Genome sequence of rheinheimera sp strain A13L, isolated from pangong lake, india - Gupta, Hemant Kumar; Gupta, Rinkoo Devi; Singh, Ajit; Chauhan, Nar Singh; Sharma, Rakesh (Journal of Bacteriology, 2011)
Rheinheimera sp. strain A13L, which has antimicrobial activity, was isolated from alkaline brackish water of the high-altitude Pangong Lake of Ladakh, India. Here we report the draft genome sequence of Rhienheimera sp. strain A13L (4,523,491 bp with a G + C content of 46.23%). The genome is predicted to contain genes for marinocine and colicin V production, which may be responsible for the antimicrobial activity of the strain.

Glycerol mediated low temperature synthesis of nickel nanoparticles by solution reduction method - Singh, Kalpana; Kate, Kunal H.; Chilukuri, V. V. Satayanarayana; Khanna, P. K. (Journal of Nanoscience and Nanotechnology, 2011)
Phase pure Nickel nano-particles were synthesized by in-situ generation of nickel hydrazine hydrate complex (Ni-HH) followed by its decomposition in an alkaline glycerol medium. The synthesis can be performed in an open beaker with or without the use of surface protective reagents. By using the present method, Ni nano-particles can be prepared in large scale. The black nano-powders so-obtained were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red (FTIR) spectroscopy and thermal analysis (TGA). XRD and SAED analysis revealed that the synthesized particles were pure crystalline nickel with FCC structure.
Keywords: Chemical Reduction; Nano-Particles; synthesis; Transition Metal; XRD

Greener ullmann-type coupling of aryl halides for preparing biaryls using reusable Pd/ZrO2 catalyst - Dumbre, Deepa K.; Wakharkar, Radhika D.; Choudhary, Vasant R. (Synthetic Communications, 2011)
Biaryls with excellent yields can be prepared by the Ullmann-type coupling of aryl halides in the presence of potassium carbonate (as a base) and dimethylformamide (as a solvent), at 140 degrees C, using a reusable Pd (2.5wt%)/ZrO2 catalyst. The product yield of 4-iodoanisole coupling is strongly influenced by the catalyst preparation method, solvent, and base.
Keywords: Aryl halides; Biaryls; Pd; Ullmann coupling reaction; ZrO2

Growth of hydrothermally stable meso-porous silica structure interconnected around micro-porous zeolite crystals - Kinage, Anil K.; Prashar, Atul K.; Berlier, Gloria; Chaturvedi, Rajiv K. (Materials Characterization, 2011)
The growth of hydrothermally stable ordered meso-porous silica with M41S type structure interconnected around zeolite crystals was achieved from seeds normally nucleating the crystallization of micro-porous zeolite. The solid state NMR and FT-IR showed species like Si(OSi)(3)OH and Si(OSi)(2)(OH)(2) (or Q(3) and Q(2) sites, respectively) are formed during first hydrothermal treatment with surfactant and NaOH. These species and surface silanol group of zeolite crystal condense to give meso-porous silica structure interconnected around zeolite crystal during re-crystallization at lower pH. Resulting meso-micro-porous hybrid material is found to be highly active, selective and stable in the synthesis of 2-(phenylamino) ethanol from aniline and ethylene carbonate compare to parent ZSM-5 and pure MCM-41. (C) 2011 Elsevier Inc. All rights reserved.
Keywords: Hydrothermal stability; Interconnected meso-porous silica; Meso-micro hybrid material; Synthesis of amino alcohol

Improved performance of phosphonated carbon nanotube-polybenzimidazole composite membranes in proton exchange membrane fuel cells - Kannan, Ramaiyan; Kagalwala, Husain N.; Chaudhari, Harshal D.; Kharul, Ulhas K.; Kurungot, Sreekumar; Pillai, Vijayamohanan K. (Journal of Materials Chemistry, 2011)
Development of thermally stable polymer electrolyte membranes with higher proton conductivity as well as mechanical stability is a key challenge in commercializing PEM fuel cells operating above 100 degrees C. Polybenzimidazole membranes are one of the promising candidates in this category although with limited mechanical stability and moderate proton conductivity. Here the incorporation of functionalized MWCNT is shown to increase both these key parameters of the polybenzimidazole membranes. Further, formation of a domain like structure after the incorporation of phosphonated MWCNTs (P-MWCNTs) in phosphoric acid doped polybenzimidazole membranes is demonstrated. The enhanced performance has been attributed to the formation of proton conducting networks that formed along the sidewalls of P-MWCNTs with a domain size of 17 nm as estimated from the small angle X-ray scattering measurements. Membrane electrode assembly (MEA) impedance measurements further reveal that the activation energy of oxygen reduction reaction (ORR) reduced for the composite membranes with enhanced proton conductivity. In addition, the mechanical strength measurements reveal a significant improvement in the yield strength and ultimate strength. Also, the mechanical strength of the composite membrane has been increased significantly as indicated by the improvement in the ultimate strength from 65 MPa to 100 MPa for the pristine and composite membranes, respectively. The optimum loading of P-MWCNTs is found to be 1% as inferred from the polarization measurements carried out using pure hydrogen and oxygen. Thus, this study provides a unique opportunity to tune the properties of polymer electrolytes to prepare application oriented hybrid membranes using CNTs with tailor-made functional groups.

