisha; Kiran, K. J.; Bhat, Suresh; Suar, Mrutyunjay; Mohanty, P. S. (Materials Today: Proceedings, 2016)
Hybrid polymer metal nanoparticles have advantages over conventional metal nanoparticles with respect to their stability, chemical resistance, antibacterial activity and drug delivery properties. In the current work, we have synthesized novel stimuli-responsive polymer hybrid silver nanoparticles using green synthesis method, where the plant extract is used as a reducing agent in the synthesis. Encapsulating metal nanoparticles with stimuli-responsive soft-polymeric system is novel and provides additional versatility whose functions and properties can be tailored by controlling any of the stimuli such as pH, temperature, ionic strength with respect to their antibacterial activity and physiological condition. Moreover, green synthesis methods have advantages over conventional methods involving chemical reducing agents that are often associated with environmental toxicity because of their enhanced antibacterial and other biological effects. The synthesized hybrid particles were characterized using Dynamic light scattering, UV-Visible spectroscopy and Small angle x-ray scattering. Further, we have investigated the antibacterial and cytotoxicity effect of these hybrid particles against different bacterial cells ( Salmonella) and mammalian cell lines (HCT116) respectively. These results are discussed in the light of previous studied work and these results suggest that our synthesized polymer hybrid nanoparticles are more antibacterial and less cytotoxic than the usual silver nanoparticles. (C) 2015Elsevier Ltd.All rights reserved.
Keywords: Antibacterial effect; Cytotoxicity; Polymeric hybrid particless; silver nanoparticles

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 and self-assembly of dumbbell shaped ZnO sub-micron structures using low temperature chemical bath deposition technique - Borade, P.; Joshi, K. U.; Gokarna, A.; Lerondel, G.; Walke, P.; Late, Dattatray J.; Jejurikar, S. M. (Materials Chemistry and Physics, 2016)
We report well dispersed horizontal growth of ZnO sub-micron structures using simplest technique ever known i.e. chemical bath deposition (CBD). A set of samples were prepared under two different cases A) dumbbell shaped ZnO grown in CBD bath and B) tubular ZnO structures evolved from dumbbell shaped structures by dissolution mechanism. Single phase wurtzite ZnO formation is confirmed using X-ray diffraction (XRD) technique in both cases. From the morphological investigations performed using scanning electron microscopy (SEM), sample prepared under case A indicate formation of hex bit tool (HBT) shaped ZnO crystals, which observed to self-organize to form dumbbell structures. Further these microstructures are then converted into tubular structures as a fragment of post CBD process. The possible mechanism responsible for the self-assembly of HBT units to form dumbbell structures is discussed. Observed free excitonic peak located at 370 nm in photoluminescence (PL) spectra recorded at 18 K indicate that the micro/nanostructures synthesized using CBD are of high optical quality. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Electron microscopy (STEM; Microstructure; Nanostructures; Optical properties; Photoluminescence spectroscopy; Raman spectroscopy and scattering; TEM and SEM)

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 4H-chromenes by an unexpected, K3PO4-mediated intramolecular rauhut–currier type reaction - Bhunia, Anup; Yetra, Santhivardhana Reddy; Gonnade, Rajesh G.; Biju, Akkattu T. (Organic & Biomolecular Chemistry, 2016)
In an attempt to develop the umpolung of Michael acceptors using chalcones having an enoate moiety under N-heterocyclic carbene (NHC) catalysis, a K3PO4-mediated intramolecular Rauhut–Currier type reaction was observed. This C(sp2)–C(sp2) coupling reaction afforded the biologically important 4H-chromenes in moderate to good yields. It is likely that the enol ether functionality acts as the nucleophilic trigger in this reaction.

Synthesis of Au@Ni bimetallic core shell nanoparticle and nanochains in soyabean oil and their catalytic hydrogenation reactions - Bharathan, Vysakh A.; Yadukiran, V.; Lazar, Anish; Singh, Anand. P.; Vinod, Chathakudath P. (ChemistrySelect, 2016)
Synthesis of Au@Ni bimetallic core shell nanostructures using commercially available soya bean oil as the solvent through a sequential reduction strategy is reported. The energy efficiency and economic viability comes from the much milder temperatures and replacement of expensive and environmentally hazardous solvents like long chain organic amines and acids previously reported for synthesis. Thus, core shell nanoparticles having size regime of 10-15 nm with an excellent control over the nickel shell thickness (2 nm) over the gold core (8-10 nm) and Au@Ni nanochains is achieved. The synthesized materials are demonstrated to synergistically catalyze hydrogenation of nitro and C-C multiple bonds with much better efficiency as compared to individual nanoparticle counterparts.
Keywords: Bimetallic nanoparticles; Gold catalysis; hydrogenation reactions; synergistic effects

Synthesis of functionalized amino epoxides by a three-component coupling involving aziridines, arynes and aldehydes - Roy, Tony; Thangaraj, Manikandan; Gonnade, Rajesh G.; Biju, Akkattu T. (Chemical Communications, 2016)
A transition-metal-free three-component coupling involving N-substituted aziridines, arynes and aldehydes resulting in the formation of trisubstituted N-aryl alpha-amino epoxides has been demonstrated. The reaction likely proceeds via the highly strained cyclic nitrogen ylide intermediates generated from aziridines and arynes.

Synthesis of Ni-doped ZnO nanostructures by low-temperature wet chemical method and their enhanced field emission properties - Rana, Amit Kumar; Bankar, Prashant; Kumar, Yogendra; More, Mahendra A.; Late, Dattatray J.; Shirage, Parasharam M. (RSC Advances, 2016)
In this study, we report an enhancement in the field emission (FE) properties of ZnO nanostructures obtained by doping with Ni at a base pressure of similar to 1 x 10(-8) mbar, which were grown by a simple wet chemical process. The ZnO nanostructures exhibited a single-crystalline wurtzite structure up to a Ni doping level of 10%. FESEM showed a change in the morphology of the nanostructures from thick nanoneedles to nanoflakes via thin nanorods with an increase in the Ni doping level in ZnO. The turn-on field required to generate a field emission (FE) current density of 1 mu A cm(-2) was found to be 2.5, 2.3, 1.8 and 1.7 V mu mcm(-2) for ZnO (Ni0%), ZnO (Ni5%), ZnO (Ni7.5%) and ZnO (Ni10%), respectively. A maximum current density of similar to 872 mu A cm(-2) was achievable, which was generated at an applied field of 3.1 V mu m cm(-2) for a Ni doping level of 10% in ZnO. Long-term operational current stability was recorded at a preset value of 5 mA for a duration of 3 h and was found to be very high. The experimental results indicate that Ni-doped ZnO-based field emitters can open up many opportunities for their potential use as an electron source in flat panel displays, transmission electron microscopy, and the generation of X-rays. Thus, the simple low-temperature (similar to 80 degrees C) wet chemical synthesis approach and the robust nature of the ZnO nanostructure field emitter can provide prospects for the future development of cost-effective electron sources.

Targeted quantification of N-1-(carboxymethyl) valine and N-1-(carboxyethyl) valine peptides of beta-hemoglobin for better diagnostics in diabetes - Jagadeeshaprasad, Mashanipalya G.; Batkulwar, Kedar B.; Meshram, Nishita N.; Tiwari, Shalbha; Korwar, Arvind M.; Unnikrishnan, Ambika G.; Kulkarni, Mahesh J. (Clinical Proteomics, 2016)
Background: N-1-(Deoxyfructosyl) valine (DFV) beta-hemoglobin (beta-Hb), commonly referred as HbA1c, is widely used diagnostic marker in diabetes, believed to provide glycemic status of preceding 90-120 days. However, the turnover of hemoglobin is about 120 days, the DFV-beta-Hb, an early and reversible glycation product eventually may undergo irreversible advanced glycation modifications such as carboxymethylation or carboxyethylation. Hence quantification of N-1-(carboxymethyl) valine (CMV) and N-1-(carboxyethyl) valine (CEV) peptides of beta-Hb would be useful in assessing actual glycemic status. Results: Fragment ion library for synthetically glycated peptides of hemoglobin was generated by using high resolution-accurate mass spectrometry (HR/AM). Using parallel reaction monitoring, deoxyfructosylated, carboxymethylated and carboxyethylated peptides of hemoglobin were quantified in clinical samples from healthy control, pre-diabetes, diabetes and poorly controlled diabetes. For the first time, we report N-1-beta-valine undergoes carboxyethylation and mass spectrometric quantification of CMV and CEV peptides of beta-hemoglobin. Carboxymethylation was found to be the most abundant modification of N-1-beta-valine. Both CMV-beta-Hb and CEV-beta-Hb peptides showed better correlation with severity of diabetes in terms of fasting glucose, postprandial glucose and microalbuminuria. Conclusions: This study reports carboxymethylation as a predominant modification of N-1-beta-valine of Hb, and quantification of CMV-beta-Hb and CEV-beta-Hb could be useful parameter for assessing the severity of diabetes.
Keywords: Diabetes; Diagnosis; Glycation; Glycemic control; HbA1c; Mass spectrometry

Is there any real effect of low dimensional morphologies towards light harvesting? a case study of Au-rGO-TiO2 nanocomposites - Melvin, Ambrose A.; Bharad, Pradnya A.; Illath, Kavya; Lawrence, Meenu P.; Gopinath, Chinnakonda S. (Chemistry Select, 2016)
Nanotube and nanosheet morphologies have been celebrated for their electron transport properties. Present work has been explored to exploit the same by combining 1D TiO2 nanotube (1D-TN) with 2D reduced graphene oxide (rGO) along with nano gold for visible light sensitization for photocatalytic H2 generation under one sun condition and visible light (λ≥ 400 nm). Vertical and horizontal electron transport in 1D-TN and rGO, respectively, is combined with the visible light absorption capability of Au nanoparticle. H2 yield (HY) varies between 100 and 655 µmol/g.h with an apparent quantum yield between 0.45 and 3.2 %, respectively, depending on Au/rGO/1D-TN preparation method and reaction conditions. It has been demonstrated that interfacial contact between rGO/1D-TN and Au is crucial for high photocatalytic HY. Preparation method influences charge utilization, and hence HY, to a large extent. Nonetheless, the maximum HY reported in the present work is just comparable to HY reported in literature with the most commonly found spherical morphology, and this leads to a question of, is there any real influence of 1D and/or 2D materials, particularly, towards light harvesting applications?

Three-phase slurry reactors - Buwa, V. V.; Roy, S.; Ranade, V. V. (Multiphase catalytic reactors: theory, design, manufacturing, and applications, 2016)
Many of the chemical reactors employed in various sectors of the process andchemical industries, suchas petroleumrefining,downstream processing and petrochemicals, bulk and specialty chemicals, and pharmaceuticals, involve reactants and products in three phases. The ubiquitous presence of three-phase reactors comes from the fact that many of the reactants are liquids under reaction conditions, to be treated with a gas like hydrogen, and in the presence of a heterogeneous catalyst that is usually a solid. This requirement leads to two broad modes of contacting one in which the catalyst is held stationary in a "fixed" or a "packed bed" and one in which the catalyst is set free to move, along with the flowing fluid phases, during their sojourn through the reactor vessel.The choice ofwhether the catalyst should be fixed ormoving is usually dictated by the relative dominance of transport rates and intrinsic kinetics. If the reaction chemistry is intrinsically slow (when external and internalmass transfer of chemical species from the fluid phases to the porous catalyst is not rate limiting), packed bed reactor that allows very high catalyst loading is usually preferred. Packed beds, however, do not constitute the main topic of discussion in this monograph. Still, three-phase packed beds and slurry reactors are really parts of the same continuum of three-phase catalytic reactors andhave beendiscussedcomprehensively about three decades back in the classic book by P.A. Ramachandran and R.V. Chaudhari (Three Phase Catalytic Reactors. NewYork:Gordon and Breach Science Publishers; 1983). The same authors published earlier a review of three-phase slurry reactors (Chaudhari RV, Ramachandran PA. Three phase slurry reactors. AIChE J. 1980;26(2):177-199). This chapter builds on these authors' works and attempts to update the reader on developments in the field over the past few decades while retaining the essential reactionandreactorengineering aspects.The focus isonthe design, scale-up, and operation of three-phase slurry reactor systems

Total synthesis of isocladosporin and 3-epi-isocladosporin - Mohapatra, Debendra K.; Maity, Saurabh; Banoth, Shivalal; Gonnade, Rajesh G.; Yadav, J. S. (Tetrahedron Letters, 2016)
A convergent total synthesis of isocladosporin and 3-epi-isocladosporin is reported starting from commercially available homoallyl alcohol in 10 longest linear steps with 28% overall yield. The key steps involved in the synthesis are cross-metathesis, tandem isomerization followed by C-O and C-C bond formation reactions for the synthesis of trans-2,6-disubstituted dihydropyrans developed by us, acylation reaction and Luche reaction. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Acylation reaction; Cross-metathesis; Iodocyclization; Isocladosporin 3-epi-Isodadosporin; Luche reduction

Toughening of epoxy novolac resin using cardanol based flexibilizers - Gour, Rajeshwari S.; Kodgire, Vivek V.; Badiger, Manohar V. (Journal of Applied Polymer Science, 2016)
In this work, two different cardanol based epoxies (Cardolite NC-514 and Cardanol NC-547) were employed as flexibilizers to toughen an epoxy novolac resin namely, poly[(phenylglycidyl ether)-co-formaldehyde] (PPGEF). 4,4-Diamino-3,3-dimethyl dicyclohexyl methane (BMCHA) was used as a curing agent. Differential scanning calorimetry and dynamic mechanical thermal analysis of the composites showed a gradual decrease in glass transition temperatures (T-g) with increase in cardolite content confirming the incorporation of flexible moieties into the brittle resin matrix. Improvement in toughening of PPGEF/Cardolite composites was manifested by increase in the izod impact strength of both the composites. The tensile strength increased marginally for composites with increasing amount of Cardolite NC-514 but decreased for the composites containing Cardolite NC-547. This was attributed to the lack of rotational motion in the chain due to close proximity of rigid phenyl rings in NC-547. SEM of the cryo-fractured surfaces of composites showed good compatibility between PPGEF and cardanol based flexibilizers. (c) 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43318.
Keywords: composites; crosslinking; glass transition

Transfer hydrogenation of biomass-derived levulinic acid to gamma-valerolactone over supported Ni catalysts - Hengne, Amol M.; Kadu, Brijesh S.; Biradar, Narayan S.; Chikate, Rajeev C.; Rode, Chandrashekhar V. (RSC Advances, 2016)
A sustainable process of catalytic transfer hydrogenation (CTH) of levulinic acid (LA) to gamma-valerolactone (GVL) was investigated over Ni on various supports (Al2O3, ZnO, MMT and SiO2) in the presence of isopropanol (IPA) as the H-donor. Among these, the montmorillonite (MMT) supported Ni catalyst showed almost complete LA conversion (>99%) and selectivity (>99%) to GVL within 1 h. XRD and XPS results showed that the concentration of the metallic species significantly enhanced (two to four times) in the recovered sample as compared to the freshly prepared Ni/MMT. This was due to the in situ reduction of Ni2+ species present on the catalyst surface, through liberated H-2 under the reaction conditions. The strong acid strength of MMT, evidenced by NH3-TPD and py-IR, facilitated the esterification of LA as well as cyclization to GVL. The conversion-selectivity pattern was found to decrease in the IPA-water mixture while, it remained unchanged in the IPA-acetone mixture. Our catalyst could be efficiently recycled up to five times with consistent CTH activity and selectivity to GVL. The plausible mechanism of LA to GVL conversion involves the formation of a levulinate ester with IPA that favours its simultaneous hydrogenation and cyclization in a spontaneous manner to give GVL and regenerating IPA for sustainability.

Transferability of different classical force fields for right and left handed alpha-helices constructed from enantiomeric amino acids - Biswas, Santu; Sarkar, Sujit; Pandey, Prithvi Raj; Roy, Sudip (Physical Chemistry Chemical Physics, 2016)
Amino acids can form D and L enantiomers, of which the L enantiomer is abundant in nature. The naturally occurring L enantiomer has a greater preference for a right handed helical conformation, and the D enantiomer for a left handed helical conformation. The other conformations, that is, left handed helical conformations of the L enantiomers and right handed helical conformations of the D enantiomers, are not common. The energetic differences between left and right handed alpha helical peptide chains constructed from enantiomeric amino acids are investigated using quantum chemical calculations (using the M06/6-311g(d,p) level of theory). Further, the performances of commonly used biomolecular force fields (OPLS/AA, CHARMM27/CMAP and AMBER) to represent the different helical conformations (left and right handed) constructed from enantiomeric (D and L) amino acids are evaluated. 5- and 10-mer chains from D and L enantiomers of alanine, leucine, lysine, and glutamic acid, in right and left handed helical conformations, are considered in the study. Thus, in total, 32 a-helical polypeptides (4 amino acids x 4 conformations of 5-mer and 10-mer) are studied. Conclusions, with regards to the performance of the force fields, are derived keeping the quantum optimized geometry as the benchmark, and on the basis of phi and psi angle calculations, hydrogen bond analysis, and different long range helical order parameters.

Treatment of the pesticide industry effluent using hydrodynamic cavitation and its combination with process intensifying additives (H2O2 and ozone) - Raut-Jadhav, Sunita; Badve, Mandar P.; Pinjari, Dipak V.; Saini, Daulat R.; Sonawane, Shirish H.; Pandit, Aniruddha B. (Chemical Engineering Journal, 2016)
Hydrodynamic cavitation (HC) and its combination with H2O2 and ozone have been applied in the present work for the treatment of industrial pesticide effluent. Initially, the effect of dilution of the effluent on the efficacy of hydrodynamic cavitation has been studied using circular venturi as a cavitator. Although an increase in the extent of dilution has not shown any beneficial effect on the actual moles of pollutant degraded, hybrid processes have been studied using 1:5 dilution due to very high TDS content of the effluent. Treatment of the industrial pesticide effluent using HC + ozone (3 gbh) process has demonstrated that the biodegradability index (BI) of the effluent increases from 0.123 to 0.324 after 2 h of operation. The rate of COD and TOC reduction has also increased by many folds by using HC in combination with ozone. In addition this, the treatment of industrial pesticide effluent using HC + H2O2 has also indicated that the rate of COD and TOC reduction increases significantly by using HC in combination with various loadings of H2O2. The study of interference of added H2O2 on the COD analysis has exhibited that the COD equivalence is 0.441 mg/L for 1 mg/L of H2O2. The energy efficiency and operating cost of various hybrid processes have been compared based on the cavitational yield and the cost of electricity. The combined process of HC and H2O2 has observed to be the most cost-effective one due to its higher cavitational yield and lower power consumption. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Biodegradability index; Hydrodynamic cavitation; Hydrogen peroxide; Industrial pesticide effluent; Ozone; Venturi

Understanding endothelial dysfunction in diabetic cardiovascular complications using mass spectrometry-based proteomics - Banarjee, Reema; Sharma, Akshay; Bai, Shakuntala; Deshmukh, Arati; Kazi, Rubina; Kulkarni, Mahesh J. (Heart, 2016)

Understanding positive and negative deviations in polarity of ionic liquid mixtures by pseudo-solvent approach - Beniwal, Vijay; Kumar, Anil (Physical Chemistry Chemical Physics, 2016)
Physico-chemical properties of liquid mixtures in general display large deviations from linear behaviour, arising out of complex specific and non-specific intermolecular interactions. The polarity of liquid mixtures displaying large positive and negative deviations can be minimized and linear mixing can be achieved in liquids using a pseudo-solvent methodology. The work described herein is designed to investigate the influence of different physical parameters on the linear pseudo-solvent composition in ionic liquid mixtures. For this purpose, we have determined the deviations from linearity, Delta E-T(N) values (defined as Delta E-T(N) = E-Texp.(N) - E-Tlin mix.(N) with E-Tlin mix.(N) given by Sigma(n)(i=0) E-Ti(N0) x(i)) for binary mixtures of a variety of ionic liquids, including two molecular solvents, DMSO and formamide. Firstly, the investigations were carried out in three 1-butyl-3-methylimidazolium cation based aprotic ionic liquids and the roles of anionic structure and hydrogen bond acceptor basicities (beta values) of the ionic liquids were determined. The influence of the cationic structure, i.e., the hydrogen bond donor acidity (alpha values) and non-associative nature of the ionic liquids, was determined using C2-methylated analogs, 1-butyl-2,3-dimethylimidazolium cation based ionic liquids. The role of the protic nature of ionic liquids was studied in two protic ionic liquids, viz., 1-methylimidazolium formate and 1-methylimidazolium acetate. The effects of the temperature, pseudo-solvent structure and solvatochromic probe structure on the Delta E-T(N) values were also explored.

Understanding the role of Keggin type heteropolyacid catalysts for glycerol acetylation using toluene as an entrainer - Kale, S. S.; Armbruster, U.; Eckelt, R.; Bentrup, U.; Umbarkar, Shubhangi B. (Applied Catalysis A-General, 2016)
The heterogeneously catalyzed esterification (acetylation) of glycerol toward triacetin in batch mode in presence of toluene as entrainer was studied. Silicotungstic acid, tungstophosphoric acid and phosphomolybdic acid as heteropolyacids (HPAs) supported on silica, alumina or silica-alumina were used as catalysts. The course of the reaction was found to be very sensitive to the nature of the HPA as well as the support. Solid characterization by Raman spectroscopy, XRD, and pyridine-FTIR revealed that only combinations of tungsten-based HPAs and silica support were able to preserve the structure of active component throughout the preparation process, which was essential to obtain active and selective catalysts. The interaction between HPA and support was decisive for stability and dispersion of the catalytically active species. With the best performing catalyst H4SiW12O40/SiO2, selectivity to triacetin reached 71% at complete conversion within 24h. The high selectivity to triacetin is attributed the Brensted acidic sites originated from stabilized Keggin structure and continuous removal of water during course of reaction. Toluene is able to form azeotropic mixtures with water and acetic acid and keeps the reaction temperature below the boiling point of acetic acid. Thus, water-free reaction conditions can be established. The catalyst was reusable; however, the activity and selectivity towards triacetin slightly decreased in a repetition run due to loss of active sites. (C) 2016 Elsevier B.V. All rights reserved.

Urinary proteome alterations in HER2 enriched breast cancer revealed by multipronged quantitative proteomics - Gajbhiye, Akshada; Dabhi, Raju; Taunk, Khushman; Vannuruswamy, Garikapati; RoyChoudhury, Sourav; Adhav, Ragini; Seal, Shubhendu; Mane, Anupama; Bayatigeri, Santhakumari; Santra, Manas K.; Chaudhury, Koel; Rapole, Srikanth (Proteomics, 2016)
Globally, breast cancer is the second most common cancer among women. Although biomarker discoveries through various proteomic approaches of tissue and serum samples have been studied in breast cancer, urinary proteome alterations in breast cancer are least studied. Urine being a noninvasive biofluid and a significant source of proteins, it has the potential in early diagnosis of breast cancer. This study used complementary quantitative gel-based and gel-free proteomic approaches to find a panel of urinary protein markers that could discriminate HER2 enriched (HE) subtype breast cancer from the healthy controls. A total of 183 differentially expressed proteins were identified using three complementary approaches, namely 2D-DIGE, iTRAQ, and sequential window acquisition of all theoretical mass spectra. The differentially expressed proteins were subjected to various bioinformatics analyses for deciphering the biological context of these proteins using protein analysis through evolutionary relationships, database for annotation, visualization and integrated discovery, and STRING. Multivariate statistical analysis was undertaken to identify the set of most significant proteins, which could discriminate HE breast cancer from healthy controls. Immunoblotting and MRM-based validation in a separate cohort testified a panel of 21 proteins such as zinc-alpha2-glycoprotein, A2GL, retinol-binding protein 4, annexin A1, SAP3, SRC8, gelsolin, kininogen 1, CO9, clusterin, ceruloplasmin, and alpha 1-antitrypsin could be a panel of candidate markers that could discriminate HE breast cancer from healthy controls.
Keywords: 2D-DIGE; Biomedicine; Breast cancer; HER2 enriched; SWATH; Urinary biomarkers

Valorization of coffee bean waste: a coffee bean waste derived multifunctional catalyst for photocatalytic hydrogen production and electrocatalytic oxygen reduction reactions - Unni, SreeKuttan M.; George, Leena; Bhange, Siddheshwar N.; Devi, R. Nandini; Kurungot, Sreekumar (RSC Advances, 2016)
Here, we report the valorization of coffee bean waste (CBW) by producing nitrogen doped porous carbon (p-Cof) having both photocatalytic and electrocatalytic properties using a silica templating method. Morphological investigation of p-Cof reveals the presence of assemblies of highly porous flat carbon blocks. p-Cof exhibits a high surface area (1213 m(2) g(-1)) and a wide range of micro-and mesopores with good electrical conductivity. Along with this, the surface of p-Cof displays the presence of graphitic and pyridone-type nitrogen coordinations, which help p-Cof to perform as a multifunctional catalyst as revealed from its catalytic activities towards photocatalytic hydrogen production (PHP) and electrocatalytic oxygen reduction reactions. p-Cof produces 334 mu mol h(-1) g(-1) of hydrogen from water under visible light and 575 mmol h(-1) g(-1) of hydrogen under solar light irradiation with excellent stability. Along with this, p-Cof also displays improved oxygen reduction reaction (ORR) activity in alkaline medium. A better onset potential (0.91 V vs. RHE) and half-wave potential (0.75 V vs. RHE) are displayed by p-Cof compared to the catalyst derived from the simple annealing of CBW without employing the silica template. Along with the better electrochemical activity, p-Cof shows excellent ORR kinetics and electrochemical stability compared to the current state-of-the-art Pt/C.

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

[3+2]-Annulation of platinum-bound azomethine ylides with distal C[double bond, length as m-dash]C bonds of N-allenamides - Chakrabarty, Indradweep; Inamdar, Suleman M.; Akram, Manjur O.; Gade, Amol B.; Banerjee, Subhrashis; Bera, Saibal; Patil, Nitin T. (Chemical Communications, 2017)
A Pt-catalyzed, highly regioselective reaction between N-allenamides and imino-alkynes leading to pyrrolo[1,2-a] indoles is described. This represents the first example of [3+2]-annulation of Pt-bound azomethine ylides with the distal CQC bond of N-allenamides. The mechanism of the reaction was established by computational studies.

Abundance matters: role of albumin in diabetes, a proteomics perspective - Bhat, Shweta; Jagadeeshaprasad, Mashanipalya G.; Venkatasubramani, Vinashya; Kulkarni, Mahesh J. (Expert Review of Proteomics, 2017)
Introduction: Human serum albumin (HSA) is a multifaceted protein with vital physiological functions. It is the most abundant plasma protein with inherent capability to bind to diverse ligands, and thus susceptible to various post-translational modifications (PTMs) which alter its structure and functions. One such PTM is glycation, a non-enzymatic reaction between reducing sugar and protein leading to formation of heterogeneous advanced glycation end products (AGEs). Glycated albumin (GA) concentration increases significantly in diabetes and is implicated in development of secondary complications. Areas covered: In this review, we discuss in depth formation of GA and its consequences, approaches used for characterization and quantification of GA, milestones in GA proteomics, clinical relevance of GA as a biomarker, significance of maintaining abundant levels of albumin and future perspectives. Expert commentary: Elevated GA levels are associated with development of insulin resistance as well as secondary complications, in healthy and diabetic individuals respectively. Mass spectrometry (MS) based approaches aid in precise characterization and quantification of GA including early and advanced glycated peptides, which can be useful in prediction of the disease status. Thus GA has evolved to be one of the best candidates in the pursuit of diagnostic markers for prediction of prediabetes and diabetic complications.

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.

Acyclic αγα-tripeptides with fluorinated- and nonfluorinated-furanoid sugar framework: importance of fluoro substituent in reverse-turn induced self-assembly and transmembrane ion-transport activity - Burade, S. S.; Shinde, S. V.; Bhuma, N.; Kumbhar, N.; Kotmale, A.; Rajamohanan, P. R.; Gonnade, R. G.; Talukdar, P.; Dhavale, D. D. (Journal Of Organic Chemistry, 2017)
Acyclic αγα-tripeptides derived from fluorinated-furanoid sugar amino acid frameworks act as reverse-turn inducers with a U-shaped conformation, whereas the corresponding nonfluorinated αγα-tripeptides show random peptide conformations. The NMR studies showed the presence of bifurcated weak intramolecular hydrogen bonding (F···HN) and N+···Fδ- charge-dipole attraction compel the amide carbonyl groups to orient antiperiplanar to the C-F bond, thus, demonstrating the role of the fluorine substituent in stabilizing the U-shaped conformation. The NOESY data indicate that the U-shaped tripeptides self-assembly formation is stabilized by the intermolecular hydrogen bonding between C=O···HN with antiparallel orientation. This fact is supported by ESI-MS data, which showed mass peaks up to the pentameric self-assembly, even in the gas phase. The morphological analysis by FE-SEM, on solid samples, showed arrangement of fibers into nanorods. The antiparallel self-assembled pore of the fluorinated tripeptides illustrates the selective ion-transport activity. The experimental findings were supported by DFT studies.

AgOTf-catalyzed dehydrative [3+2] annulation of aziridines with 2-naphthols - Kaicharla, Trinadh; Jacob, Anu; Gonnade, Rajesh G.; Biju, Akkattu T. (Chemical Communications, 2017)
The reaction of 2-naphthols with aziridines in the presence of AgOTf resulting in a dehydrative, formal [3+2] annulation is reported. The reaction allows the synthesis of functionalized benzoindolines, and tolerates a broad range of functional groups. A preliminary study on themechanism of this reaction indicates an SN1-type ring-opening of aziridines. This method is demonstrated for the one-pot synthesis of benzoindoles.

Agro-industrial wastes for production of biosurfactant by bacillus subtilis ANR 88 and its application in synthesis of silver and gold nanoparticles - Rane, Ashwini N.; Baikar, Vishakha V.; Kumar, D. V. Ravi; Deopurkar, Rajendra L. (Frontiers in Microbiology, 2017)
Biosurfactants, surface-active amphiphilic compounds, despite having a wide range of applications, have a high cost of production, which severely restricts their use. For cheaper production of biosurfactant, we investigated the potential of the indigenously isolated biosurfactant producing organism, Bacillus subtilis ANR 88, to grow on different cheap carbon sources (molasses, whey, and extracts of potato peels, orange peels, banana peels, and bagasse). We found that, B. subtilis ANR 88 used significant amounts of total sugar to produce cell biomass and biosurfactant. The biosurfactant production in minimal medium containing glucose as sole source of carbon was 0.207 g/l and the same with molasses as carbon source was 0.241 g/l. With whey as carbon source, isolate failed to produce biosurfactant. Amongst the extracts of the agro-wastes, the extracts of bagasse and orange peels gave 0.127 and 0.089 g/l of biosurfactant respectively. One-variable-at-a-time (OVAT) studies carried out to optimize the production of biosurfactant by B. subtilis ANR 88 resulted into maximum biosurfactant yield of 0.513 g/l in medium: molasses 4%, ammonium ferric citrate 0.25%, pH 7. Plackett-Burman design based statistical method for optimization increased the production of biosurfactant to 0.746 g/l, which is 3.6-fold of that produced on glucose. The biosurfactant produced by B. subtilis ANR 88 was analyzed by Fourier Transform Infrared Spectroscopy (FT-IR); it showed that the biosurfactant contained alkyl as well as peptide groups. The biosurfactant of B. subtilis ANR 88 was found effective in the synthesis of silver as well as gold nanoparticles in the total absence of conventional chemical reducing agents. Interestingly, nanoparticles produced were almost uniform in their size and shapes i.e., spherical silver (4-18 nm) and hexagonal gold nanoparticles (40-60 nm), as evident in TEM images.

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.

Ammonia-modified graphene sheets decorated with magnetic Fe3O4 nanoparticles for the photocatalytic and photo-Fenton degradation of phenolic compounds under sunlight irradiation - Boruah, Purna K.; Sharma, Bhagyasmeeta; Karbhal, Indrapal; Shelke, Manjusha V.; Das, Manash R. (Journal of hazardous materials, 2017)
Synthesis of easily separable and eco-friendly efficient catalyst with both photocatalytic and photo-Fenton degradation properties is of great importance for environment remediation application. Herein, ammonia-modified graphene (AG) sheets decorated with Fe3O4 nanoparticles (AG/Fe3O4) as a magnetically recoverable photocatalyst by a simple in situ solution chemistry approach. First, we have functionalized graphene oxide (GO) sheets by amide functional group and then Fe3O4 nanoparticles (NPs) are doped onto the functionalized GO surface. The AG/Fe3O4 nanocomposite showed efficient photocatalytic activity towards degradation of phenol (92.43%), 2-nitrophenol (2-NP) (98%) and 2-chlorophenol (2-CP) (97.15%) within 70–120 min. Consequently, in case of photo-Fenton degradation phenomenon, 93.56% phenol, 98.76% 2-NP and 98.06% of 2-CP degradation were achieved within 50–80 min using AG/Fe3O4 nanocomposite under sunlight irradiation. The synergistic effect between amide functionalized graphene and Fe3O4 nanoparticles (NPs) enhances the photocatalytic activity by preventing the recombination rate of electron-hole-pair in Fe3O4 NPs. Furthermore, the remarkable reusability of the AG/Fe3O4 nanocomposite was observed up to ten cycles during the photocatalytic degradation of these phenolic compounds.

Anti-microbial activity of chrysomycin a produced by streptomyces sp. against mycobacterium tuberculosis - Balaji, Muralikrishnan; Dan, Vipin Mohan; Joseph, Vinodh; Jamsheena, Vellekkatt; Ramachandran, Ranjit; Thomas, Sabu; Dastager, Syed Gulam; Kumar, K. Santhosh; Lankalapalli, Ravi Shankar; Kumar, R. Ajay (RSC Advances, 2017)
Limited efficacy of the BCG (Bacillus Calmette–Guérin) vaccine against adult tuberculosis and the emergence of resistance to existing anti-tuberculosis drugs compel discovery of novel antibiotics against Mycobacterium tuberculosis. Actinomycetes are still an attractive platform for the discovery of new antimicrobials, especially from untapped natural hotspots, despite the belief that they are an exhausted resource after repeated re-discoveries. Herein we report the isolation and identification of chrysomycin A from an actinomycete isolated from a coastal area in Kerala. We show for the first time that it has antimycobacterial activity. It was found to be bactericidal to planktonic and intracellular M. tuberculosis with an MIC of 3.125 μg mL⁻¹; it is non-hemolytic and has negligible cytotoxicity. The actinomycete that produces chrysomycin A was found to be a Streptomyces sp. through 16S rRNA gene sequencing.

Aromatic polyesters containing pendent 4-(phenylsulfonyl)phenyl groups: synthesis and characterization - Bapat, Snehalata P.; Jadhav, Sushilkumar A.; Valsange, Nitin G.; Tawade, Bhausaheb V.; Honkhambe, Pandurang N.; Chavan, Nayaku N.; Wadgaonkar, Prakash P. (Journal of Polymer Research, 2017)
A new bisphenol, 1,1-bis-[(4-hydroxyphenyl)-1-(4-phenylsulfonyl) phenyl)] ethane (DPSBP) was synthesized starting from diphenylsulfide and was characterized by spectroscopic methods. DPSBP was polycondensed with isophthalic acid chloride (IPC), terephthalic acid chloride (TPC) and a mixture of IPC and TPC (50: 50 mol%) by phase-transfer catalysed interfacial polymerization method to obtain aromatic polyesters containing pendent 4-(phenylsulfonyl)phenyl groups. A series of copolyesters was also obtained by polycondensation of varying molar proportions of DPSBP and bisphenol-A (BPA) with TPC. (Co) polyesters exhibited inherent viscosities in the range 0.56-1.57 dLg(-1) and number average molecular weights (Mn) were in the range 28,650-80,230 g/mol. Polyesters dissolved readily in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and aprotic polar solvents such as N-methylpyrrolidone, and N, N-dimethylacetamide. Tough, transparent and flexible films of polyesters could be cast from their chloroform solutions. X-Ray diffraction studies indicated amorphous nature of aromatic polyesters. Polyesters showed T-g values in the range 223-257 degrees C while T-10 values were in the range of 469-484 degrees C indicating their excellent thermal stability.
Keywords: Aromatic polyesters; Bulky pendent group; solubility; thermal stability

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

Base-free and catalyst-free synthesis of functionalized dihydrobenzoxazoles via vinylogous carbonate to carbamate rearrangement - Das, Tamal Kanti; Mondal, Santigopal; Gonnade, Rajesh G.; Biju, Akkattu T. (Organic Letters, 2017)
An unexpected, catalyst-free, and base-free intramolecular cyclization of N-aryloxyacrylate aldimines, under thermal conditions leading to the synthesis of functionalized dihydrobenzoxazoles, is reported. The reaction features a unique rearrangement of vinylogous carbonates to vinylogous carbamates resulting in a new carbon–oxygen and carbon–nitrogen bond construction. The reaction tolerates a broad range of functional groups and the desired products are formed in moderate to good yields.

Biology and development of xanthopimpla pedator (hymenoptera: ichneumonidae): pupal endoparasitoid of antheraea mylitta (Lepidoptera: Saturniidae) - Gathalkar, Ganesh B.; Barsagade, Deepak D.; Sen, Avalokiteswar (Annals of the Entomological Society of America, 2017)
The Antheraea mylitta (Drury) (Lepidoptera: Saturniidae) is a commercially important species for the production of tasar silk. However, the Xanthopimpla pedator (F.) (Hymenoptera: Ichneumonidae) is a major pupal endoparasitoid of A. mylitta, which affects the total tasar silk production in India. A gravid female X. pedator parasitizes the pupae of A. mylitta by depositing an egg, which produces a single offspring per host. We studied the development of immature forms of X. pedator by dissecting parasitized pupae of A. mylitta under laboratory conditions at 28-30 degrees C and 40-60% relative humidity. All immature stages of the parasitoid develop within the host in 20-22 d, by devouring the entire pupal content, resulting in dead or seedless cocoons. The total life cycle of X. pedator is completed inside the host pupa and the adult emerges out by rupturing the peduncle end of the cocoon. During development of X. pedator, five preimaginal stages, viz., egg, larval instars, prepupa, pupa, and a pharate adult, were observed. Xanthopimpla pedator passes through five larval instars identified by structural and morphometric variations. These include primary larva (L1), the intermediate larvae (L2-L4), and the finalinstar larva (L5). Biometric study and larval head width permitted the morphological separation of all five larval instars. In the present study, the biology and development of X. pedator inside the pupa of A. mylitta are reported for the first time with detailed photomicrographs. Therefore, the study may enable the information concerning physiological interactions between A. mylitta and its endoparasitoid, X. pedator.

Biomimetic total synthesis of angiopterlactone B and other potential natural products - Kotammagari, Tharun K.; Gonnade, Rajesh G.; Bhattacharya, Asish K. (Organic Letters, 2017)
A one-pot biomimetic synthesis of (-)-angiopterlactone B and its enantiomer (+)-angiopterlactone B has been accomplished via TBAF-catalyzed tandem ring contraction followed by oxa-Michael/Michael addition sequence. Comparison of specific optical rotations, absolute configurations, and CD spectra of natural, synthesized (-)-angiopterlactone B and (+)-angiopterlactone B unequivocally proves that the isolated angiopterlactone B must be levorotatory. Synthesis of hitherto undiscovered natural products 18 and 20 and analogues of angiopterlactone B demonstrate the versatility of this method.

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.

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.

Cascade energy transfer and tunable emission from nanosheet hybrids: locating acceptor molecules through chiral doping - Goudappagouda; Wakchaure, Vivek Chandrakant; Ranjeesh, Kayaramkodath Chandran; Abhai, Chalona Antony Ralph; Babu, Sukumaran Santhosh (Chemical Communications, 2017)
Light harvesting donor-acceptor assemblies are indispensable to efficiently tap photons. In an attempt to improve the light harvesting efficiency of an acceptor doped assembly, we design and synthesize a donor-acceptor-donor triad which exhibits an exceptional intramolecular energy transfer with excellent efficiency. Moreover, a facile cascade energy transfer (energy funnelling) is observed in the presence of a series of second acceptors (63-91% efficiency) with tunable emission colours. Self-assembled nanosheets formed by the triad in the presence of acceptors exhibit cascade energy transfer assisted tunable emission. In addition, use of chiral acceptors induces chirality to the triad and results in the formation of chiral nanosheets alongwith cascade energy transfer. Here chiral induction, nanosheet formation and cascade energy transfer in the presence of chiral acceptors are used as tools to probe the intercalation of acceptor molecules in the donor scaffold.

Catalytic branching cascades in diversity oriented synthesis - Bansode, Avinash H.; Chimala, Prathyusha; Patil, Nitin T. (ChemCatChem, 2017)
Diversity oriented synthesis (DOS) aims to generate small molecules with great structural diversity in an efficient manner. Recent years have witnessed significant achievements in the field, which help to validate the usefulness of DOS as a tool for the discovery of novel, biologically interesting small molecules. Catalytic branching cascades have emerged as a promising strategy because of their potential to transform a common type of substrate into diverse and distinct molecular frameworks. The details of the concept are presented herein.