Incorporation of zirconium in medium-pore aluminophosphate molecular sieves with AFO framework - Chakrabortty, Dhruba; Ganguli, J. N.; Satyanarayana, C. V. V. (Microporous and Mesoporous Materials, 2011)
Zirconium substituted medium pore microporous aluminophosphate molecular sieve ZrAPO-41 was prepared by hydrothermal synthesis under autogenous pressure The formation of the pure phase was confirmed by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM)The thermal behaviour of the material was investigated by carrying out thermogravimetric/differential thermal analysis (TGA/DTA) The zirconium environment was studied by magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy which suggests incorporation of zirconium into the framework UV-Visible diffuse reflectance study also supports the claim The temperature programmed desorption (TPD) of ammonia reveals that the acidity of ZrAPO 41 samples is higher than that of pure AlPO4-41 The catalytic activity of the samples was investigated through phenol hydroxylation reaction The result show hi E her catalytic activity for ZrAPO-41 samples compared to AlPO4-41 (C) 2010 Elsevier Inc All rights reserved
Keywords: AFO; Aluminophosphate; catalysis; Molecular sieve; ZrAPO 41

Isobutrin from butea monosperma (flame of the forest): a promising new natural sensitizer belonging to chalcone class - Agarkar, Shruti A.; Kulkarni, Roshan R.; Dhas, Vivek V.; Chinchansure, Ashish A.; Hazra, Partha; Joshi, Swati P.; Ogale, Satishchandra B. (ACS Applied Materials & Interfaces, 2011)
In this work, ``isobutrin'', an ecofriendly sensitizer that is extracted from Butea monosperma (commonly known as ``Flame of the Forest'') flowers, is introduced. It is a bright yellow pigment belonging to the chalcone class and is examined as a sensitizer for optoelectronic applications. It is observed that chelation of this dye with Ti ions results into a strong dye-TiO(2) charge transfer (DTCT) band in the visible region. This Ti-Isobutrin chelate is stable, irreversible and its formation is studied using Benesi-Hildebrand plot. The locations of HOMO-LUMO states of the Ti-isobutrin chelate and the corresponding band alignment with TiO(2) are obtained. Also, a thermal stability test revealed that isobutrin is stable above 100 degrees C.
Keywords: Butea monosperma; chalcone; dye-sensitized solar cell; isobutrin; sensitizer; TiO(2)

Maghemite (hematite) core (shell) nanorods via thermolysis of a molecular solid of Fe-complex - Chaudhari, N. S.; Warule, S. S.; Muduli, Subas; Kale, B. B.; Jouen, Samuel; Lefez, Benoit; Hannoyer, Beatrice; Ogale, Satishchandra B. (Dalton Transactions, 2011)
An Fe-metal complex with 2'-hydroxy chalcone (2'-HC) ligands [Fe(III) (2'-hydroxy chalcone) 3] is synthesized by a chemical route and is subjected to different thermal treatments. Upon thermolysis in air at 450 degrees C for 3 h the complex yields maghemite (gamma-Fe(2)O(3)) nanorods with a thin hematite (alpha-Fe(2)O(3)) shell. X-Ray diffraction (XRD), Mossbauer spectroscopy, diffuse reflectance spectroscopy (UV-DRS), high resolution transmission electron microscopy (HR-TEM), field emission scanning electron microscopy (FE-SEM) and vibrating sample magnetometry (VSM) are used to characterize the samples. The stability of the ligand and the Fe-complex is further examined by using thermogravimmetric/differential thermal analysis (TGA/DTA). We suggest a residual ligand controlled mechanism for the formation of an anisotropic nanostructure in a crumbling molecular solid undergoing ligand decomposition. Since the band gap of iron oxide is in the visible range, we explored the use of our core shell nano-rod sample for photocatalytic activity for H(2) generation by H(2)S splitting under solar light. We observed high photocatalytic activity for hydrogen generation (75 ml h(-1)).