Cerium-based metal-organic framework having inherent oxidase-like activity applicable for colorimetric sensing of biothiols and aerobic oxidation of thiols - Dalapati, Rana; Sakthivel, Balasubramanian; Ghosalya, Manoj K.; Dhakshinamoorthy, Amarajothi; Biswas, Shyam (Crystengcomm, 2017)
A cerium-basedmetal-organic framework (MOF; 1) with a UiO-66 (UiO: University of Oslo) framework topology was synthesized solvothermally by employing 3,4-dimethylthieno[2,3-b] thiophene-2,5-dicarboxylic acid as a ligand. The MOF was thoroughly characterized by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction, infrared spectroscopy, and thermogravimetric and N-2 sorption analyses. The activated material (1') retained its structural integrity in water, acetic acid and 1 M HCl solution. XPS investigation reveals the presence of both Ce(III) and Ce(IV) ions in 1. Owing to the presence of mixed-valence cerium ions, 1' was able to oxidize the chromogenic peroxidase substrate 3,3', 5,5'-tetramethylbenzidine (TMB) or 2,2'azinobis.3- ethylbenzothizoline-6-sulfonic acid) (AzBTS) in the absence of an external oxidizing agent. Thus, it showed inherent oxidase-like catalytic properties. Inspired by the excellent oxidase-mimicking activity of 1', a protocol was developed for the rapid colorimetric sensing of biothiols in NaAc buffer (0.2 M, pH = 4). The sensing ability of 1' towards cysteine was also demonstrated in human blood plasma. Furthermore, the redox-active cerium ions enabled 1' to exhibit excellent heterogeneous catalytic performance in aerobic oxidation catalysis of thiol compounds. The material is reusable (both as a sensor and as a catalyst), lowcost and highly stable, which renders it a promising candidate for the monitoring of biothiols in immunoassays and medical diagnosis as well as for industrial oxidation catalysis.

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

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).

Constructing ultraporous covalent organic fameworks in seconds via an organic terracotta process - Karak, S.; Kandambeth, S.; Biswal, B. P.; Sasmal, H. S.; Kumar, S.; Pachfule, P.; Banerjee, R. (Journal of the American Chemical Society, 2017)
Research on covalent organic frameworks (COFs) has recently gathered significant momentum by the virtue of their predictive design, controllable porosity, and long-range ordering. However, the lack of solvent-free and easy-to-perform synthesis processes appears to be the bottleneck toward their greener fabrication, thereby limiting their possible potential applications. To alleviate such shortcomings, we demonstrate a simple route toward the rapid synthesis of highly crystalline and ultraporous COFs in seconds using a novel salt-mediated crystallization approach. A high degree of synthetic control in interlayer stacking and layer planarity renders an ordered network with a surface area as high as 3000 m(2) g-(1). Further, this approach has been extrapolated for the continuous synthesis of COFs by means of a twin screw extruder and in situ processes of COFs into different shapes mimicking the ancient terracotta process. Finally, the regular COF beads are shown to outperform the leading zeolites in water sorption performance, with notably facile regeneration ability and structural integrity.

Copper and silver nanoparticles stabilized by bistriazole-based dendritic amphiphile micelles for 4-nitrophenol reduction - Patil, Naganath G.; Basutkar, Nitin B.; Ambade, Ashootosh V. (New Journal of Chemistry, 2017)
Copper and silver nanoparticles were fabricated in aqueous solution using micellar assemblies of dendritic amphiphiles containing triazole rings. Dendritic amphiphiles displaying a bistriazole unit between a hydrophobic benzyl ether dendron and two oligo(ethylene glycol) (OEG) chains were synthesized using click chemistry. Micelles were characterized by DLS, TEM, CMC determination, and dye encapsulation. Micellar size was dependent on the dendron backbone structure and OEG chain length. Metal nanoparticles were characterized by TEM and UV-Vis spectroscopy. The Cu NPs had a smaller average particle diameter than the Ag NPs. The micelle-stabilized nanoparticles, at a concentration of 7.5 ppm, were shown to efficiently catalyze the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4 in aqueous solution without stirring, using up to 1 ppm of substrate. The reaction catalyzed by Cu NPs followed zero order kinetics (k = 3.48 x 10(-3) M s(-1)), while the Ag NP-catalyzed reaction followed pseudo-first order kinetics (k = 1.28 x 10(-3) s(-1)).

Copper oxide supported on three-dimensional ammonia-doped porous reduced graphene oxide prepared through electrophoretic deposition for non-enzymatic glucose sensing - Maaoui, H.; Singh, S. K.; Teodorescu, F.; Coffinier, Y.; Barras, A.; Chtourou, R.; Kurungot, S.; Szunerits, S.; Boukherroub, R. (Electrochimica Acta, 2017)
The paper reports on the preparation of N-doped porous reduced graphene oxide/copper oxide (ammonia-doped-prGO/CuO) nanocomposite on gold electrodes using electrophoretic deposition (EPD) from an ethanolic suspension of ammonia-doped-prGO and Cu(ClO4)(2) by applying a DC voltage. The ammonia-doped-prGO/CuO nanocomposite film thickness is controlled by varying the deposition time. Morphological analysis using scanning electron microscopy (SEM) showed the formation of a 3 dimensional structure with CuO nanoparticles being homogeneously embedded in the graphene layer. Xray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman analysis revealed that the deposited copper was in its oxidized form, mainly CuO. The Au/ammonia-doped-prGO/CuO electrode was successfully applied for non-enzymatic amperometric detection of glucose. Under optimized conditions, the electrode exhibited a sensitivity of 1210 mu mM(-1) cm(-2) with a detection limit of 0.25 p,M (S/N =3) over a wide concentration range (0.25 mu M to 6 mM) at an applied potential of +0.50 V vs. Ag/AgCl. The electrode material displayed good stability, excellent selectivity, and accurate measurement in healthy and diabetic human serum samples.

Corrigendum: Agro-Industrial wastes for production of biosurfactant by bacillus subtilis ANR 88 and its application in synthesis of silver and gold nanoparticles [Front. Microbiol. 8, (492)] DOI: 10.3389/fmicb.2017.00492 - Rane, A.N.; Baikar, V. V.; Ravi Kumar, V.; Deopurkar, R. L. (Frontiers in Microbiology, 2017)

Covalent organic frameworks and organic cage structures - Banerjee, Rahul; Champness, Neil R. (CrystEngComm, 2017)

Critical role of select peptides in the loop region of G-rich PNA in the preferred G-quadruplex topology and stability - Bose, Tanaya; Kumar, Vaijayanti A. (Tetrahedron, 2017)
An uncharged PNA 15mer sequence formed unimolecular antiparallel G-quadruplex similar to that observed for DNA-TBA. Replacement of `tt' loop regions by peptides which induce helices or turns were found to have unpresidented effect on the quadruplex topology and stability. This study opens up a completely new strategy of utilizing G-quadruplex formation to display the array of functional groups in the three dimensional space thus creating a possibility of getting closer to the dream of designed peptides with three dimensional structures as observed in catalytic protein folds. (C) 2017 Elsevier Ltd. All rights reserved.
Keywords: ESI-MS study; G-quadruplex; Peptide nucleic acid; topology

CuCo2O4 nanowall morphology as Li-ion battery anode: Enhancing electrochemical performance through stoichiometry control - Bhardwaj, M.; Suryawanshi, A.; Fernandes, R.; Tonda, S.; Banerjee, A.; Kothari, D.; Ogale, S. (Materials Research Bulletin, 2017)
We have employed template-free synthesis of CuCo2O4 (CCO) system to achieve unique ultrathin porous nanowall type morphology, and evaluated for Li-Ion battery anode application. We observe that under the hydrothermal growth a starting stoichiometric mixture of cationic precursor's leads to a bi-phasic constitution comprising of defect-spinel CCO and a small quantity of CuO. Use of the excess but optimum cobalt in the precursor mix leads to single phase defect-spinel. We have carefully examined the implications of off-stoichiometry for different cases of interest (including the case of Cu-excess) for morphology, microstructure, the physical/electrochemical properties, and the evolution of the Li-ion battery anode under cycling for different active materials loading. In case of optimum Cu excess based CCO renders an impressive performance as Li-ion battery anode with high rate performance, 836 mAh g−1 and 757 mAh g−1 at 1.25C and 2.5C, respectively, and good cycling stability. © 2016 Elsevier Ltd

On demand electrochemical release of drugs from porous reduced graphene oxide modified flexible electrodes - Boulahneche, Samia; Jijie, Roxana; Barras, Alexandre; Chekin, Fereshteh; Singh, Santosh K.; Bouckaert, Julie; Medjram, Mohamed Salah; Kurungot, Sreekumar; Boukherroub, Rabah; Szunerits, Sabine (Journal of Materials Chemistry B, 2017)
Despite the advantages of an electrochemical control for drug release, only a handful of electrochemical-based release systems have been developed so far. We report herein on the development of an electrochemically activatable platform for on-demand delivery of drugs. It is based on flexible gold thin film electrodes coated with porous reduced graphene oxide (prGO) nanosheets onto which the drug of interest has been integrated beforehand. Two different drugs are investigated here: ondansetron hydrochloride (ODS), a selective 5-HT3 receptor antagonist used for preventing nausea and vomiting caused by chemotherapy and radiotherapy, and ampicillin (AMP), an antibiotic to prevent and treat a number of bacterial infections such as respiratory tract infections, urinary tract infections, and meningitis. In the case of ODS, application of a negative potential bias of -0.8 V results in a sustained slow ODS release with an ODS flux of 47 mu g cm(-2) h(-1). In the case of AMP, we show that polyethyleneimine modified prGO (prGO/PEI) is an extremely efficient matrix. Upon the application of +0.8 V, 24% of AMP could be released from the electrical interface in a time span of 2 h. The released AMP kept its antibacterial activity as demonstrated by antimicrobial tests. These examples illustrate the major benefits of the developed approach for biomedical applications.

Design and development of trivalent aluminum ions induced self healing polyacrylic acid novel hydrogels - Anjum, Sadiya; Gurave, Pramod; Badiger, Manohar V.; Tiwari, Neha; Gupta, Bhuvanesh (POLYMER, 2017)
Development of ionically crosslinked superabsorbent polyacrylic acid (PAA) self-healing hydrogels using trivalent aluminum ions was investigated. The PAA hydrogels exhibited excellent self-healing behavior depending on the amount of the aluminum within the matrix. The migration of these ions within the polymer matrix was responsible for the physical crosslinking of the hydrogel and the origin of self healing ability. The PAA-Al hydrogels were insoluble in water and exhibited significantly high degree of swelling (similar to 4000%). Hydrogel also exhibited good mechanical properties with high level of elongation. Excellent self-healing efficiency was observed under dynamic as well as oscillatory Theological measurements. The presence of Al ions within PAA hydrogel facilitated the self-healing ability because of the ionic interaction in these gels which plays the key role of dynamic reversible sacrificial bonds which reforms upon reversal of the deformative force. (C) 2017 Elsevier Ltd. All rights reserved.
Keywords: Aluminum chloride; Behavior; Complex; Composite; crosslinking; Delivery; High-Mechanical Strength; hydrogels; Network; Polyacrylic acid; Polymeric Materials; Self-healing; swelling; Tough; pH

Designing multicomponent nanosystems for rapid detection of circulating tumor cells - Banerjee, Shashwat S.; Khobragade, Vrushali; Khandare, Jayant J. (Methods in Molecular Biology, 2017)
Detection of circulating tumor cells (CTCs) in the blood circulation holds immense promise as it predicts the overall probability of patient survival. Therefore, CTC-based technologies are gaining prominence as a “liquid biopsy” for cancer diagnostics and prognostics. Here, we describe the design and synthesis of two distinct multicomponent magnetic nanosystems for rapid capture and detection of CTCs. The multifunctional Magneto-Dendrimeric Nano System (MDNS) composed of an anchoring dendrimer that is conjugated to multiple agents such as near infrared (NIR) fluorescent cyanine 5 NHS (Cy5), glutathione (GSH), transferrin (Tf), and iron oxide (Fe3O4) magnetic nanoparticle (MNP) for simultaneous tumor cell-specific affinity, multimodal high resolution confocal imaging, and cell isolation. The second nanosystem is a self-propelled microrocket that is composed of carbon nanotube (CNT), chemically conjugated with targeting ligand such as transferrin on the outer surface and Fe3O4 nanoparticles in the inner surface. The multicomponent nanosystems described here are highly efficient in targeting and isolating cancer cells thus benefiting early diagnosis and therapy of cancer.

Determination of onset temperature from the entropy for fragile to strong liquids - Banerjee, Atreyee; Nandi, Manoj Kumar; Sastry, Srikanth; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2017)
In this paper, we establish a connection between the onset temperature of glassy dynamics with the change in the entropy for a wide range of model systems. We identify the crossing temperature of pair and excess entropies as the onset temperature. Below the onset temperature, the residual multiparticle entropy, the difference between excess and pair entropies, becomes positive. The positive entropy can be viewed as equivalent to the larger phase space exploration of the system. The new method of onset temperature prediction from entropy is less ambiguous, as it does not depend on any fitting parameter like the existing methods. Published by AIP Publishing.

Determination of triazines and triazoles in grapes using atmospheric pressure matrix-assisted laser desorption/ionization high-resolution mass spectrometry - Mahale, Vishal; Singh, Ajeet; Phadke, Gayatri S.; Ghanate, Avinash D.; Oulkar, Dasharath P.; Banerjee, Kaushik; Panchagnula, Venkateswarlu (Journal of Aoac International, 2017)
A chromatography-free atmospheric pressure matrix-assisted laser desorption/ionization high-resolution mass spectrometry (AP-MALDI HRMS) method is described for the simultaneous and quantitative detection of triazines and triazoles in grapes. The analytes were detected reproducibly with high mass accuracy (mass error within 5 ppm) and further confirmed by collision-induced dissociation fragmentation in tandem MS. The LODs and LOQs for all the analytes were found to be in the nanogram per gram level (15-20 ng/g LOQ). Internal standard normalized high-resolution accurate mass extracted (HR-AM) peak intensities of the detected ions were used to generate the concentration response curves. Linearity (with R-2 values around 0.99) was obtained for these curves within a concentration range of 20-200 ng/g of the individual analytes. The accuracy and precision of the method were further established using QC samples. Validation and performance comparison of the AP-MALDI HRMS method with an existing standard method using LC with :triple quadrupole MS was carried out (evaluating sensitivity, accuracy, precision, and analysis time) using 20 table-grape field samples after QuEChERS extraction.

Developing techno-economically sustainable methodologies for deep desulfurization using hydrodynamic cavitation - Suryawanshi, N.B. (Fuel, 2017)
The present work, for the first time, describes the efficacy of the cavitation process and compares the cavitation yield for two types of cavitation devices-one employing linear flow for the generation of cavities and other employing vortex flow. The process involves pre-programmed mixing of the organic and aqueous phases, and can be carried out using simple mechanical cavitating devices such as orifice or vortex diode. The process essentially exploits in situ generation of oxidising agents such as hydroxyl radicals for oxidative removal of sulfur. The efficiency of the process is strongly dependent on the nature of device apart from the nature of the organic phase. The effects of process parameters and engineering designs were established for three organic solvents (n-octane, toluene, n-octanol) for model sulfur compound-Thiophene. A very high removal to the extent of 95% was demonstrated. The results were also verified using commercial diesel. The cavitation yield is significantly higher for vortex diode compared to the orifice. The process has potential to provide a green approach for desulfurization of fuels or organics without the use of catalyst or external chemicals/reagents apart from newer engineering configurations for effective implementation of hydrodynamic cavitation in industrial practice and also appears to be economically sustainable.
Keywords: Fuel; Oxidation; Petroleum; Pollution Control; Sulphur Removal

Diverse reactivity trends of Ni surfaces in Au@Ni core-shell nanoparticles probed by near ambient pressure (NAP) XPS - Bharathan, Vysakh A.; Jain, Ruchi; Gopinath, Chinnakonda S.; Vinod, C. P. (Catalysis Science & Technology, 2017)
A mild temperature sequential reduction method in aqueous medium is reported for the synthesis of Au@Ni nanoparticles with a core-shell morphology. The nickel shell thickness with a gold core in the nanostructure can be tuned from 2 nm up to about 10 nm. Near ambient pressure XPS (NAPXPS) studies under oxygen atmosphere show that Au-80@Ni-20 with an extremely thin nickel shell (similar to 2 nm) follows a distinctly different decomposition pathway of metastable Ni(OOH) species compared to those with larger shell thickness which behave more like individual nickel surfaces. Thus, Ni(OOH) on Au-80@Ni-20 decomposes to metallic Ni at 100 degrees C and is found to resist oxidation at 0.1 mbar oxygen at this temperature. Those with a larger nickel shell thickness behave more like monometallic Ni in terms of their decomposition and oxidation properties. The Au@Ni system with an ultra thin metallic nickel overlayer (2 nm) shows high catalytic activity and selectivity for phenylacetylene hydrogenation under mild conditions which outweighs their monometallic counterparts and those with higher nickel shell thickness.

Docetaxel-titanate nanotubes enhance radiosensitivity in an androgen-independent prostate cancer model - Mirjolet, C.; Martin, E.; Boudon, J.; Loiseau, A.; Chevrier, S.; Boidot, R.; Oudot, A.; Collin, B.; Joy, P. A.; Millot, N.; Créhange, G. (International Journal of Nanomedicine, 2017)
Around 40% of high-risk prostate cancer patients who undergo radiotherapy (RT) will experience biochemical failure. Chemotherapy, such as docetaxel (DTX), can enhance the efficacy of RT. Multidrug resistance mechanisms often limit drug efficacy by decreasing intracellular concentrations of drugs in tumor cells. It is, therefore, of interest to develop nanocarriers of DTX to maintain the drug inside cancer cells and thus improve treatment efficacy. The purpose of this study was to investigate the use of titanate nanotubes (TiONts) to develop a TiONts-DTX nanocarrier and to evaluate its radiosensitizing in vivo efficacy in a prostate cancer model. In vitro cytotoxic activity of TiONts-DTX was evaluated using an MTS assay. The biodistribution of TiONts-DTX was analyzed in vivo by single-photon emission computed tomography. The benefit of TiONts-DTX associated with RT was evaluated in vivo. Eight groups with seven mice in each were used to evaluate the efficacy of the nanohybrid combined with RT: control with buffer IT injection ± RT, free DXL ± RT, TiONts ± RT and TiONts-DXL ± RT. Mouse behavior, health status and tumor volume were monitored twice a week until the tumor volume reached a maximum of 2,000 mm3. More than 70% of nanohybrids were localized inside the tumor 96 h after administration. Tumor growth was significantly slowed by TiONts-DTX associated with RT, compared with free DTX in the same conditions (P=0.013). These results suggest that TiONts-DTX improved RT efficacy and might enhance local control in high-risk localized prostate cancer.
Keywords: Docetaxel Nanocarrier; nanoparticle; Prostate Cancer; Radiosensitivity; Titanate nanotubes

Draft genome sequence of lactobacillus plantarum strains E2C2 and E2C5 isolated from human stool culture - Suryavanshi, Mangesh V.; Paul, Dhiraj; Doijad, Swapnil P.; Bhute, Shrikant S.; Hingamire, Tejashri B.; Gune, Rahul P.; Shouche, Yogesh S. (Standards in Genomic Sciences, 2017)
Probiotic Lactobacillus species offer various health benefits, thus have been employed in treatment and prevention of various diseases. Due to the differences in the isolation source and the site of action, most of the lactobacilli tested in-vitro for probiotics properties fail to extend similar effects in-vivo. Consequently, the search of autochthonous, efficacious and probably population specific probiotics is a high priority in the probiotics research. In this regards, whole genome sequencing of as many Lactobacillus as possible will help to deepen our understanding of biology and their health effects. Here, we provide the genomic insights of two coherent oxalic acid tolerant Lactobacillus species (E2C2 and E2C5) isolated from two different healthy human gut flora. These two isolates were found to have higher tolerance towards oxalic acid (300 mM sodium oxalate). The draft genome of strain E2C2 consists of 3,603,563 bp with 3289 protein-coding genes, 94 RNA genes, and 43.99% GC content, while E2C5 contained 3,615,168 bp, 3293 coding genes (93.4% of the total genes), 95 RNA genes and 43.97% GC content. Based on 16S rRNA gene sequence analysis followed by in silico DNA-DNA hybridization studies, both the strains were identified as Lactobacillus plantarum belonging to family Lactobacillaceae within the phylum Firmicutes. Both the strains were genomically identical, sharing 99.99% CDS that showed 112 SNPs. Both the strains also exhibited deconjugation activity for the bile salts while genome analysis revealed that the L. plantarum strains E2C2 and E2C5 also have the ability to produce vitamins, biotin, alpha-and beta-glucosidase suggesting potential probiotic activities of the isolates. The description presented here is based on the draft genomes of strains E2C2 and E2C5 which are submitted to GenBank under the accession numbers LSST00000000.1 and LTCD00000000.1, respectively.

Drug-triggered self-assembly of linear polymer into nanoparticles for simultaneous delivery of hydrophobic and hydrophilic drugs in breast cancer cells - Palvai, Sandeep; Anandi, Libi; Sarkar, Sujit; Augustus, Meera; Roy, Sudip; Lahiri, Mayurika; Basu, Sudipta (ACS Omega, 2017)
Breast cancer is the most devastating disease among females globally. Conventional chemotherapeutic regimen relies on the use of highly cytotoxic drugs as monotherapy and combination therapy leading to severe side effects to the patients as collateral damage. Moreover, combining hydrophobic and hydrophilic drugs create erratic biodistribution and suboptimal medicinal outcome. Hence, packaging multiple drugs of diverse mechanisms of action and biodistribution for safe delivery into tumor tissues with optimal dosages is indispensable for next-generation breast cancer therapy. To address these, in this report, we describe a unique cisplatin-triggered self-assembly of linear polymer into 3D-spherical sub 200 nm particles. These nano-particles comprise a hydrophobic (paclitaxel) and hydrophilic drug (cisplatin) simultaneously in a single particle. Molecular dynamics simulation revealed hydrophilic-hydrophilic interaction and interchain H-bonding as underlying mechanisms of self-assembly. Confocal microscopy studies evidently demonstrated that these novel nanoparticles can home into lysosomes in breast cancer cells, fragment subcellular nuclei, and prevent cell division, leading to improved breast cancer cell death compared to free drug combination. Moreover, 3D-breast tumor spheroids were reduced remarkably by the treatment of these nanoparticles within 24 h. These dual-drug-loaded self-assembled polymeric nanoparticles have prospective to be translated into a clinical strategy for breast cancer patients.

Effect of reduction protocol of Pd catalysts on product distribution in furfural hydrogenation - Date, N. S.; Biradar, N. S.; Chikate, R. C.; Rode, C. V. (ChemistrySelect, 2017)
Single step conversion of furfural to ring hydrogenation and decarbonylation products, 2-methyltetrahydrofuran (2-MeTHF) and tetrahydrofuran (THF) in high selectivity was achieved by controlling the particle size of Pd/C catalyst. The particle size variation of Pd/C catalysts in the range of 3.8 to 22 nm could be achieved by employing different reducing agents. Of particular interest was the NaBH4 reduced catalyst (Pd-B/C), which gave the lowest crystallite size of 4.8 nm due to incorporation of B into the inner lattices of Pd-Pd. This phase was evidenced by a characteristic XRD peak of Pd-B at 2q=38.85 degrees as well as a shift of (111) peak (40.07 degrees) of Pd towards the lower value (39.8 degrees). As compared to formaldehyde reduced catalyst (Pd-F/C), Pd-B/C catalyst completely suppressed the formation of furfuryl alcohol to give > 65% selectivity to 2-MeTHF and THF. At 180 degrees C, almost equal distribution of side chain hydrogenation and ring opening products, 2-MF (45%) and PeDO (37 %), respectively, was observed while, higher temperature clearly favoured ring hydrogenation and decarbonylation reactions to give 2-MeTHF and THF.

Effect of viscoelastic relaxation modes on stability of extrusion film casting process modeled using multi-mode Phan-Thien-Tanner constitutive equation - Dhadwal, Renu; Banik, Sourya; Doshi, Pankaj; Pol, Harshawardhan (Applied Mathematical Modelling, 2017)
Extrusion film casting (EFC) is a commercially important process that is used to produce a significant quantity of polymer films, sheets and coatings for both industrial and household applications. Recently, we have demonstrated the influence of polymer chain architecture on the extent of necking under isothermal as well as non-isothermal film casting operation for commercially relevant polyolefin based materials [1-4]. In the present research, we focus on another instability that frequently occurs in high-speed EFC process called as draw resonance. Draw resonance manifests itself as an instability that causes periodic fluctuations in both the width as well as thickness of the extruded molten film above a critical draw ratio (DR). In this work, we have carried out a linear stability analysis of the isothermal EFC process using a multi-mode Phan-Thien-Tanner (PTT) constitutive equation to determine the onset of draw resonance. We show that as the number of relaxation modes is increased there is a dramatic change in the stability regions. In particular, there is a marked variation in the stability regions obtained by Simulating the multi-mode model and those obtained by taking averaged relaxation time of the modes. Additionally, as the number of faster-relaxing modes in a multi-mode spectrum is progressively increased, the process becomes increasingly stable as the level of elasticity in the melt decreases. Finally, the addition of a long relaxation mode in a multi-mode spectrum is akin to adding a long chain branch to a linear polymer that leads to a reduction in film necking and in many cases to enhanced process stability. (C) 2017 Elsevier Inc. All rights reserved.

Effective degradation of organic water pollutants by atmospheric non-thermal plasma torch and analysis of degradation process - Bansode, Avinash H.; More, Supriya Eknath; Siddiqui, Ejaz Ahmad; Satpute, Shruti; Ahmad, Absar; Bhoraskar, Sudha V.; Mathe, Vikas L. (Chemosphere, 2017)
The paper reports the use of atmospheric non-thermal plasma torch as a catalyst for degradation of various organic pollutants dissolved in water. A flow of He mixed with air was used to produce the dielectric barrier discharge (DBD), at the tip of the torch, using pulsed electric excitation at 12 kV. The torch, operated at a power of 750 mW/mm², was seen to completely degrade the aqueous solutions of the pollutants namely methylene blue (MB), methyl orange (MO) and rhodamine-B (RB), at around 10⁻⁴ M concentrations, the concentration of polluants is one order higher than of routinely used heterogeneous photocatalytic reactions, within 10 min of irradiation time at room temperature. UV Visible spectra of the organic dye molecules, monitored after different intervals of plasma-irradiation, ranging between 1 and 10 min, have been used as tools to quantify their sequential degradation. Further, instead of using He, only air was used to form plasma plume and used for degradation of organic dye which follow similar trend as that of He plasma. Further, Liquid Chromatography Mass Spectroscopy (LCMS) technique has been used to understand degradation pathway of methylene blue (MB) as a representative case. Total organic carbon (TOC) measurements indicates significant decrease in its content as a function of duration of plasma exposure onto methylene blue as a representative case. Toxicity studies were carried out onto Gram negative Escherichia coli. This indicated that methylene blue, without plasma treatment, shows growth inhibition, whereas with plasma treatment no inhibition was observed.

Effects of micellization on growth kinetics of methane hydrate - Bhattacharjee, Gaurav; Kushwaha, Omkar Singh; Kumar, Asheesh; Khan, Muzammil Yusuf; Patel, Jay Narayan; Kumar, Rajnish (Industrial & Engineering Chemistry Research, 2017)
Surfactants are Specific functional materials, that form various types of self-assemblies and affect local water ordering alongside solution properties. Such surface active agents are used extensively in gas hydrate based applications as kinetic hydrate promoters. To understand the effect of surfactant micelles on hydrate formation kinetics, a novel surfactant system capable of producing micelles at hydrate forming temperature was developed. The presence of surfactant micelles in this new system (a combination of anionic surfactant SDS and zwitterionic surfactant CAPB) was determined through DLS measurements. Pure methane and a coal bed methane mixture were individually used to assess the efficacy of the surfactant mixture for hydrate formation. This study conclusively proves for the first time that the presence of surfactant micelles enhances hydrate formation kinetics. The findings reported here can contribute significantly toward improving the utility of surfactants in gas hydrate based technological applications such as gas separation and methane storage.

Efficient and durable oxygen reduction electrocatalyst based on CoMn alloy oxide nanoparticles supported over N-doped porous graphene - Singh, Santosh K.; Kashyap, Varchaswal; Manna, Narugopal; Bhange, Siddheshwar N.; Soni, Roby; Boukherroub, Rabah; Szunerits, Sabine; Kurungot, Sreekurnar (ACS Catalysis, 2017)
Transition metal oxide derived materials are very important for various applications, such as electronics, magnetism, catalysis, electrochemical energy conversion, and storage. Development of efficient and durable catalysts for the oxygen reduction reaction (ORR), an important reaction in fuel cells and metal air batteries, is highly desirable. Moreover, the futuristic catalysts for these applications need to be costeffective in order to ensure a competitive edge for these devices in the energy market. This article describes the synthesis of a cost-effective and efficient electrocatalyst for ORR It is based on supporting CoMn alloy oxide nano particles on N-doped porous graphene through a simple and scalable microwave irradiation method. Microwave irradiation was found to be very crucial for the fast creation of pores in the graphene framework with a concomitant formation of the CoMn alloy oxide nanoparticles. A series of catalysts have been synthesized by varying the Co:Mn ratio, among which, the one with the Co:Mn ratio of 2:1 [designated as CoMn/pNGr(2:1)] displayed remarkably higher ORR activity in 0.1 M KOH solution. It showed a similar to 60 mV potential shift with a low Tafel slope of 74 mV/decade, which is comparable to that derived from the commercial Pt/C catalyst. This high activity of CoMn/pNGr(2:1) has been credited to the cooperative effect arising from the metal entities and the defects present in the N-doped porous graphene. Finally, real system-level validations of the use of CoMn/pNGr(2:1) as cathode catalyst could be performed by fabricating and testing single-cells of an anion-exchange membrane fuel cell (AEMFC) and a primary Zn-air battery, which successfully demonstrated the efficiency of the catalyst to facilitate ORR in real integrated systems of the single-cell assemblies.
Keywords: anion-exchange membrane fuel cell; cooperativity effect; microwave synthesis; oxygen reduction reaction; porous N-doped graphene; Zn-air battery

Efficient exciton to dopant energy transfer in Mn2+-Doped (C4H9NH3)2PbBr4 two-dimensional (2D) layered perovskites - Biswas, A. (Chemistry of Materials, 2017)
Three-dimensional ABX3 perovskite material has attracted immense interest and applications in optoelectronic devices, because of their enabling properties. Recently, Mn2+ doping directly into APbCl3-type three-dimensional (3D) nanocrystals, manifesting host-to-dopant energy transfer, have been reported for LED display applications. Strongly bound excitons in the doped system can enhance the dopant-carrier exchange interactions, leading to efficient energy transfer. Here, we report the simple and scalable synthesis of Mn2+-doped (C4H9NH3)2PbBr4 two-dimensional (2D) layered perovskites. The Mn2+-doped 2D perovskite shows enhanced energy transfer efficiency from the strongly bound excitons of the host material to the d electrons of Mn2+ ions, resulting in intense orange-yellow emission, which is due to spin-forbidden internal transition (4T1 → 6A1) with the highest quantum yield (Mn2+) of 37%. Because of this high quantum yield, stability in ambient atmosphere, and simplicity and scalability of the synthetic procedure, Mn2+-doped 2D perovskites could be beneficial as color-converting phosphor material and as energy down-shift coating for perovskite solar cells. The newly developed Mn2+-doped 2D perovskites can be a suitable material to tune dopant-exciton exchange interactions to further explore their magneto-optoelectronic properties.
Keywords: Doping (additives); Energy Efficiency; Energy Transfer; Exchange interactions; Excitons; Light Emitting Diodes

Efficient Sn(II)-catalyzed one-pot synthesis of a 3-substituted azetidine-2,4-dione framework - Chavan, Santosh S.; Supekar, Mrudul V.; Burate, Pralhad A.; Rupanwar, Bapurao D.; Shelke, Anil M.; Suryavanshi, Gurunath (Organic & Biomolecular Chemistry, 2017)
A novel Sn(II)-catalyzed tandem cyclization reaction of aromatic aldehydes with ethyl cyanoacetate has been achieved to afford a series of 3-substituted azetidine-2,4-diones in good to excellent yields. This protocol provides straightforward access to construct the azetidine core through sequential Knoevenagel condensation, hydration and the C-N cyclization reaction.

Efficient synthesis of functionalized olefins by wittig reaction using amberlite resin as a mild base - Valkute, Tushar R.; Aratikatla, Eswar K.; Bhattacharya, Asish K. (Synthetic Communications, 2017)
A convenient procedure for the synthesis of olefins by the reaction of stabilized, semistabilized, and nonstabilized phosphorous ylides with various aldehydes or ketone using Amberlite resin as a mild base is described. Our developed method offers facile and racemization-free synthesis of ,-unsaturated amino esters and chiral allylic amine. The developed methodology offers mild reaction conditions, high efficiency, and facile isolation of the final products, a practical alternative to known procedures

Efficient trifluoromethylation of C(sp(2))-H functionalized alpha-oxoketene dithioacetals: a route to the regioselective synthesis of functionalized trifluoromethylated pyrazoles - Sharma, N.; Kumari, N.; Chundawat, T. S.; Kumar, S.; Bhagat, S. (RSC Advances, 2017)
An operationally simple approach for the regioselective construction of diversely substituted trifluoromethylated pyrazoles via nucleophilic trifluoromethylation of iodo-substituted alpha-oxoketene dithioacetals is described. X-ray crystallographic studies confirmed the trifluoromethylation as well as formation of a regioselective cyclized product. Furthermore, trifluoromethylated pyrazoles bearing thiomethyl groups may allow further functionalization and are of considerable interest in medicinal chemistry.

Efficient valorisation of palm shell powder to bio-sorbents for copper remediation from aqueous solutions - Kushwaha, Shilpi; Soni, Harnish; Bojja, Sreedhar; Padmaja, P. (Journal of Environmental Chemical Engineering, 2017)
Alternative bio-sorbents, prepared from cost effective pre-treatment of biomass have been used to remediate toxic heavy metals. Palm shell powder (PSP) and acid treated palm shell powder (APSP) provide an attractive approach for the removal of Cu(II) from aqueous solutions and further use of the copper loaded adsorbents as catalysts. PSP was charred with sulfuric acid (H2SO4) to oxidize ligno-cellulosic groups present in PSP, resulted in acid treated palm shell powder (APSP). Structure property relationship was explored with the help of sophisticated spectroscopic tools (¹³C nuclear magnetic resonance (¹³C NMR), X-Ray photoelectron spectroscopy (XPS), X-Ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy). Pretreatment lead to conversion of ligno-cellulosic content to more valuable and easily process-able polysaccharide content.APSP and PSP displayed a maximum adsorption capacity of 125 and 36 mg/g respectively for copper. Copper adsorption was found to be more in APSP due to presence of COOH groups which rendered the surface more hydrophilic and amenable to enhanced Cu²⁺ sorption. Furthermore the adsorbents loaded with copper could be used as catalysts for oxidation of styrene. The developed adsorbents promise advantages such as low cost, high adsorption capacity, environmental friendliness as well as zero sludge.

Electrochemical water oxidation catalyzed by an in situ generated alpha-Co(OH)(2) film on zeolite-Y surface - Bose, Suranjana; Debgupta, Joyashish; Ramsundar, Rani M.; Das, Samar K. (Chemistry-A European Journal, 2017)
The design and synthesis of an efficient and robust water-oxidation catalyst with inexpensive materials remains an important challenge in the context of artificial photosynthesis. Herein, a simple but unique technique is reported to in situ generate a thin-film of alpha-Co(OH)(2) on the surface of zeolite-Y [hereafter referred to as Y-alpha-Co(OH)(2)] that acts as an efficient and stable catalyst for electrochemical water oxidation in alkaline medium. Catalyst Y-alpha-Co(OH)(2) is so stable that it retains its catalytic activity even after 2000 cyclic voltammetric cycles of water oxidation. Expectedly, the chemical composition of alpha-Co(OH)(2) on the surface of zeolite-Y remains same as that of parent Y-alpha-Co(OH)(2) after 2000 electrocatalytic cycles. A Tafel slope as low as 59 mV decade(-1) in 0.1m KOH (pH 13) suggests faster oxygen evolution kinetics (overpotential = 329 mV; turnover frequency = 0.35 mol O-2 (mol Co)(-1)s(-1) at 1 mA cm(-2)) than the existing alpha-Co(OH)(2)-based electrocatalysts operating in alkaline medium.

Electrostatic origin of the red solvatochromic shift of DFHBDI in RNA spinach - Bose, Samik; Chakrabarty, Suman; Ghosh, Debashree (Journal of Physical Chemistry B, 2017)
Interactions with the environment tune the spectral properties of biological chromophores, e.g., fluorescent proteins. Understanding the relative contribution of the various types of noncovalent interactions in the spectral shifts can provide rational design principles toward developing new fluorescent probes. In this work, we investigate the origin of the red shift in the absorption spectra of the difluoro hydroxybenzylidene dimethyl imidazolinone (DFHBDI) chromophore in RNA spinach as compared to the aqueous solution. We systematically decompose the effects of various components of interactions, namely, stacking, hydrogen bonding, and long-range electrostatics, in order to elucidate the relative role of these interactions in the observed spectral behavior. We find that the absorption peak of DFHBDI is red-shifted by similar to 0.35 eV in RNA relative to the aqueous solution. Earlier proposals from Huang and co-workers have implicated the stacking interactions between DFHBDI and nucleic acid bases to be the driving force behind the observed red shift. In contrast, our findings reveal that the long-range electrostatic interactions between DFHBDI and negatively charged RNA. make the most significant contribution. Moreover, we notice that the opposing electrostatic fields due to the RNA backbone and the polarized water molecules around the RNA give rise to the resultant red shift. Our results emphasize the effect of strong heterogeneity in the various environmental factors that might be competing with each other.

Elucidation of molecular mechanism of stability of the heme-regulated eIF2α kinase upon binding of its ligand, hemin in its catalytic kinase domain - Bhavnani, V. (Journal of Biomolecular Structure and Dynamics, 2017)
The eIF2α kinase activity of the heme-regulated inhibitor (HRI) is regulated by heme which makes it a unique member of the family of eIF2α kinases. Since heme concentrations create an equilibrium for the kinase to be active/inactive, it becomes important to study the heme binding effects upon the kinase and understanding its mechanism of functionality. In the present study, we report the thermostability achieved by the catalytic kinase domain of HRI (HRI.CKD) upon ligand (heme) binding. Our CD data demonstrates that the HRI.CKD retains its secondary structure at higher temperatures when it is in ligand bound state. HRI.CKD when incubated with hemin loses its monomeric state and attains a higher order oligomeric form resulting in its stability. The HRI.CKD fails to refold into its native conformation upon mutation of H377A/H381A, thereby confirming the necessity of these His residues for correct folding, stability, and activity of the kinase. Though our in silico study demonstrated these His being the ligand binding sites in the kinase insert region, the spectra-based study did not show significant difference in heme affinity for the wild type and His mutant HRI.CKD.
Keywords: Heme Regulated Inhibitor (HRI); HRI-eIF2α Complex; Protein–Ligand Modeling; Thermostability

Enantioselective synthesis of functionalized β-lactones by NHC-catalyzed aldol lactonization of ketoacids - Mondal, Santigopal; Mukherjee, Subrata; Das, Tamal Kanti; Gonnade, Rajesh G.; Biju, Akkattu T. (Journal of Organic Chemistry, 2017)
N-Heterocyclic carbene (NHC)-catalyzed intramolecular aldol lactonization of readily available ketoacids leading to the enantioselective synthesis of cyclopentane-fused β-lactones is presented. The reaction proceeds via the generation of NHC-bound enolate intermediates formed from the ketoacids in the presence of the peptide coupling reagent HATU and NHC generated from the chiral triazolium salt. The functionalized β-lactones are formed under mild conditions in high yields and enantioselectivities.

Enantioselective synthesis of spiro γ-butyrolactones by N-heterocyclic carbene (NHC)-catalyzed formal [3+2] annulation of enals with 3-hydroxy oxindoles - Mukherjee, Subrata; Joseph, Sumi; Bhunia, Anup; Gonnade, Rajesh Ghanshyam; Reddy, Santhi Vardhan; Biju, Akkattu T. (Organic & Biomolecular Chemistry, 2017)
The N-heterocyclic carbene (NHC)-catalyzed enantioselective formal [3 + 2] annulation of α,β-unsaturated aldehydes with 3-hydroxy oxindoles is presented. Under oxidative conditions using the bisquinone oxidant, the reaction resulted in the synthesis of spiro γ-butyrolactones in moderate to good yields, enantioselectivity and diastereoselectivity. The reaction likely proceeds via the generation of the NHC-bound α,β-unsaturated acylazolium intermediate from enals, which was intercepted by the dioxindoles in a formal [3 + 2] pathway to form the spirocyclic compounds. However, a deeper mechanistic investigation revealed that the reaction can also proceed via the homoenolate intermediate. In this case, the dioxindole was oxidized to the corresponding isatin derivative using traces of air under basic conditions, and was intercepted with the NHC-bound homoenolate intermediate in a formal [3 + 2] pathway to afford the spiro compound.