Novel hybrids of fluconazole and furanones: design, synthesis and antifungal activity - Borate, Hanumant B.; Sawargave, Sangmeshwer P.; Chavan, Subhash P.; Chandavarkar, Mohan A.; Iyer, Ramki; Tawte, Amit; Rao, Deepali; Deore, Jaydeep V.; Kudale, Ananada S.; Mahajan, Pankaj S.; Kangire, Gopinath S. (Bioorganic & Medicinal Chemistry Letters, 2011)
During our efforts to develop new antifungal agents, a number of hybrid molecules containing furanones and fluconazole pharmacophores were designed and synthesized. The new chemical entities thus synthesized were tested for their potential as antifungal agents against various fungal strains and it was observed that the compounds with general structure 7 were potent inhibitors of Candida albicans ATCC 24433, Candida glabrata ATCC 90030, Candida tropicalis ATCC 750 and Candida neoformans ATCC 34664 while the fluconazole analogues 12 exhibited antifungal activity against Candida albicans ATCC 24433 and Candida glabrata ATCC 90030. The structure-activity relationship for these compounds is discussed. The synthetic strategies used in the present work have potential to prepare a large number of compounds for further refinement of structures to obtain molecules suitable for development as antifungal drugs. (C) 2011 Elsevier Ltd. All rights reserved.
Keywords: Antifungal activity; Fluconazole; Furanones

Novel pyrazole-3-carboxamide derivatives as cannabinoid-1 (CB1) antagonists: journey from non-polar to polar amides - Sasmal, Pradip K.; Reddy, D. Srinivasa; Talwar, Rashmi; Venkatesham, B.; Balasubrahmanyam, D.; Kannan, M.; Srinivas, P.; Kumar, K. Shiva; Devi, B. Neelima; Jadhav, Vikram P.; Khan, Sanjoy K.; Mohan, Priya; et al. (Bioorganic & Medicinal Chemistry Letters, 2011)
The synthesis and biological evaluation of novel pyrazole-3-carboxamide derivatives as CB1 antagonists are described. As a part of eastern amide SAR, various chemically diverse motifs were introduced. In general, a range of modifications were well tolerated. Several molecules with high polar surface area were also indentified as potent CB1 receptor antagonists. The in vivo proof of principle for weight loss is exemplified with a lead compound from this series. (C) 2010 Elsevier Ltd. All rights reserved.

Novel synthesis of nano-calcium carbonate (CaCO3)/polystyrene (PS) core-shell nanoparticles by atomized microemulsion technique and its effect on properties of polypropylene (PP) composites - Mishra, Satyendra; Chatterjee, Aniruddha; Singh, RajPal (Polymers for Advanced Technologies, 2011)
Calcium carbonate (CaCO3)/polystyrene (PS) nanoparticles (< 100 nm) with core-shell structure were synthesized by atomized microemulsion technique. The polymer chains were anchored onto the surface of nano-CaCO3 through triethoxyvinyl silane (TEVS) as a coupling agent. Ammonium persulfate (APS), sodium dodecyl sulfate (SDS) and n-pentanol were used as initiator, surfactant, and cosurfactant, respectively. Polymerization mechanism of core-shell latex particles was discussed. Encapsulation of nano-CaCO3 by PS was confirmed by using transmission electron microscope (TEM). Grafting percentage of core-shell particles was investigated by Thermogravimetric Analyzer (TGA). Nano-CaCO3/PS core-shell particles were characterized by Fourier transform infrared (FTIR) spectrophotometer and differential scanning calorimeter (DSC). The results of FTIR revealed existence of a strong interaction at the interface of nano-CaCO3 particle and PS, which implies that the polymer chains were successfully grafted onto the surface of nano-CaCO3 particle through the link of the coupling agent. In addition, TGA and DSC results indicated an enhancement of thermal stability of core-shell materials compared with the pure nano-PS. Nano-CaCO3/PS particles were blended with polypropylene (PP) matrix on Brabender Plastograph by melt process with different wt% of loading (i.e. 0.1-1 wt%). The interfacial adhesion between nano-CaCO3 particles and PP matrix was significantly improved when the nano-CaCO3 particles were grafted with PS, which led to increased thermal, rheological, and mechanical properties of (nano-CaCO3/PS)/PP composites. Scanning electron microscope (SEM) and atomic force microscope (AFM) images showed a perfect dispersion of the nano-CaCO3 particles in PP matrix. Copyright (C) 2011 John Wiley & Sons, Ltd.
Keywords: atomized microemulsion; core-shell nanoparticles; mechanical properties; polypropylene (PP); Rheological properties; Thermal properties