Engineering molecular topology: A pseudopeptidic macrocyclic figure-eight motif - Sharma, Sakshi; Thorat, Shridhar H.; Gonnade, Rajesh G.; Jasinski, Jerry P.; Butcher, Ray; Haridas, V. (European Journal of Organic Chemistry, 2017)
We herein present a rational-design strategy for the synthesis of molecules with figure-eight topology. The design concept is based on the incorporation of turn units in the back-bone of the macrocycle. The molecular structures and the folding are studied by X-ray crystallography and NMR, FT-IR, and CD spectroscopy.
Keywords: Macrocycles; noncovalent interactions; Pi interactions; topology; X-ray diffraction

Enhanced field emission performance of MoO3 nanorods and MoO3-rGO nanocomposite - Bankar, Prashant K.; Khandare, Lina N.; Late, Dattatray J.; More, Mahendra A. (ChemistrySelect, 2017)
The graphene and semiconducting hybrid based nanostructures have emerged as a new class of multifunctional materials with improved performance in comparison to the pristine semiconductors. Here, as-synthesized MoO3-reduced graphene oxide (rGO) nanocomposite emitter exhibits enhanced field emission (FE) behavior as compared to the pristine 1D MoO3 nanorods. The hydrothermally synthesized 1D MoO3 nanorods (1D) are grafted on the rGO sheet (2D) using a simple room temperature sonochemical method. The morphological and structural analysis confirms the attachment of MoO3 nanorods with rGO and the improved conductivity of the sample indicates a strong electronic interaction between them. Furthermore, the FE studies of as-synthesized MoO3 nanorods and MoO3-rGO nanocomposite emitters, carried out at a base pressure -1 x 10(-8) mbar, reveals the values of turn on field (required to draw an emission current density of 1 mu A/cm(2)) as 1.6 and 1.4 V/mu m, respectively. Interestingly, the maximum emission current density of 2810 mA/cm(2) is achieved at a lower applied field of 2.7 V/mu m from the MoO3-rGO nanocomposite emitter. The enhancement in FE performance of MoO3-rGO nanocomposite is attributed to the improved electrical conductivity, mechanical properties and higher concentration of protruding edges (emission sites). This observation can be extended to other graphene-based 1D inorganic hybrid semiconductor nanocomposites, which can provide a valuable opportunity to explore novel hybrid materials for vacuum nano-electronic devices.

Enhanced field emission performance of NiMoO4 nanosheets by tuning the phase - Bankar, Prashant K.; Ratha, Satyajit; More, Mahendra A.; Late, Dattatray J.; Rout, Chandra Sekhar (Applied Surface Science, 2017)
In this paper we report, large scale synthesis of a and beta-NiMoO4 by a facile hydrothermal method and we observed that urea plays important role on the growth of beta-NiMoO4 nanosheets. We have also carried out field emission (FE) investigations of alpha and beta-NiMoO4 at a base pressure of similar to 1 x 10(-8) mbar. The obtained turn-on field at emission current density of 1 mu A/cm(2) for beta-NiMoO4 nanosheets and alpha-NiMoO4 is 1.3V/mu m and 2.2V/mu m respectively were observed. The maximum field emission current density of 1.006 mA/cm(2) at an applied electric field of 2.7V/mu m was achieved for beta-NiMoO4 nanosheets. Furthermore, we found that the beta-NiMoO4 nanosheets possess good field emission performance compared to alpha-NiMoO4. The results indicate that NiMoO4 can be used as a promising material in FE applications with possibility of tuning field emission performance by controlling the phase. (C) 2017 Elsevier B.V. All rights reserved.

Enhanced field emission performance of NiMoO4 nanosheets by tuning the phase - Bankar, P. K. (Applied Surface Science, 2017)
In this paper we report, large scale synthesis of α and β-NiMoO4 by a facile hydrothermal method and we observed that urea plays important role on the growth of β-NiMoO4 nanosheets. We have also carried out field emission (FE) investigations of α and β-NiMoO4 at a base pressure of ∼1 × 10−8 mbar. The obtained turn-on field at emission current density of 1 μA/cm2 for β-NiMoO4 nanosheets and α −NiMoO4 is 1.3 V/μm and 2.2 V/μm respectively were observed. The maximum field emission current density of 1.006 mA/cm2at an applied electric field of 2.7 V/μm was achieved for β-NiMoO4 nanosheets. Furthermore, we found that the β-NiMoO4 nanosheets possess good field emission performance compared to α-NiMoO4. The results indicate that NiMoO4can be used as a promising material in FE applications with possibility of tuning field emission performance by controlling the phase.
Keywords: Current stability; field emission; nanosheets; NiMoO4

Environmentally benign bioderived carbon microspheres-supported molybdena nanoparticles as catalyst for the epoxidation reaction - Doke, Dhananjay S.; Umbarkar, Shubhangi B.; Gawande, Manoj B.; Zbori, Radek; Biradar, Ankush V. (ACS Sustainable Chemistry & Engineering, 2017)
A one pot synthesis of molybdenum oxide nanoparticles (NPs supported on bioderived carbon microspheres is reported. The catalyst was synthesized by the low temperature hydrothermal (LTH) method using D-glucose and bagasse as the carbon source. The carbonization of bagasse resulted in the formation of nonuniform carbon microspheres while glucose resulted in uniform carbon spheres. SEM and STEM elemental mapping show the uniform distribution of molybdenum oxide NPs over the carbon microspheres. XPS spectroscopy confirmed that molybdenum was in the Mo6+ oxidation state. The 1% MoO3 supported on carbon microspheres derived from D-glucose showed excellent catalytic activity up to 100% olefin conversion with 100% epoxide selectivity using organic tent-butyl hydroperoxide as an oxidant. The catalyst was successfully used for up to five cycles without losing substantial activity and selectivity.
Keywords: Carbon microspheres; epoxidation; heterogeneous catalysis; Hydrothermal synthesis; TBHP

Epalrestat-cytosine cocrystal and salt structures: attempt to control E,Z -> Z,Z isomerization - Nangia, Ashwini Kumar; Battini, Swapna (Crystal Growth & Design, 2017)
Cocrystallization of the anti-diabetic drug Eparlestat (EPR) with cytosine (CYT) gave EPR‒‒CYT-H+ form I, a salt-cocrystal hybrid structure, salt hydrate (EPR‒‒CYT-H+‒H2O, 1:2:1), and non-stoichiometric solvates of EPR‒‒CYT-H+ with EtOH/n-PrOH included in the rhombohedral symmetry voids, referred to as form II. Desolvation of EPR‒‒CYT-H+ form II solvates resulted in an unsolvated form II of EPR‒‒CYT-H+ which was characterized by DSC, TGA and NMR. The carboxylate•••cytosinium synthon was observed in the salts structure along with the uncommon CYT-H+•••H+-CYT base pairing in the structures of salt-cocrystal hybrid and salt hydrate. The crystalline forms were characterized by spectroscopic (IR, NMR), thermal (DSC, HSM, TGA), powder X-ray diffraction (PXRD) and single crystal X-ray diffraction (SC-XRD) techniques. The intent of using the salt/ salt-cocrystal forms as a means to stop the E,Z  Z,Z isomerization of EPR was not successful in photo-irradiation experiments.

Exploiting the dual role of ethynylbenziodoxolones in gold-catalyzed C(sp)-C(sp) cross-coupling reactions - Banerjee, Somsuvra; Patil, Nitin T. (Chemical Communications, 2017)
Reported herein is the gold-catalyzed alkynylation of terminal alkynes using ethynylbenziodoxolones (EBXs), where EBXs serve a dual role as oxidants as well as alkyne transfer agents to access unsymmetrical 1,3-diynes. Hence, the catalytic system requires no external oxidants and is compatible with a broad range of substrates, including those with polar functional groups such as NH, OHand B(OH)(2).

Exploring the effect of hydroxylic and non-hydroxylic solvents on the reaction of [(VO)-O-IV(beta-diketonate)2] with 2-aminobenzoyl-hydrazide in aerobic and anaerobic conditions - Biswas, Nirmalendu; Patra, Debashis; Mondal, Bipul; Bera, Sachinath; Acharyya, Swarnali; Biswas, Anup Kumar; Mukhopadhyay, Titas Kumar; Pal, Amrita; Drew, Michael G. B.; Ghosh, Tapas (Dalton Transactions, 2017)
Refluxing [(VO)-O-IV(beta-diketonate)(2)], namely [(VO)-O-IV(acetylacetonate)(2)] and [(VO)-O-IV(benzoylacetonate)(2)], separately with an equivalent or excess amount of 2-aminobenzoylhydrazide (ah) in laboratory grade (LG) CH3OH in aerobic conditions afforded non-oxidovanadium(IV) and oxidovanadium(V) complexes of the type [V-IV(L-1)(2)] (1), [(VO)-O-V(L-1)(OCH3)](2) (3) and [V-IV(L-2)(2)] (2), and [(VO)-O-V(L-2)(OCH3)] (4), respectively. (L-1)(2-) and (L-2)(2-) represent the dianionic forms of 2-aminobenzoylhydrazone of acetylacetone (H2L1) and benzoylacetone (H2L2), respectively, (general abbreviation, H2L), which was formed by the in situ condensation of ah with the respective coordinated [beta-diketonate] in medium-to-good yield. The yield of different resulting products was dependent upon the ratio of ah to [(VO)-O-IV(beta-diketonate)(2)]. For example, the yield of 1 and 2 complexes increased significantly associated with a decrease in the amount of 3 and 4 with an increase in the molar ratio of ah. Upon replacing CH3OH by a non-hydroxylic solvent, LG CHCl3, the above reaction yielded only oxidovanadium(V) complexes of the type [(VO)-O-V(L-1)(OH)](2) (5), [(VO)-O-V(L-2)(OH)] (6) and [(V2O3)-O-V(L)(2)] (7, 8) whereas, upon replacing CHCl3 by another non-hydroxylic solvent, namely LG CH3CN, only the respective [(V2O3)-O-V(L)(2)] (7, 8) complex was isolated in 72-78% yield. However, upon performing the above reactions in the absence of air using dry CH3OH or dry CHCl3, only the respective [V-IV(L)(2)] complex was obtained, suggesting that aerial oxygen was the oxidising agent and the type of pentavalent product formed was dependent upon the nature of solvent used. Complexes 3 and 4 were converted, respectively, to 7 and 8 on refluxing in LG CHCl3 via the respective unstable complex 5 and 6. The DFT calculated change in internal energy (Delta E) for the reactions 2[(VO)-O-V(L-2)(OCH3)] + 2H(2)O -> 2[(VO)-O-V(L-2)(OH)] + 2CH(3)OH and 2[(VO)-O-V (L-2)(OH)] -> [(V2O3)-O-V(L-2)(2)] + H2O was, respectively, +3.61 and -7.42 kcal mol(-1), suggesting that the [(VO)-O-V(L-2) (OH)] species was unstable and readily transformed to the stable [(V2O3)-O-V(L-2)(2)] complex. Upon one-electron reduction at an appropriate potential, each of 7 and 8 generated mixed-valence [(L) (VO)-O-V-(mu-O)-OVIV(L)]species, which showed valence-delocalisation at room temperature and localisation at 77 K. Some of the complexes showed a wide range of toxicity in a dose-dependent manner against lung cancer cells comparable with that observed with cis-platin.
Keywords: Effective Core Potentials; Lung-cancer cells; Molecular-Orbital Methods; Non-oxido vanadium(iv); Non-Oxo; Oxovanadium(iv) Complexes; Tridentate ono ligand; Ray crystal-structure; Trigonal-prismatic Co-ordination; V-IV complex

Exploring the role of GS-GOGAT cycle in microcystin synthesis and regulation - a model based analysis - Banerjee, Swarnendu; Subramanian, Abhishek; Chattopadhyay, Joydev; Sarkar, Ram Rup (Molecular Biosystems, 2017)
Toxic cyanobacteria blooms populate water bodies by consuming external nutrients and releasing cyanotoxins that are detrimental for other aquatic species, producing a significant impact on the plankton ecosystem and food web. To exercise population-level control of toxin production, understanding the biochemical mechanisms that explain cyanotoxin regulation within a bacterial cell is of utmost importance. In this study, we explore the mechanistic events to investigate the dependence of toxin microcystin on external nitrogen, a known regulator of the toxin, and for the first time, propose a kinetic model that analyzes the intracellular conditions required to ensure nitrogen dependence on microcystin. We hypothesize that the GS-GOGAT cycle is manipulated by variable influx of different intracellular metabolites that can either disturb or promote the balance between the enzyme microcystin synthetase and substrate glutamate to produce variable microcystin levels. As opposed to the popular notion that nitrogen starvation increases microcystin synthesis, our analyses suggest that under certain intracellular metabolite regimes, this relationship can either be completely lost or reversed. External nitrogen can only complement the conditions fixed by intracellular glutamate, glutamine and 2-oxoglutarate. This mechanistic understanding can provide an experimentally testable hypothesis for exploring the less-known biology of microcystin synthesis and designing specific interventions.

Facile synthesis and self-cleaning application of bimetallic (CuSn, CuNi) dendrites - Biswas, Anupam; Kulkarni, Mayuresh A.; Bakthavatsalam, Rangarajan; Mondal, Sourik K.; Dwivedi, Pravin K.; Shelke, Manjusha V.; Devi, Radhamonyamma N.; Banpurkar, Arun G.; Kundu, Janardan (Chemistryselect, 2017)
Bimetallic dendrites (Au, Ag, Pt, Pd) have received intense research interest due to their applications in catalysis and sensing. However, reports on rational synthesis of non-noble bimetallic dendrites that finds self-cleaning applications are scanty. Here, we demonstrate one step co-reduction based galvanic replacement reaction (GRR) for synthesis of alloyed bimetallic dendrites (CuSn, CuNi) with controlled surface roughness and chemical composition. Probing their growth process reveals that i) for CuSn dendrites, co-reduction of Cu2+ and Sn2+ is observed throughout GRR; ii) for CuNi dendrites, Cu nanoparticle, that deposits initially, augments the reduction of Ni2+ which leads to CuNi alloy phase formation during later stages of GRR. These dendrites, naturally having dual degree of surface roughness (micro/nano), have been exploited here for fabricating superhydrophobic surfaces (SHS) with excellent self-cleaning abilities. They show enabling properties such as high contact angle, minimal contact angle hysteresis, and excellent Cassie state stability with no impalement. They maintain superhydrophobicity when exposed to different environmental conditions (low temperature, high temperature, exposure to corroding solutions and UV radiation). The present facile methodology for fabrication of bimetallic dendrites is beneficial for low-cost production of functional nano/micro-materials.

Facile synthesis of Al2O3-Pt nanocomposite and its catalytic activity - Das, Subhasis; Bordoloi, Ankur; Ghosalya, Manoj Kumar; Gopinath, Chinnakonda S.; Bala, Tanushree (Materials Research Express, 2017)
Pt nanoparticles were synthesized on gamma-alumina support in presence of oleic acid which was found to prevent clustering of Pt nanoparticles on the support. Various percentage of Pt loading on the alumina changed the catalytic activity for preferential oxidation of CO at relatively low temperature in H-2 rich stream. Pt nanoparticles when synthesized in absence of oleic acid, were all clustered and did not have any catalytic activity. The presence of oleic acid promoted stability preventing agglomeration of Pt nanoparticles. The catalyst thus prepared was characterized thoroughly and their catalytic activity was studied in details.

Facile synthesis of N-acyl 2-aminobenzothiazoles by NHC-catalyzed direct oxidative amidation of aldehydes - Premaletha, Sethulekshmi; Ghosh, Arghya; Joseph, Sumi; Reddy, Santhi Vardhan; Biju, Akkattu T. (Chemical Communications, 2017)
A mild, general, and high yielding synthesis of N-acyl 2-aminobenzothiazoles has been demonstrated by N-heterocyclic carbene (NHC)-organocatalyzed direct amidation of aldehydes with 2-aminobenzothiazoles proceeding via acyl azolium intermediates. The carbene generated from the triazolium salt under oxidative conditions was the key for the success of this reaction. The method was subsequently applied to the synthesis of various biologically important N-acyl 2-aminobenzothiazoles.

Facile synthesis of ZnO-Ag nanocomposite and its photocatalytic activity - Sardar, Debasmita; Maity, Jayeta; Ghosalya, Manoj Kumar; Gopinath, Chinnakonda S.; Bala, Tanushree (Materials Research Express, 2017)
The evolution of photoactive hybrid materials (e.g. noble metal-semiconductor) has resulted in heterogeneous photocatalysis. We report a facile route for the synthesis of ZnO-Ag nanocomposites with varying percentage of loading of the noble metal, expecting a great boost in the photocatalytic behavior of ZnO. The as prepared material was thoroughly characterized by UV-Vis, FTIR, TEM, FESEM, XRD, XPS analyses. The photocatalytic activities of the nanocomposites have been assessed from the ability to degrade methylene blue dye in aqueous solution. The results suggest that incorporation of Ag nanoparticles on the surface of ZnO particles can enhance catalytic activity in comparison to pure ZnO particles under visible light by minimizing the recombination of photogenerated electron-hole pairs.

Fault detection and analysis of Kapton film in fuel cells using image processing - Firdous, R.; Aherrao, S.; Narute, B.; Borkar, V. (International Conference on Computing, Analytics and Security Trends, CAST 2016, 2017)
Fuel cell is one of the best alternatives of fossil energy in the modern scenario. But still there are some shortcomings such as durability and reliability, which block the wide application of fuel cells. To overcome these barriers, fault diagnosis is an efficient solution. This paper proposes a method for finding dimensional accuracies in Kapton films in membrane electrode assemblies (MEA) of fuel cells using image processing tools for offline fault analysis. © 2016 IEEE.
Keywords: Dimensional accuracy; Fault analysis; fault detection; Fossil energy; fuel cell; Gas fuel purification; image analysis; Image processing; Image processing tools; Kapton films; Membrane electrode assemblies; Offline; polyimides

Fickian yet non-Gaussian behaviour: A dominant role of the intermittent dynamics - Acharya, Sayantan; Nandi, Ujjwal Kumar; Bhattacharyya, Sarika Maitra (Journal Of Chemical Physics, 2017)
We present a study of the dynamics of small solute particles in a solvent medium where the solute is much smaller in size, mimicking the diffusion of small particles in crowded environment. The solute exhibits Fickian diffusion arising from non-Gaussian Van Hove correlation function. Our study shows that there are at least two possible origins of this non-Gaussian behaviour: the decoupling of the solute-solvent dynamics and the intermittency in the solute motion, the latter playing a dominant role. In the former scenario when averaged over time long enough to explore different solvent environments, the dynamics recovers the Gaussian nature. In the case of intermittent dynamics the non-Gaussianity remains even after long averaging and the Gaussian behaviour is obtained at a much longer time. Our study further shows that only for an intermediate attractive solute-solvent interaction the dynamics of the solute is intermittent. The intermittency disappears for weaker or stronger attractions. Published by AIP Publishing.

Flexible epoxy novolac coatings: use of cardanol-based flexibilizers - Gour, Rajeshwari S.; Raut, Kundalik G.; Badiger, Manohar V. (Journal of Applied Polymer Science, 2017)
Flexible epoxy novolac coatings were developed by reacting an epoxy novolac resin, Poly[(phenylglycidyl ether)-co-formaldehyde] (PPGEF) with an amine curing agent, 4,4′-diamino-3,3′-dimethyldicyclohexyl methane (BMCHA), cardanol based reactive diluent (Cardolite NC-513) and two different cardanol-based flexibilizers (Cardolite NC-514 and Cardolite NC-547). The flexibilizer content was varied from 5 to 10% by weight of the resin. These resins were coated onto the stainless steel panels and tested for their gloss, cross-hatch adhesion, falling weight impact resistance, flexibility, abrasion, scratch hardness, solvent scrub resistance, and chemical resistance. The thermo-mechanical properties of these coatings were determined by TGA, DSC, DMTA, and tensile strength measurements. The cryofractured specimens were subjected to SEM analysis. The influence of structural differences of two flexibilizers on the coating properties was investigated. These coatings exhibited excellent properties and have great potential in industrial applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44920.

From lignocellulosic biomass to furfural: insight into the active species of a silica-supported tungsten oxide catalyst - Bhaumik, Prasenjit; Dhepe, Paresh Laxmikant (ChemCatChem, 2017)
A sol–gel-synthesized silica-supported tungsten oxide catalyst that has Lewis acidity was characterized and employed as a solid acid catalyst in the synthesis of furfural directly from lignocellulosic biomass (isolated xylans and crop wastes). In a one-pot method, 71 % furfural formation from isolated xylan was possible using a water/toluene (1:2 v/v) biphasic solvent system at 170 °C after 10 h over 10 wt % WO3/SiO2. The WO3/SiO2 catalyst in the selective conversion of pentosan from crop wastes (bagasse, wheat straw, and rice husk) yielded 72–87 % furfural under the optimum reaction conditions. Additionally, the catalyst presented excellent recyclability in at least eight runs after simple water washing. From the catalyst characterization studies, it was suggested that silicotungstic-type acid species are anchored on the WO3/SiO2 catalyst that help to achieve a good catalytic activity.

G - C3N4 (2D)/CdS (1D)/rGO (2D) dual-interface nano-composite for excellent and stable visible light photocatalytic hydrogen generation - Tonda, Surendar (International Journal of Hydrogen Energy, 2017)
A 2D/1D/2D dual-interface nano-composite configuration in the form of CdS nanorods sandwiched between g-C3N4 and rGO sheets with intimate interfacial contact is synthesized by a facile wet-chemical method and is shown to exhibit excellent photocatalytic H2 generation under visible-light irradiation. In particular, the optimal g-C3N4/CdS/rGO dual-interface nano-composite shows H2 production rate of ∼4800 μmol h-1 g-1, which is almost 44, 11 and 2.5 times higher than that shown by pure g-C3N4 nanosheets, and the g-C3N4/rGO and g-C3N4/CdS single interface heterostructures, respectively. It is shown that the synergic effects involving the band structure match and close interfacial contact, which can accelerate the separation and transfer of photoinduced charge carriers, and the enhanced visible-light absorption together contribute to the impressive photocatalytic performance and photostability of the g-C3N4/CdS/rGO ternary nano-composite system. Specific advantages of a dual-interface triple-composite system over a single interface case(s) are also brought out.
Keywords: charge transfer; Dual Interface; G - CN; H Generation; Hetero Structure; Nano - Composite

Galvanic replacement-based Cu2O self-templating strategy for the synthesis and application of Cu2O–Ag heterostructures and monometallic (Ag) and bimetallic (Au–Ag) hollow mesocages - Bakthavatsalam, Rangarajan; Kundu, Janardan (Crystengcomm, 2017)
Polyhedral Cu2O microparticles as self-templates have been well-demonstrated for the synthesis of Cu2O–M heterostructures (M = Au, Pd, Pt) and Au nano/mesocages utilizing the galvanic replacement reaction (GRR) strategy. However, reports on GRR-based fabrication of Cu2O–Ag heterostructures and the ensuing Ag mesocages are scanty. There is no report that describes the phenomenon of facet selectivity during the GRR-based deposition of Ag on Cu2O template particles. Here, we have identified the underlying rationale behind the observed difficulty in nucleating Ag nanoparticles on an octahedral Cu2O self-template particle. Utilization of an appropriately chosen surfactant/complexant for the silver precursor helps in demonstrating the successful fabrication of Cu2O–Ag heterostructures (octahedral, cubic) with a tunable loading density of Ag NPs on the Cu2O surfaces. This is achieved using Cu2O template particles that undergo GRR with silver nitrate in the presence of nitric acid, and 5-sulfosalicylic acid as the surfactant (key role players). We provide evidence that supports facet selectivity during the deposition of Ag NPs on Cu2O cuboctahedral particles. Hollow octahedral Ag and Au–Ag bimetallic mesocages are fabricated that have rough surfaces, uniform morphology, and excellent shape retention. The fabricated heterostructures and mesocages act as an excellent SERS substrate. This is the first report on the rational synthesis of octahedral Cu2O–Ag heterostructures and octahedral hollow metallic mesocages utilizing the Cu2O self-templating strategy along with the demonstration of facet selectivity of Ag deposition on Cu2O template particles through GRR. The current approach offers a facile and versatile protocol for the synthesis of Cu2O–metal heterostructures and hollow noble metal mesocages.

Genetically engineered crops: Opportunities, constraints, and food security at a glance of human health, environmental impact, and food quality - Dawkar, V.V.; , Chougale, A.D.,; Barvkar, V., (Genetically Engineered Foods, 2017)
Genetic modification (GM) is an incredible technology and it will be among the top 10 technologies developed in the 20th century. People believe that GM technology will answer the future food demand and enable the world to feed millions of people; however, there are apprehensions about the impact of GM crops on human health, the environment, and food quality. Due to the controversy over GM crops, it is important to think about their economic and social effects. GM plants are likely to have increased nutrient levels, produce pharmaceuticals, and show resistance to disease, cold, and drought, and thus increase food security. Conversely, they may also lead to the emergence of new allergens. When thinking about food quality, these crops have the ability to generate more nutritious varieties, which may be of benefit to malnourished populations. However, with the exception of Golden Rice (which was developed to face vitamin A deficiency) achievements in this field are a long way off. These crops also have the potential to have a positive environmental impact as herbicide-tolerant plants can be cultivated on all types of land; however, this also brings about the possibility of generating herbicide-resistant weeds. Overall, GM crops can increase incomes for farmers and aid in drug production; however, care should be taken before releasing GM crops into the environment because once they are planted there will be no turning back.

Genomic and functional characterization of coleopteran insect-specific alpha-amylase inhibitor gene from amaranthus species - Bhide, Amey J.; Channale, Sonal M.; Yadav, Yashpal; Bhattacharjee, Kabita; Pawar, Pankaj K.; Maheshwari, V. L.; Gupta, Vidya S.; Ramasamy, Sureshkumar; Giri, Ashok P. (Plant Molecular Biology, 2017)
The smallest 32 amino acid alpha-amylase inhibitor from Amaranthus hypochondriacus (AAI) is reported. The complete gene of pre-protein (AhAI) encoding a 26 amino acid (aa) signal peptide followed by the 43 aa region and the previously identified 32 aa peptide was cloned successfully. Three cysteine residues and one disulfide bond conserved within known alpha-amylase inhibitors were present in AhAI. Identical genomic and open reading frame was found to be present in close relatives of A. hypochondriacus namely Amaranthus paniculatus, Achyranthes aspera and Celosia argentea. Interestingly, the 3'UTR of AhAI varied in these species. The highest expression of AhAI was observed in A. hypochondriacus inflorescence; however, it was not detected in the seed. We hypothesized that the inhibitor expressed in leaves and inflorescence might be transported to the seeds. Sub-cellular localization studies clearly indicated the involvement of AhAI signal peptide in extracellular secretion. Full length rAhAI showed differential inhibition against alpha-amylases from human, insects, fungi and bacteria. Particularly, alpha-amylases from Helicoverpa armigera (Lepidoptera) were not inhibited by AhAI while Tribolium castaneum and Callosobruchus chinensis (Coleoptera) alpha-amylases were completely inhibited. Molecular docking of AhAI revealed tighter interactions with active site residues of T. castaneum alpha-amylase compared to C. chinensis alpha-amylase, which could be the rationale behind the disparity in their IC50. Normal growth, development and adult emergence of C. chinensis were hampered after feeding on rAhAI. Altogether, the ability of AhAI to affect the growth of C. chinensis demonstrated its potential as an efficient bio-control agent, especially against stored grain pests.

Glycation inhibitors extend yeast chronological lifespan by reducing advanced glycation end products and by back regulation of proteins involved in mitochondrial respiration - Kazi, Rubina S.; Banarjee, Reema M.; Deshmukh, Arati B.; Patil, Gouri V.; Jagadeeshaprasad, Mashanipalya G.; Kulkarni, Mahesh J. (Journal of Proteomics, 2017)
Advanced Glycation End products (AGEs) are implicated in aging process. Thus, reducing AGEs by using glycation inhibitors may help in attenuating the aging process. In this study using Saccharomyces cerevisiae yeast system, we show that Aminoguanidine (AMG), a well-known glycation inhibitor, decreases the AGE modification of proteins in non-calorie restriction (NR) (2% glucose) and extends chronological lifespan (CLS) similar to that of calorie restriction (CR) condition (0.5% glucose). Proteomic analysis revealed that AMG back regulates the expression of differentially expressed proteins especially those involved in mitochondrial respiration in NR condition, suggesting that it switches metabolism from fermentation to respiration, mimicking CR. AMG induced back regulation of differentially expressed proteins could be possibly due to its chemical effect or indirectly by glycation inhibition. To delineate this, Metformin (MET), a structural analog of AMG and a mild glycation inhibitor and Hydralazine (HYD), another potent glycation inhibitor but not structural analog of AMG were used. HYD was more effective than MET in mimicking AMG suggesting that glycation inhibition was responsible for restoration of differentially expressed proteins. Thus glycation inhibitors particularly AMG, HYD and MET extend yeast CLS by reducing AGEs, modulating the expression of proteins involved in mitochondrial respiration and possibly by scavenging glucose. Significance: This study reports the role of glycation in aging process. In the non-caloric restriction condition, carbohydrates such as glucose promote protein glycation and reduce CLS. While, the inhibitors of glycation such as AMC, HYD, MET mimic the caloric restriction condition by back regulating deregulated proteins involved in mitochondria( respiration which could facilitate shift of metabolism from fermentation to respiration and extend yeast CLS. These findings suggest that glycation inhibitors can be potential molecules that can be used in management of aging. (C) 2017 Elsevier B.V. All rights reserved.

Glycoprotein alpha-amylase inhibitor from Withania somnifera differentially inhibits various alpha-amylases and affects the growth and development of Tribolium castaneum - Kasar, Sainath S.; Marathe, Kiran R.; Bhide, Amey J.; Herwade, Abhijeet P.; Giri, Ashok P.; Maheshwari, Vijay L.; Pawar, Pankaj K. (PEST Management Science, 2017)
BACKGROUND: Identification and characterisation of plant defensive molecules enrich our resources to design crop protection strategies. In particular, plant-derived proteinaceous inhibitor(s) of insect digestive enzymes appear to be a safe, sustainable and attractive option. RESULTS: A glycoprotein having non-competitive alpha-amylase inhibitory activity with a molecular weight of 8.3 kDa was isolated and purified from seeds of Withania somnifera alpha-amylase inhibitor (WSAI). Its mass spectrometry analysis revealed 59% sequence coverage with Wrightide II-type alpha-amylase inhibitor from Wrightia religiosa. A dose-dependent inhibition of alpha-amylases from Aspergillus oryzae, Bacillus subtilis, Helicoverpa armigera and Tribolium castaneumwas recorded. Interestingly, WSAI did not inhibit human salivary alpha-amylase significantly. When adults of T. castaneum were fed with WSAI (1.6mg g(-1)), decrease inconsumption, growthandefficiency of conversion of ingested foodwas evident, along withover fourfold increases in feedingdeterrence index. Adecline inlarval residual alpha-amylase activity after feedingofWSAI resulted ina reduction in longevity of T. castaneum. CONCLUSION: The study reflects the significance of WSAI in affecting the overall growth and development of T. castaneum. Pre-and post-harvest pest resistive capability makes WSAI a potential candidate for insect pest management. Further, the effectiveness of this inhibitor could be explored either in formulations or through a transgenic approach. (C) 2016 Society of Chemical Industry

Helical preorganization of molecules drives solid-state intermolecular acyl-transfer reactivity in crystals: structures and reactivity studies of solvates of racemic 2,6-Di-O-(4-fluorobenzoyl)-myo-inositol 1,3,5-orthoformate - Krishnaswamy, Shobhana; Shashidhar, Mysore S.; Bhadbhade, Mohan M. (Crystal Growth & Design, 2017)
Racemic 2,6-di-O-(4-fluorobenzoyl)-myo-inositol 1,3,5-orthoformate yielded structurally dissimilar solvent-free and solvated crystals depending upon the solvent of crystallization. The solvated crystals exhibited helical assembly of host molecules, due to the interaction of the guest molecules with the orthoformate moiety of the host. Some of the solvates showed specific but incomplete benzoyl group transfer reactivity below the phase transition temperature, whereas the reaction in solvent-free crystals led to a mixture of several products. These results reveal the necessity of helical molecular packing of the reacting molecules in their crystals to facilitate specific intermolecular acyl transfer reactivity. The crystal, structures of the fluorobenzoate solvates were similar to those of the solvates of the analogous chloro and bromobenzoates. The latter could be thermally :transformed into their solvent-free form via melt crystallization, resulting in the conversion of a helical molecular packing into a nonhelical molecular packing.

Heteroatom facilitated preparation of electrodes for sodium ion batteries - Bhosale, Manik E.; Banerjee, Abhik; Krishnamoorthy, Kothandam (RSC Advances, 2017)
A conjugated polymer comprising heterocycles was prepared and carbonized to obtain carbon with interlayer spacings between 0.42 and 0.37 nm and exhibited a specific capacity of 250 mA h g(-1).

High quality hybrid perovskite semiconductor thin films with remarkably enhanced luminescence and defect suppression via quaternary alkyl ammonium salt based treatment - Naphade, Rounak A.; Zhao, Baodan; Richter, Johannes M.; Booker, Edward; Krishnamurthy, Shrreya; Friend, Richard H.; Sadhanala, Aditya; Ogale, Satishchandra B. (Advanced Materials Interfaces, 2017)
Significant enhancement in the luminescence and superior photophysical properties of CH3NH3PbBr3 thin films prepared via simple single step spin coating process involving a novel additive mediated solvent extraction step is reported. This process results in significantly lower disorder in CH3NH3PbBr3 perovskites with Urbach energies reducing from ≈35 to ≈17 meV, which is the lowest reported value to date. The additive mediated process also results in a remarkable improvement in the photoluminescence quantum yields (PLQYs) from 1% to 30%. Coupled with the overall increase in surface roughness, a significant increase in the internal PLQY from 7% to 77% is estimated, indicating the superior quality of the treated thin films. The resultant high quality CH3NH3PbBr3 perovskites with remarkable photophysical properties can be used in realizing highly efficient optoelectronic devices. Highly efficient light emitting diodes using these perovskites are demonstrated here.

High-level supercapacitive performance of chemically reduced graphene oxide - Jha, Plawan Kumar; Singh, Santosh Kumar; Kumar, Vikash; Rana, Shammi; Kurungot, Sreekumar; Ballav, Nirmalya (Chem, 2017)
Reduction of graphene oxide (GO) is an important process because it holds promise for the production of reduced graphene oxide (rGO) with physicochemical properties similar to those of pristine graphene. In conventional chemical reduction, strong reducing agents, such as sodium borohydride and hydrazine, cannot be recycled. Also, fast reaction kinetics bring an imbalance in the desirable properties of rGO. Here, we present one-pot chemical reduction of GO in aqueous medium by an unconventional mild reducing agent (FeCl2/HCl) where rGOis isolated as the precipitate and the reducing agent is recycled upon simple treatment of the filtrate with HCl. The fabricated all-solid-state supercapacitors of as-synthesized rGO exhibited significantly higher specific capacitance than those obtained with rGO derived from conventional reducing agents. The cycling stability of the all-solid-state supercapacitor (> 80% retention of capacitance beyond 100,000 continued cycles) and its flexibility (> 500 bending cycles) were remarkable. Use of commercially available organic electrolyte further boosted the supercapacitor performance.

High-throughput mass spectrometry analysis revealed a role for glucosamine in potentiating recovery following desiccation stress in chironomus - Thorat, Leena; Oulkar, Dasharath; Banerjee, Kaushik; Gaikwad, Sushama M.; Nath, Bimalendu B. (Scientific Reports, 2017)
Desiccation tolerance is an essential survival trait, especially in tropical aquatic organisms that are vulnerable to severe challenges posed by hydroperiodicity patterns in their habitats, characterized by dehydration-rehydration cycles. Here, we report a novel role for glucosamine as a desiccation stress-responsive metabolite in the underexplored tropical aquatic midge, Chironomus ramosus. Using high-throughput liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF-MS) analysis, biochemical assays and gene expression studies, we confirmed that glucosamine was essential during the recovery phase in C. ramosus larvae. Additionally, we demonstrated that trehalose, a known stress-protectant was crucial during desiccation but did not offer any advantage to the larvae during recovery. Based on our findings, we emphasise on the collaborative interplay of glucosamine and trehalose in conferring overall resilience to desiccation stress and propose the involvement of the trehalose-chitin metabolic interface in insects as one of the stress-management strategies to potentiate recovery post desiccation through recruitment of glucosamine.

Hyaluronic acid layered chimeric nanoparticles: targeting MAPK-P13K signaling hub in colon cancer cells - Palvai, Sandeep; Kuman, Meenu Mahesh; Sengupta, Poulonu; Basu, Sudipta (ACS Omega, 2017)
Colon cancer has emerged as one of the most devastating diseases in the whole world. Mitogen-activated protein kinase (MAPK)-phosphatidylinsitol-3-kinase (PI3K) signaling hub has gained lots of attention due to its deregulation in colon cancer cells. However, selective targeting of oncogenic MAPK-PI3K hub in colon cancer has remained highly challenging, hence it has mostly been unexplored. To address this, we have engineered a hyaluronic acid layered lipid-based chimeric nanoparticle (HA-CNP) consisting of AZD6244 (MAPK inhibitor), PI103 (PI3K inhibitor), and cisplatin (DNA impairing drug) ratiometrically in a single particle. Electron microscopy (field emission scanning electron microscopy and atomic force microscopy) and dynamic light scattering were utilized to characterize the size, shape, morphology, and surface charge of the HA-CNPs. Fluorescent confocal laser scanning microscopy and flow cytometry analysis confirmed that HA-CNPs were taken up by HCT-116 colon cancer cells by merging of clathrin and CD44 receptor-mediated endocytosis along with macropinocytosis to home into acidic organelles (lysosomes) within 1 h. A gel electrophoresis study evidently established that HA-CNPs simultaneously inhibited MAPK-PI3K signaling hub with DNA damage in HCT-116 cells. These HA-CNPs stalled the cell cycle into G0/G1 phase, leading to induction of apoptosis (early and late) in colon cancer cells. Finally, these HA-CNPs exerted remarkable cytotoxicity in HCT-116 colon cancer cells at 24 h compared to that of the free triple drug cocktail as well as HA-coated dual drug-loaded nanoparticles without showing any cell death in healthy L929 fibroblast cells. These HA-coated CNPs have potential to be translated into clinics as a novel platform to perturb various oncogenic signaling hubs concomitantly toward next-generation targeted colon cancer therapy.

Hybrids of thienopyrimidinones and thiouracils as anti-tubercular agents: SAR and docking studies - Pisal, Mahesh M.; Nawale, Laxman U.; Patil, Manoj; Bhansali, Sujit G.; Gajbhiye, Jayant M.; Sarkar, Dhiman; Chavan, Subhash P.; Borate, Hanumant B. (European Journal of Medicinal Chemistry, 2017)
A number of hybrid molecules containing thienopyrimidinones and thiouracil moieties were designed, synthesized and tested against Mycobacterium tuberculosis H37Ra wherein it was observed that the compounds 11-1514 exhibited antitubercular activity in vitro (MIC 7.6–19.1 μg/ml, 12–35 μM) against dormant stage while compound 15 exhibited antitubercular activity in vitro against dormant (MIC 23.4 μg/ml, 41 μM) as well as active (MIC 25.4 μg/ml, 45 μM) stage. Structural modifications of compound 15 were carried out to study the structure-activity relationship and it was observed that compound 18 exhibited antitubercular activity comparable to compound 15. Cytotoxicity studies revealed that these molecules were non-toxic. The docking study of compound 15 showed that there was binding with the active site of mycobacterial pantothenate synthetase. Further docking studies led to the synthesis of the compounds 16 and 17 and the antitubercular activity screening results showed that these compounds have significant antitubercular activity. The compounds 15-18 (MIC 11–29 μg/ml, 19–51 μM) can be used as starting points for further optimization. The synthetic strategies used in the present work have potential to prepare a large number of compounds for further refinement of structures and the present results will be very useful in the development of a new class of antimycobacterial agents.

Hydrogenolysis of sorbitol over Ni, Pt and Ru supported on SBA-15 - Banu, M.; Sankaranarayanan, T. M.; Venuvanalingam, P.; Magesh, G.; Sivasanker, S. (Indian Journal of Chemistry. Section A: Inorganic, Physical, Theoretical & Analytical Chemistry, 2017)
Hydrogenolysis of sorbitol (15% aqueous solution) has been carried out in a batch reactor over Ni (6 wt%), Pt (1 wt%) and Ru (1 wt%) supported on SBA-15 and carbon coated SBA-15 (SBA-15(C)). For comparison, the three metals have also been supported on activated carbon (AC). The catalysts are characterized by XRD, N-2 and H-2 adsorption measurements. Addition of Ca(OH)(2) to the reaction mixture increases conversion and selectivity for the dihydroxy compounds, 1,2-propanediol (PD) and ethylene glycol (EG). Based on yield of dihydric alcohols (PD+EG), the performance of the catalysts at 220 degrees C and 60 bar in the presence of Ca(OH)(2) is in the order: Ru-AC similar to Ru-SBA-15(C) > Ru-SBA-15 similar to Ni-SBA-15, the yields being 40, 39, 31 and 29 wt%, respectively.

Identification of new anti-inflammatory agents based on nitrosporeusine natural products of marine origin - Philkhana, Satish Chandra; Verma, Abhishek Kumar; Jachak, Gorakhnath R.; Hazra, Bibhabasu; Basu, Anirban; Reddy, D. Srinivasa (European Journal of Medicinal Chemistry, 2017)
Nitrosporeusines A and B are two recently isolated marine natural products with novel skeleton and exceptional biological profile. Interesting antiviral activity of nitrosporeusines and promising potential in curing various diseases, evident from positive data from various animal models, led us to investigate their anti-inflammatory potential. Accordingly, we planned and synthesized nitrosporeusines A and B in racemic as well as enantiopure forms. The natural product synthesis was followed by preparation of several analogues, and all the synthesized compounds were evaluated for in vitro and in vivo anti-inflammatory potential. Among them, compounds 25, 29 and 40 significantly reduced levels of nitric oxide (NO), reactive oxygen species (ROS) and pro-inflammatory cytokines. In addition, these compounds suppressed several pro-inflammatory mediators including inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2), nuclear factor-kappa B (NF -kappa B), and thereby can be emerged as potent anti-inflammatory compounds. Furthermore, all possible isomers of lead compound 25 were synthesized, characterized and profiled in same set of assays and found that one of the enantiomer (-)-25a was superior among them. (C) 2017 Elsevier Masson SAS. All rights reserved.

Implementation of QbD for development of a downstream process for a therapeutic biosimilar - Rathore, Anurag; Bhambure, Rahul (253rd National Meeting of the American-Chemical-Society (ACS) on Advanced Materials, Technologies, Systems, and Processes, 2017)

Improved tolerance against helicoverpa armigera in transgenic tomato over-expressing multi-domain proteinase inhibitor gene from capsicum annuum - Tanpure, Rahul S.; Barbole, Ranjit S.; Dawkar, Vishal V.; Waichal, Yashashree A.; Joshi, Rakesh S.; Giri, Ashok P.; Gupta, Vidya S. (Physiology and Molecular Biology of Plants, 2017)
Plant proteinase inhibitors (PIs) are plant defense proteins and considered as potential candidates for engineering plant resistances against herbivores. Capsicum annuum proteinase inhibitor (CanPI7) is a multi-domain potato type II inhibitor (Pin-II) containing four inhibitory repeat domains (IRD), which target major classes of digestive enzymes in the gut of Helicoverpa armigera larvae. Stable integration and expression of the transgene in T1 transgenic generation, were confirmed by established molecular techniques. Protein extract of transgenic tomato lines showed increased inhibitory activity against H. armigera gut proteinases, supporting those domains of CanPI7 protein to be effective and active. When T1 generation plants were analyzed, they exhibited antibiosis effect against first instar larvae of H. armigera. Further, larvae fed on transgenic tomato leaves showed delayed growth relative to larvae fed on control plants, but did not change mortality rates significantly. Thus, better crop protection can be achieved in transgenic tomato by overexpression of multi-domain proteinase inhibitor CanPI7 gene against H. armigera larvae.

In situ grown nickel nanoparticles in a calixarene nanoreactor on a graphene-MoS2 support for efficient water electrolysis - Waghmode, Babasaheb J.; Bhange, Siddheshwar N.; Unni, SreeKuttan M.; Patil, Kashinath R.; Malkhede, Dipalee D. (Sustainable Energy & Fuels, 2017)
Electrochemical production of hydrogen, facilitated in electrolysers, holds great promise for energy storage and solar fuel production. Catalysis of the oxygen evolution reaction (OER) is a bottleneck of this process. However, the sluggish OER kinetics and the utilization of precious metal catalysts are key obstacles in the broad deployment of this energy technology. We report the preparation and use of an inexpensive GrMoS(2)SC(8)Ni nanocomposite material as a highly effective OER catalyst in an alkaline electrolyte. Experimental investigations have shown that improvements can be realized in the catalytic performance of Ni metal if it is a component of the composite material. We propose an explanation for these enhancements based on a hydrogen acceptor concept. This concept comprises the stabilization of an *-OOH intermediate, which effectively lowers the potential needed for breaking bonds on the surface. Herein, an inexpensive immobilized SC8 layer was used as the nanoreactor to synthesize metallic Ni nanoparticles (NPs) through an in situ redox process. The process was applied to form immobilized NPs on flat and curved 2D surfaces. The outstanding OER performance of Ni NPs could be attributed to their large surface area, efficient mass and charge transport, and high structural stability arising from the unique SC8 cage structure, built on the GrMoS(2) substrate. The GrMoS(2)SC(8)Ni nanocomposite shows the highest activity, exhibiting a 214 mV overpotential at 10 mA cm(-2) (equivalent to 10% efficiency of solarto-fuel conversion) and a Tafel slope of 31 mV dec(-1) in 1 M KOH solution. It further demonstrates high stability as there is no apparent OER activity loss (based on a chronoamperometry test) or particle aggregation (based on SEM image observation) after a 10 h anodization test. The facile preparation method and high efficiency and durability enable this electrocatalyst to be a promising candidate for future large-scale applications in water splitting. Thus, this work opens a new avenue toward the development of highly efficient, inexpensive OER catalysts.

Interaction energy driven biased sampling technique: a faster route to ionization spectra in condensed phase - Bose, Samik; Ghosh, Debashree (Journal of Computational Chemistry, 2017)
We introduce a computationally efficient approach for calculating spectroscopic properties, such as ionization energies (IEs) in the condensed phase. Discrete quantum mechanical/molecular mechanical (QM/MM) approaches for spectroscopic properties in a dynamic system, such as aqueous solution, need a large sample space to obtain converged estimates, especially for the cases where particle (electron) number is not conserved, such as IEs or electron affinities (EAs). We devise a biased sampling technique based on an approximate estimate of interaction energy between the solute and solvent, that accelerates the convergence and therefore, reduces the computational cost significantly. The approximate interaction energy also provides a good measure of the spectral width of the chromophores in the condensed phase. This technique has been tested and benchmarked for (i) phenol, (ii) HBDI anion (hydroxybenzylidene dimethyl imidazolinone), and (iii) thymine in water. (c) 2017 Wiley Periodicals, Inc.

Interplaying anions in a supramolecular metallohydrogel to form metal organic frameworks - Karak, Suvendu; Kumar, Sushil; Bera, Saibal; Diaz Diaz, David; Banerjee, Subhrashis; Vanka, Kumar; Banerjee, Rahul (Chemical Communications, 2017)
The remarkable effect of anions on the transition from supramolecular gels to crystalline phases has been described. An amino acid-based metallohydrogel was transformed into different metal-organic frameworks through the selective picking of anions. The metallohydrogel and the resulting metal-organic frameworks (MOFs) were thoroughly characterized. The results demonstrated controlled access over the binding of a particular anion to selectively form a particular MOF.

Intramolecular ipso-arylative cyclization of aryl-alkynoates and N-arylpropiolamides with aryldiazonium salts through merged gold/visible light photoredox catalysis - Bansode, Avinash H.; Shaikh, Samir R.; Gonnade, Rajesh G.; Patil, Nitin T. (Chemical Communications, 2017)
A visible-light-promoted merged gold/photoredox catalyzed ipsoarylative cyclization has been reported. For instance, the reaction of aryl-alkynoates and N-arylpropiolamides with aryldiazonium salts in the presence of catalytic amounts of [(4-OCH3)C6H4](3)PAuCl and Ru(bpy)(3)(PF6)(2) under irradiation using a 32WCFL bulb gave arylated spirocarbocycles in moderate to good yields.

Introducing the bipolar solvent media using the aqueous mixtures of amino acid anion-based ionic liquids - Beniwal, Vijay; Kumar, Anil (Journal of Physical Chemistry B, 2017)
To carry out a chemical reaction between the reactants with largely different polarities, it becomes important to have a reaction medium that possesses both the polar and nonpolar solvation environments. In an attempt to explore the reaction media with such unique polarity properties, the present study provides a thorough understanding of the bipolar solvent media using the aqueous mixtures of amino acid anion-based ionic liquids. The highly polar behavior of the binary mixtures used in the study has been ascribed to the pure ionic liquid state. However, the less polar solvation shells have been attributed to the presence of a neutral form of the anions. Addition of water in the amino acid anion-based ionic liquids causes the protonation of a certain fraction of the anions of the ionic liquids, resulting into the formation of a less polar nonionic protonated form along with the highly polar natural anionic form. This results into the formation of two solvation spheres with different polarities, which can be seen very clearly from the presence of two absorption bands (lower wavelength absorption band and higher wavelength absorption band) in the UV-vis absorption spectrum of Reichardt's E-T(30) dye and two emission bands (lower wavelength emission band and higher wavelength emission band) in the fluorescence emission spectrum of C481 dye. The values of the E-T(N) polarity parameter corresponding to the two solvation shells having different polarities have been calculated from the deconvoluted absorption spectra of the Reichardt's E-T(30) and were analyzed in three amino acid anion-based ionic liquids. Generation of the neutral form of anions in the aqueous mixtures formed via a protonation transfer reaction has been confirmed by the H-1 NMR spectroscopy and UV-vis absorption spectrum of 18DHAQ dye. The study also establishes that the Reichardt's E-T(30) dye can be used as a valid polarity probe to study the solvatochromic behavior of the binary mixtures of amino acid-based ionic liquids.

Iron-based nanocatalyst for the acceptorless dehydrogenation reactions - Jaiswal, Garima; Landge, Vinod G.; Jagadeesan, Dinesh; Balaraman, Ekambaram (Nature Communications, 2017)
Development of sustainable catalytic systems for fundamentally important synthetic transformations and energy storage applications is an intellectually stimulating challenge. Catalytic dehydrogenation of feedstock chemicals, such as alcohols and amines to value-added products with the concomitant generation of dihydrogen is of much interest in the context of hydrogen economy and is an effective alternative to the classical oxidation reactions. Despite a number of homogeneous catalysts being identified for the acceptorless dehydrogenation, the use of high price and limited availability of precious metals and poor recovery of the catalyst have spurred interest in catalysis with more earth-abundant alternatives, especially iron. However, no report has described a reusable iron-based heterogeneous catalyst for oxidant-free and acceptorless dehydrogenation reactions. Here we replace expensive noble metal catalysts with an inexpensive, benign, and sustainable nanoscale iron catalyst for the efficient acceptorless dehydrogenation of N-heterocycles and alcohols with liberation of hydrogen gas.

Iron-catalyzed dehydrogenation reactions and their applications in sustainable energy and catalysis - Balaraman, Ekambaram; Nandakumar, Avanashiappan; Jaiswal, Garima; Sahoo, Manoj K. (Catalysis Science & Technology, 2017)
Inspired by nature, chemists have designed new catalysts in the pursuit of selective bond activation and chemical transformations. Emergent biological systems often use earth-abundant first-row transition elements as catalytically active sites to facilitate specific and highly selective chemical processes. The design of a new catalytic system based on abundant and inexpensive catalysts, particularly the iron-based catalysts, for fundamentally significant synthetic transformations under environmentally benign conditions is an important paradigm in chemical synthesis. In recent times, iron-based catalytic systems have shown unprecedented reactivity in the acceptorless dehydrogenation reactions of feedstock chemicals, with the liberation of molecular hydrogen as the by-product, and have enabled greener chemical synthetic methods and alternative energy storage systems. Indeed, it has been demonstrated that the proper design of iron catalysts by judiciously choosing ligands, can aid in the development of new sustainable energy storage systems and catalysis. This tutorial review focuses on the recent development of iron-based dehydrogenation reactions of fundamentally important feedstock, as a route to sustainable chemical synthesis and energy storage applications. The emerging area of the iron-based dehydrogenation strategy provides an opportunity to make industrially applicable, cost-effective and environmentally benign catalytic systems.

Kinetics and thermodynamics of transpeptidation catalysed by Bacillus subtilis gamma glutamyl transferase - Balakrishna, Sharath; Prabhune, Asmita A. (Indian Journal of Biochemistry and Biophysics, 2017)
Gamma glutamyl transferases (GGT) catalyse the removal (deglutamylation) of the terminal gamma-glutamate residue from compounds such as glutathione and poly-gamma-glutamic acid and its transfer either to a water molecule (hydrolysis) or to a peptide/amino acid (transpeptidation). We analysed the kinetics of Bacillus subtilis GGT (BsGGT) catalysed transpeptidation using gamma-glutamyl-(3-carboxyl)-4-nitroaniline as the gamma-glutamate-donor and glycylglycine (Gly-Gly) as the gamma-glutamate acceptor. Addition of Gly-Gly improved the affinity (Km) of the enzyme for gamma-glutamyl-(3-carboxyl)-4-nitroaniline by nearly 25 times with negligible impact on the rate of deglutamylation (V-max). The asymmetric changes in the kinetic parameters improved the specificity constant (K-cat/K-m.) by about 43 times. BsGGT catalysed transpeptidation was pronounced in conditions that are unfavorable for hydrolysis. Maximum transpeptidation occurred near neutral pH and when the concentration of the gamma-glutamate-donor substrate is lower. The effect of Gly-Gly on the kinetics of BsGGT is contrastingly different from that observed for eukaryotic GGTs. In the case of mammalian GGTs, the addition of Gly-Gly increases both Km and k(cat); and, the specificity constant (K-cat/K-m) remains unaltered

Linking catalyst-coated isotropic colloids into ``active'' flexible chains enhances their diffusivity - Biswas, Bipul; Manna, Raj Kumar; Laskar, Abhrajit; Kumar, P. B. Sunil; Adhikari, Ronojoy; Kumaraswamy, Guruswamy (ACS Nano, 2017)
Active colloids are not constrained by equilibrium: ballistic propulsion, superdiffusive behavior, or enhanced diffusivities have been reported for active Janus particles. At high concentrations, interactions between active colloids give rise to complex emergent behavior. Their collective dynamics result in the formation of several hundred particle-strong flocks or swarms. Here, we demonstrate significant diffusivity enhancement for colloidal objects that neither have a Janus architecture nor are at high concentrations. We employ uniformly catalyst-coated, viz. chemo-mechanically, isotropic colloids and link them into a chain to enforce proximity. Activity arises from hydrodynamic interactions between enchained colloidal beads due to reaction-induced phoretic flows catalyzed by platinum nanoparticles on the colloid surface. This results in diffusivity enhancements of up to 60% for individual chains in dilute solution. Chains with increasing flexibility exhibit higher diffusivities. Simulations accounting for hydrodynamic interactions between enchained colloids due to active phoretic flows accurately capture the experimental diffusivity. These simulations reveal that the enhancement in diffusivity can be attributed to the interplay between chain conformational fluctuations and activity. Our results show that activity can be used to systematically modulate the mobility of soft slender bodies.
Keywords: active matter; Brownian motion; colloidal assembly; diffusivity; ice templating

Ln(8) (Ln = Gd, Ho, Er, Yb) Butterfly core-exhibiting magnetocaloric effect and field-induced SMM behavior for Er analouge - Bala, Sukhen; Adhikary, Amit; Bhattacharya, Sudeshna; Sen Bishwas, Mousumi; Poddar, Pankaj; Mondal, Raju (ChemistrySelect, 2017)
In this article, we report four pyridyl-pyrazolyl based poly-nuclear cluster complexes with Ln(8) {Ln = [Gd-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](DMF)(2)(MeOH)(1), [Ho-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](2), [Er-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](DMF)(MeOH)(H2O)(3), [Yb-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](DMF)(MeOH)(4) [DEA = Diethanolamine] cores. The impetus for this study was to explore the magnetic behaviour of lanthanide ions which are often ignored or overlooked. X-ray crystal analysis show that these complexes are isostructural and exhibit an interesting butterfly like topology. The semi-rigidity and asymmetric nature of the ligand led to different coordination environment around the metal centres. The lanthanide ions adopt two types of geometry, a bicapped trigonal prism and a distorted square antiprismatic geometry around the metal center. Such dissimilar coordination environments around the lanthanide centre can have profound effects on their magnetic behaviour. Indeed, the magnetic measurements revealed significant magnetocaloric effect for octanuclear gadolinium complex 1 with magnetic entropy change (-Delta S-m ) of 31.4 J kg(-1) K-1 for Delta H = 9 T at T = 3 K whereas Er analogue complex 3 displayed SMM behavior.

Low-dimensional hybrid perovskites as high performance anodes for alkali-ion batteries - Tathavadekar, Mukta; Krishnamurthy, Shrreya; Banerjee, Aparna; Nagane, Satyawan; Gawli, Yogesh; Suryawanshi, Anil; Bhat, Suresh; Puthusseri, Dhanya; Mohite, Aditya D.; Ogale, Satishchandra (Journal of Materials Chemistry A, 2017)
State-of-the-art Li (or Na) ion batteries work by insertion/extraction of the alkali metal ions into a porous electrode material, where the overall capacity is strongly dependent on the accessibility of the host material interior to the ions. On the other hand, the performance stability depends on various factors governed by the specific constitution of the electrode. Here we show that molecularly engineered low-dimensional hybrid perovskites can work as excellent anode materials for alkali-ion batteries. We measure a high reversible capacity of 646 mA h g(-1) at 100 mA g(-1) with good stability tested up to 250 cycles for the benzidine mediated lead iodide based 1D system. An ex situ analysis of the electrodes reveals that the storage primarily occurs via the Li-x(or Na-x)Pb alloying/de-alloying process. We anticipate that these results open a new direction for the use of low-dimensional hybrid perovskites for energy storage applications.
Keywords: Generation; Inorganic-Organic Hybrid; Lead Iodide; lithiation-intramolecular electrophilic reaction; Na-Air Battery; Negative Electrodes; Organometal Halide perovskites; PB; Sequential Deposition; Solar-cells

Magnetic reduced graphene oxide loaded hydrogels: highly versatile and efficient adsorbents for dyes and selective Cr(VI) ions removal - Halouane, Fatima; Oz, Yavuz; Meziane, Dalila; Barras, Alexandre; Juraszek, Jean; Singh, Santosh K.; Kurungot, Sreekumar; Shaw, Pankaj K.; Sanyal, Rana; Boukherroub, Rabah; Sanyal, Amitav; Szunerits, Sabine (Journal of Colloid and Interface Science, 2017)
The formation of composites of reduced graphene oxide (rGO) and magnetic nanoparticles (MP) has flourished in recent years as they combine the advantages of both nanomaterials. Most of these composite materials are prepared by in situ formation of MP onto rGO or by the post-adsorption onto rGO. We report here on a simple and highly controlled method for the fabrication of different magnetic 3D rGO-loaded hydrogels. Cellulose bound magnetic nanoparticles (MP@cellulose) were synthesized by chemical co-precipitation and loaded together with rGO into poly(ethylene glycol) dimethacrylate based hydrogels during their fabrication using photo-polymerization. The magnetic rGO-loaded hydrogels proved to be highly adaptable to different applications. The as-formed composites allowed for efficient dye removal with an adsorption capacity of 111.9 +/- 4 mg g(-1) in the case of methylene blue (MB). Integration of poly(ethyleneimine) (PEI) allowed for the selective capturing of Cr6+ ions with an adsorption capacity of 313 12 mg g-1. Most importantly, independent of the application, the magnetic rGO-loaded hydrogel can be regenerated without loss of its adsorption capacity. (C) 2017 Elsevier Inc. All rights reserved.

Magnetoelastic properties of terbium substituted cobalt ferrite - Bhame, Shekhar D.; Joy, Pattayil Alias (Chemical Physics Letters, 2017)
The magnetic properties of terbium substituted cobalt ferrites CoFe(2-x)TbxO(4) (x = 0, 0.05, 0.1, 0.15 and 0.2) prepared by conventional solid state method are studied. The coercivity showed marked increase up to x = 0.1 and saturation magnetization decreased with increasing terbium content. Magnetostriction measurements did not show much decrease in the maximum value of strain but significant increase in the slope of magnetostriction was observed for x = 0.15 with moderate magnetostriction of around 144 ppm. The observed magnetic and magnetostrictive properties can be explained on the basis of structural and microstructural changes arising because of terbium substitution. (C) 2017 Elsevier B.V. All rights reserved.

Mapping of optimum operating condition for LiBr-water refrigeration cycles - Mali, Nilesh A.; Bhagwat, Sunil S. (Sadhana: Academy Proceedings in Engineering Sciences, 2017)
In this work, optimum operating condition maps are generated covering wide ranges of refrigeration and sink temperatures for single-and double-effect LiBr-water vapour absorption refrigeration cycle. These optimum condition maps will be useful to choose optimum operating conditions while designing LiBr-water cycle for desired applications. Methodology for generating such maps is discussed in detail, which can also be used for other absorption refrigeration cycles with various working fluids. Three configurations of LiBr-water absorption refrigeration cycles, single effect, double-effect series flow and double-effect parallel flow, are analysed with the most accurate thermodynamic property correlation available in the literature. Sensitivity of cycle performance to various operating variables such as generator, absorber and condenser temperatures is determined. Second law analysis shows that when a higher temperature heat source is available, double-effect cycles are more effective over single effect as they have higher coefficient of performance.

Mass spectrometry based identification of galectin-3 interacting proteins potentially involved in lung melanoma metastasis - Dange, Manohar C.; Bhonsle, Hemangi S.; Godbole, Rashmi K.; More, Shyam K.; Bane, Sanjay M.; Kulkarni, Mahesh J.; Kalraiya, Rajiv D. (Molecular Biosystems, 2017)
Adhesive interactions between molecules on tumor cells and those on target organs play a key role in organ specific metastasis. Poly-N-acetyl-lactosamine (polyLacNAc) substituted N-oligosaccharides on melanoma cell surface glycoproteins promote lung specific metastasis via galectin-3 by facilitating their arrest and extravasation. This study reports the identification and characterization of galectin-3 interacting proteins using a combination of galectin-3 sepharose affinity and leucoagglutinating phytohemagglutinin (L-PHA) columns. A total of 83 proteins were identified as galectin-3 interacting glycoproteins, of which 35 were constituents of the L-PHA bound fraction, suggesting that these proteins carry polyLacNAc substituted beta 1,6 branched N-glycans. The identities of some of these proteins, like LAMP-1, LAMP-3, basigin, embigin, and alpha 5 and beta 1 Integrin, have been confirmed by western blotting, and functional relevance with respect to metastatic properties has been established.

Metal free mild and selective aldehyde cyanosilylation by a neutral penta-coordinate silicon compound - Swamy, V. S. V. S. N.; Bisai, Milan Kumar; Das, Tamal; Sen, Sakya S. (Chemical Communications, 2017)
This study demonstrates the preparation and structural characterization of a Si(IV) hydride (PhC(NtBu)(2)SiH(CH3)Cl) (1) and its use as a catalyst for the cyanosilylation of a variety of aldehydes. Compound 1 represents the first neutral penta-coordinate silicon(IV) species that catalyzes cyanosilylation of aldehydes under mild conditions.

Metal-free, brønsted acid-catalyzed formal [3+2] annulation of quinone monoacetals with 2-naphthols - Jacob, Anu; Roy, Tony; Kaicharla, Trinadh; Biju, Akkattu T. (Journal of Organic Chemistry, 2017)
An operationally simple and metal-free cross-coupling of quinone monoacetals (QMAs) with 2-naphthols catalyzed by triflic acid is reported. This formal [3+2] annulation allowed the synthesis of diverse naphtho[2,1-b]benzofuranderivatives in moderate to good yields. Preliminary mechanistic studies reveal the initial nucleophilic substitution of QMAs with 2-naphthols in preference to the mixed acetal formation and subsequent [3,3] sigmatropic rearrangement.

Metal-free radical trifluoromethylation of beta-nitroalkenes through visible-light photoredox catalysis - Midya, Siba P.; Rana, Jagannath; Abraham, Thomas; Aswin, Bhaskaran; Balaraman, Ekambaram (Chemical Communications, 2017)
A catalytic method for functional group interconversion is immensely important in modern sciences. Here, we report an efficient catalytic conversion of nitroalkenes to highly stereoselective 1-trifluoromethylalkenes at room temperature. This unprecedented metal-free photocatalytic strategy is simple and operates under visible-light irradiation using the commercially available CF3 source.

Method for the analysis of free carbenes present after NHC-organocatalyzed transformations - Das, Tamal Kanti; Biju, Akkattu T. (European Journal of Organic Chemistry, 2017)
In N-heterocyclic carbene (NHC) based organocatalysis, usually, the free carbene is generated in situ by treatment of the azolium salt with a base. Described herein is a method for the analysis of the NHC present in the reaction flask after the NHC-organocatalyzed reaction. For this, the reaction mixture was treated with elemental sulfur after the reaction and the thus-formed thiourea/thione derivative was isolated. Common NHC-catalyzed transformations such as benzoin reactions, Stetter reactions, homoenolate annulation reactions, and reactions proceeding via the ,-unsaturated acylazolium intermediate have been studied. The results indicate that after the reactions, 28-84% of the initial carbenes exist in the free form.

Methylglyoxal attenuates insulin signaling and downregulates the enzymes involved in cholesterol biosynthesis - Deshmukh, Arati B.; Bai, Shakuntala; Aarthy, T.; Kazi, Rubina S.; Banarjee, Reema; Rathore, Rajeshwari; Vijayakumar, M. V.; H. V. Thulasiram; Bhat, Manoj Kumar; Kulkarni, Mahesh J. (Molecular Biosystems, 2017)
Methylglyoxal (MG) is a highly reactive dicarbonyl known to be elevated under the hyperglycemic conditions of diabetes and is implicated in the development of diabetic complications. Therefore, the current study investigates the role of MG in exacerbating insulin resistance at the insulin signaling level, as well as its effect on the global proteomic level. By using insulin sensitive rat muscle cells (L6) and Chinese hamster ovary (CHO) cells stably expressing the insulin receptor (IR) and a glucose transporter fused with green fluorescent protein (GLUT4-GFP), we have observed that MG impairs insulin signaling, inhibits GLUT4 translocation and reduces glucose uptake. SWATH MS analysis, a label-free quantitative mass spectrometric approach, showed altered expression of 99 proteins out of 2404 identified in response to MG treatment. These proteins are mainly involved in stress response, protein folding and proteolysis. Some of the deregulated proteins such as thioredoxin 2, glutathione S transferase, T complex protein 1 subunit beta (tcbp1), heat shock protein 90 and E3 ubiquitin ligase were previously reported to be associated with either diabetes or insulin resistance. Interestingly, aminoguanidine (AMG), a potent dicarbonyl scavenger, restored the deleterious effects of MG. For the first time, we report that MG induces downregulation of enzymes involved in cholesterol biosynthesis such as acetyl-CoA acetyltransferase, hydroxymethylglutaryl-CoA synthase, farnesyl pyrophosphate synthetase, squalene monooxygenase, and lanosterol synthase. GC MS analysis for sterol metabolites corroborated the proteomic results; MG significantly reduced cholesterol production whereas AMG treatment restored cholesterol production to levels similar to the control. Thus, MG leads to primary defects in insulin signaling and cellular abnormalities at the proteomic and metabolic levels, both of which may contribute to the development of insulin resistance.

Micelles versus Ribbons: how congeners drive the self-assembly of acidic sophorolipid biosurfactants - Dhasaiyan, Prabhu; Griel, Patrick Le; Roelants, Sophie; Redant, Emile; Bogaert, Inge N. A. Van; Prevost, Sylvain Francois; Prasad, Bhagavatula L. V.; Baccile, Niki (ChemPhysChem, 2017)
Sophorolipids (SLs), a class of microbially derived biosurfactants, are reported by different research groups to have different self-assembled structures (either micelles or giant ribbons) under the same conditions. Here we explore the reasons behind these contradictory results and attribute these differences to the role of specific congeners that are present in minute quantities. We show that a sample composed of a majority of oleic acid (C18:1) sophorolipid in the presence of only 0.5 % (or more) of congeners with stearic acid (C18:0) or linoleic acid (C18:2) results in the formation of micelles that are stable over long periods of time. Conversely, the presence of only 10 to 15 % of congeners with a stearic acid chain gives fibrillar structures instead of micelles. To study the mechanisms responsible, oleic acid SLs devoid of any other congeners were prepared. Very interestingly, this sample can self-assemble into either micelles or fibers depending on minute modifications to the self-assembly conditions. The findings are supported by light scattering, small-angle X-ray scattering, transmission electron microscopy under cryogenic conditions, high-pressure liquid chromatography, and NMR spectroscopy.

Microwave-assisted extraction of carvone from carum carvi - Borole, O. D.; Shirsath, S. R.; Gaikwad, S. G. (Novel water treatment and separation methods simulation of chemical processes, 2017)
Due to increasing demand for potable and irrigation water, new scientific research is being conducted to deal with wastewater from a variety of sources. Novel Water Treatment and Separation Methods: Simulation of Chemical Processes presents a selection of research related to applications of chemical processes for wastewater treatment, separation techniques, and modeling and simulation of chemical processes. Among the many topics are: degradation of herbicide removal of anionic dye efficient sun-light driven photocatalysis removal of copper and iron using green activated carbon defluoridation of drinking water removal of calcium and magnesium from wastewater using ion exchange resins degradation of vegetable oil refinery wastewater novel separation techniques, including microwave-assisted extraction and more The volume presents selected examples in wastewater treatment, highlighting some recent examples of processes such as photocatalytic degradation, emulsion liquid membrane, novel photocatalyst for degradation of various pollutants, and adsorption of heavy metals. The book goes on to explore some novel separation techniques, such as microwave-assisted extraction, anhydrous ethanol through molecular sieve dehydration, batch extraction from leaves of Syzygium cumini (known as jambul, jambolan, jamblang or jamun), and reactive extraction. These novel separation techniques have proved be advantageous over conventional methods. The volume also looks at modeling and simulation of chemical processes, including chapters on flow characteristics of novel solid-liquid multistage circulating fluidized bed, mathematical modeling and simulation of gasketed plate heat exchangers, optimization of the adsorption capacity of prepared activated carbon, and modeling of ethanol/water separation by pervaporation, along with topics on simulation using CHEMCAD software.

Mixed-stack charge transfer crystals of pillar[5]quinone and tetrathiafulvalene exhibiting ferroelectric features - Shivakumar, Kilingaru I.; Swathi, Kadaba; Goudappagouda; Das, Tamal C.; Kumar, Ashwani; Makde, Ravindra D.; Vanka, Kumar; Narayan, Kavassery S.; Babu, Sukumaran Santhosh; Sanjayan, Gangadhar J. (Chemistry- A European Journal, 2017)
Ferroelectric materials find extensive applications in the fabrication of compact memory devices and ultra-sensitive multifunctional detectors. Face-to-face alternate stacking of electron donors and acceptors effectuate long-range unidirectional ordering of charge-transfer (CT) dipoles, promising tunable ferroelectricity. Herein we report a new TTF-quinone system-an emerald green CT complex consisting pillar[5]quinone (P5Q) and tetrathiafulvalene (TTF). The CT crystals, as determined by single crystal synchrotron X-ray diffraction, adopt a 1:1 mixed-stack arrangement of donor and acceptor with alternating dimers of TTF and 1,4-dioxane encapsulated P5Q. The TTF-P5Q.dioxane crystal possesses a macroscopic polarization axis giving rise to ferroelectricity at room temperature. The CT complex manifests ferroelectric features such as optical polarization rotation, temperature-dependent phase transition and piezoelectric response in single crystals. Ferroelectric behavior observed in P5Q-based CT complex widens the scope for further work on this structurally intriguing and readily accessible cyclic pentaquinone.
Keywords: Acceptor; Charge-transfer complexes; Chemistry; Conductors; DDQ; Donor; ferroelectric; Macrocycles; Organic Metals; Pi-interaction; Pillar[5]quinone; salts; Transfer Complexes; Transport

Modular assembly of porous organic cage crystals: isoreticular quasiracemates and ternary co-crystal - Tothadi, Srinu; Little, Marc A; Hasell, Tom; Briggs, Michael E.; Chong, Samantha Y.; Liu, Ming; Cooper, Andrew I. (CrystEngComm, 2017)
Small changes in molecular structure and crystallisation conditions can have a profound effect on the crystal packing of molecules. Increasing the system complexity-for example, by introducing multiple components-greatly increases the number of potential outcomes. Hence, the rational design of porous cocrystals with multiple components is challenging. Here, we report a family of isoreticular quasiracemate crystalline phases for porous organic cages, FT-RCC3-R center dot CCX-S (where X = 1, 2, or 4), that were prepared in a modular and predictable fashion. By using directional intermolecular interactions between cages, we were able to prepare a rare ternary co-crystal, (CC3-S(0.5)CC4-S-0.5)center dot(CC13-S(0.5)CC3-S(0.25)CC4-S-0.25).
Keywords: cocrystals; Frameworks; Gas-chromatography; Halogen Bonds; Hydrogen-bonds; Molecular Cage; Nanoparticles; Pores; porosity; Separation

Molecular dynamics simulation and experimental study on the growth of methane hydrate in presence of methanol and sodium chloride - Choudhary, Nilesh; Kushwaha, Omkar Singh; Bhattacharjee, Gaurav; Chakrabarty, Suman; Kumar, Rajnish (Energy Procedia, 2017)
The plugging of processing and transportation lines by gas hydrate formation is a challenging problem for safe exploitation of oil and gas. The existence of water soluble third component (like methanol and sodium chloride) in the aqueous phase influence the gas hydrate formation thermodynamically also possibly affects the kinetics of hydrate growth. Inorganic salt and organic molecule (alcohols) at high concentration in the aqueous phase have been used as thermodynamic inhibitors to effectively prevent the hydrate formation. This study utilizes molecular dynamics as well as an experimental method to investigate the mechanism of the hydrate formation and the effect of additives. The MD simulation showed that at moderate temperature and pressure, a low concentration (1 wt %) of methanol and NaCl enhances methane hydrate growth kinetics. Significant numbers of methanol molecules were observed inside the gas hydrate cages whereas Na⁺/Cl⁻ ions leach out during hydrate formation.

Molecular level control of the capacitance of two-dimensional covalent organic frameworks: role of hydrogen bonding in energy storage materials - Chandra, S.; Chowdhury, D.R; Addicoat, M.; Heine, T.; Paul, A.; Banerjee, R. (Chemistry of Materials, 2017)
Two-dimensional redox-active covalent organic frameworks (COFs) are ideal materials for energy storage applications due to their high surface area, extended pi conjugated structure, tunable pore size, and adjustable functionalities. Herein, we report the synthesis and super capacitor application of two redox active COFs [TpPa-(OH)(2) and TpBD-(OH)(2)] along with the role of their redox active functional groups for the enrichment of specific capacitance. Of these COFs, TpPa-(OH)2 exhibited the highest specific capacitance of 416 F g(-1) at 0.5 A g(-1) current density in three electrode configuration while the highest specific capacitance was 214 F g(-1) at 0.2 A g(-1) current density in two electrode configuration. Superior specific capacitance was due to emergence of excellent pseudocapacitance by virtue of precise molecular level control over redox functionalities present in the COF backbone. This COF also demonstrated 66% capacitance retention after 10 000 cycles along with 43% accessibility of the redox-active hydroquinone (H2Q) moieties in three electrode configuration while the capacitance retention was 88% after 10 000 cycles in two electrode configuration. Exceptionally high specific capacitance of TpPa-(OH)(2) was due to the reversible proton-coupled electron transfer (2H(+)/2(e-)) of hydroquinone/benzoquinone (H(2)Q/Q) moieties wherein H(2)Q and Qhad comparable chemical stabilities during redox cycling that originated from H-bonding, which was supported by calculated structures.

Multi-mode hydrogen storage in nanocontainers - Shervani, Suboohi; Mukherjee, Puspal; Gupta, Anshul; Mishra, Gargi; Illath, Kavya; Ajithkumar, Thallaseril G.; Sivakumar, Sri; Sen, Pratik; Balani, Kantesh; Subramaniam, Anandh (International Journal of Hydrogen Energy, 2017)
Hydrogen can be stored in containers or in materials (in molecular or atomic forms). The atomic form can further exist as multiple phases. Molecular hydrogen can be adsorbed on the surface or can be present inside the material. By invoking multiple modes of hydrogen storage, we establish a paradigm shift in the philosophy of hydrogen storage. Using a novel strategy of storage of molecular hydrogen in metal (Pd) nanocontainers, we observe that 18% hydrogen is in molecular form. Interestingly, this is achieved at 25 °C and 1 atm pressure; which is in contrast to storage in MOFs and carbonaceous materials like nanotubes. Enhancement in storage capacity as compared to Pd nanocrystals of the same mass is observed (36% increase at 1 atm & 25 °C), along with fast kinetics (0.5 wt% hydrogen absorption in 5 s). A new mechanism for hydrogen storage involving the dual catalytic role of Pd is established.

Multiple functionalities of Ni nanoparticles embedded in carboxymethyl guar gum polymer: catalytic activity and superparamagnetism - Sardar, Debasmita; Sengupta, Manideepa; Bordoloi, Ankur; Ahmed, Md. A.; Neogi, S. K.; Bandyopadhyay, Sanjoy; Jain, Ruchi; Gopinath, Chinnakonda S.; Bala, Tanushree (Applied Surface Science, 2017)
Composites comprising of metallic nanoparticles in polymer matrices have allured significant importance due to multifunctionalities. Here a simple protocol has been described to embed Ni nanoparticles in carboxymethyl guar gum (CMGG) polymer. The composite formation helps in the stabilization of Ni nanoparticles which are otherwise prone towards aerial oxidation. Further the nanoparticles retain their superparamagnetic nature and catalytic capacity. Ni-Polymer composite catalyses the reduction of 4-Nitrophenol to 4-Aminophenol very efficiently in presence of NaBH4, attaining a complete conversion under some experimental conditions. Ni-Polymer composite is well characterized using UV–vis spectroscopy, FTIR, XPS, powder XRD, TGA, SEM and TEM. A detailed magnetic measurement using superconducting quantum interference device-vibrating sample magnetometer (SQUID-VSM) reveals superparamagnetic behaviour of the composite.

Multipronged quantitative proteomics reveals serum proteome alterations in breast cancer intrinsic subtypes - Gajbhiye, Akshada; Dabhi, Raju; Taunk, Khushman; Jagadeeshaprasad, Mashanipalya G.; RoyChoudhury, Sourav; Mane, Anupama; Bayatigeri, Santhakumari; Chaudhury, Koel; Santra, Manas K.; Rapole, Srikanth (Journal of Proteomics, 2017)
Being molecularly heterogeneous, breast cancer tends to be a complicated oncological disease with high incidence rates throughout the world. The primary aim of this study was to identify the set of serum proteins with discriminatory capabilities towards the four major subtypes of breast cancer. We employed multipronged quantitative proteomic approaches like 2D-DIGE, iTRAQ and SWATH-MS and identified 307 differentially regulated proteins. Luminal A subtype consisted of 24, Luminal B subtype 38, HER2 Enriched subtype 17 and Triple negative breast cancer subtype 10 differentially regulated subtype specific proteins. These specific proteins were further subjected to bioinformatic tools which revealed the involvement in platelet degranulation, fibrinolysis, lipid metabolism, immune response, complement activation, blood coagulation, glycolysis and cancer signaling pathways in the subtypes of the breast cancer. The significant discrimination efficiency of the models generated through multivariate statistical analysis was decent to distinguish each of the four subtypes from controls. Further, some of the statistically significant differentially regulated proteins were verified and validated by immunoblotting and mass spectrometry based selected reaction monitoring (SRM) approach. Our Multipronged proteomics approaches revealed panel of serum proteins specifically altered for individual subtypes of breast cancer. The mass spectrometry data are available via ProteomeXchange with identifier PXD006441. Biological significance: Worldwide, breast cancer continues to be one of the leading causes of cancer related deaths in women and it encompasses four major molecular subtypes. As breast cancer treatment majorly depends on identification of specific subtype, it is important to diagnosis the disease at subtype level. Our results using multipronged quantitative proteomics identified 307 differentially regulated proteins in which 24 were specific for Luminal A, 38 for Luminal B, 17 for HER2 enriched and 10 proteins were specific for TN subtype. Bioinformatic analysis of these proteins revealed certain biological processes and pathways altered at subtype level and validation experiments of some of these proteins using immunoblotting and SRM assays are consistent with discovery data. This is the first comprehensive proteomic study on serum proteome alterations at subtype level which will not only help to distinguish subtype of breast cancer but also contribute to a better understanding of the molecular characteristic of breast cancer at individual subtype level. (C) 2017 Elsevier B.V. All rights reserved.

N - heterocyclic - carbene - catalyzed umpolung of imines - Patra, Atanu; Mukherjee, Subrata; Das, Tamal Kanti; Jain, Shailja; Gonnade, Rajesh Ghanshyam; Biju, Akkattu T. (Angewandte Chemie International Edition, 2017)
N-Heterocyclic carbene (NHC) catalysis has been widely used for the umpolung of aldehydes, and recently for the umpolung of Michael acceptors. Described herein is the umpolung of aldimines catalyzed by NHCs, and the reaction likely proceeds via aza-Breslow intermediates. The NHC-catalyzed intramolecular cyclization of aldimines bearing a Michael acceptor resulted in the formation of biologically important 2-(hetero)aryl indole 3-acetic-acid derivatives in moderate to good yields. The carbene generated from the bicyclic triazolium salt was found to be efficient for this transformation.

Nanoparticle assembly: a perspective and some unanswered questions - Kumar, Sanat K.; Kumaraswamy, Guruswamy; Prasad, Bhagavatula L. V.; Bandyopadhyaya, Rajdip; Granick, Steve; Gang, Oleg; Manoharan, Vinothan N.; Frenkel, Daan; Kotov, Nicholas A. (Current Science, 2017)
In early 2016, the Royal Society of Chemistry arranged a meeting on the topic 'Nanoparticle Assemblies: from Fundamentals to Applications' which was hosted at IIT-Bombay, Mumbai. The meeting brought several leading nanoscience and nanotechnology researchers to India and is only the second Faraday Discussions meeting to have been held in the country. The papers presented at the meeting and the resulting active discussions have been summarized in a Faraday Discussion issue(1). The broad range of topics discussed at the meeting led to an understanding on where we stand in the field of nanoparticle assembly, and also enunciated some of the outstanding fundamental and practical issues that remain to be resolved before these ideas can be applied to practical situations. Driven by these ideas, here we focus on four topics/questions: (i) Can we achieve function-driven design of nanoparticle assemblies? (ii) What is the minimal information needed to build a desired assembly? (iii) How complex a structure can one build? How can one make it responsive? What are the relative roles of equilibrium versus dynamics in the assembly process, and are we at a point where we can now pursue active assembly as a viable mode for creating complex assemblies? (iv) What are the applications that are being targeted and what are the barriers to implementation? In this perspective, we do not present an exhaustive survey of the vast literature in this area, but indicate overarching themes/questions that require immediate attention, largely based on the discussions at the Mumbai meeting.