One-pot three-component kabachnik-fields synthesis of alpha-aminophosphonates using H-beta zeolite catalyst - Tillu, V. H.; Dumbre, Deepa K.; Wakharkar, R. D.; Choudhary, Vasant R. (Tetrahedron Letters, 2011)
One-pot three-component Kabachnik-Fields synthesis of alpha-aminophosphonates with high yields from the reaction between carbonyl compound, primary amine, and substituted phosphite can be carried out in a short period, using H-beta zeolite as a reusable catalyst. (C) 2010 Elsevier Ltd. All rights reserved.
Keywords: Carbonyl compound; H-beta zeolite; Primary amine; Substituted phosphite

One-step synthesis of 4-alkyl-3-aryl-2,6-dicyanoanilines and their use in the synthesis of highly functionalized 2,3,5,6,7-and 2,3,4,5,7-substituted indoles - Sawargave, Sangmeshwer P.; Kudale, Ananada S.; Deore, Jaydeep V.; Bhosale, Dattatry S.; Divse, Jaisingh M.; Chavan, Subhash P.; Borate, Hanumant B. (Tetrahedron Letters, 2011)
A three-component, one-step method for the synthesis of 4-alkyl-3-aryl-2,6-dicyanoanilines involving reaction of alkyl aldehyde, malononitrile and aryl aldehyde in presence of morpholine is reported. Highly functionalized 2,3,5,6,7- and 2,3,4,5,7-substituted indoles were prepared from these dicyanoanilines by reaction with ethyl bromoacetate. These substituted dicyanoanilines and indoles have a potential to be converted into various other compounds taking advantage of various functional groups present in these molecules. (C) 2011 Elsevier Ltd. All rights reserved.
Keywords: aldehydes; Dicyanoanilines; indoles; Malononitrile

Oxidative carbonylation of amine using water-soluble palladium catalysts in biphasic media - Didgikar, Mahesh R.; Joshi, Sunil S.; Gupte, Sunil P.; Diwakar, Makarand M.; Deshpande, Raj Madhukar; Chaudhari, Raghunath V. (Journal of Molecular Catalysis A-Chemical, 2011)
Application of water-soluble palladium catalysts for oxidative carbonylation of aniline to N,N' diphenyl urea (DPU) has been reported. The water-soluble palladium catalysts prepared from sulfonated N-containing ligands were found to be highly stable under reaction conditions and easily recyclable due to insoluble urea product in the reaction medium. This is in contrast to the sulfonated phosphine ligands, which are vulnerable to oxidation under reaction conditions, showing poor activity and stability. Commercially available as well as laboratory synthesized ligands were used for preparing water-soluble palladium catalysts, for oxidative carbonylation of aniline. The best activity was obtained for Pd complex with disodium 2,2'-bipyridine-4,4'-disulfonate (Bipy-DS) ligand. Under optimized conditions Pd(BipyDS)Pd(OAc)(2) catalyst gave TOF of similar to 210h(-1) with aniline conversion of similar to 97% with similar to 91% selectivity for N.N'-diphenyl urea. It was found that the catalyst was easily reusable up to five times, with negligible loss in the catalytic activity. The effect of reaction parameters was investigated and a plausible reaction mechanism has been proposed. (C) 2010 Elsevier B.V. All rights reserved.
Keywords: Amine; Biphasic catalysis; Carbonylation; Urea; Water-soluble palladium catalyst

Photoelectrochemical applications of In2Se3 thin films by chemical deposition - Hankare, P. P.; Rathod, K. C.; Asabe, M. R.; Jadhav, A. V.; Helavi, V. B.; Chavan, Santosh S.; Garadkar, K. M.; Mulla, Imtiaz S. (Journal of Materials Science-Materials in Electronics, 2011)
Indium selenide films have been synthesized by chemical bath deposition method onto stainless steel plate. The configuration of fabricated cell is n-In2Se3| NaOH(1 M) + S(1 M) + Na2S(1 M) |C-(graphite). Characterization of the photoelectrochemical cell was carried out by studying X-ray diffraction, current-voltage and capacitance-voltage characteristics in the dark, barrier height measurements, power output, photoresponse and spectral response. The study shows that the In2Se3 thin films are n-type semiconductor. The junction ideality factor was found to be 3.24. The flat band potential and the barrier height were found to be 0.720 V and 0.196 eV, respectively. From the study of power output characteristics, open circuit voltage, short circuit current, fill factor and efficiency were found to be 310 mV, 20 mu A, 37.64 and 0.61%, respectively. Photoresponse studies show that the lighted ideality factor is 2.78. Maximum current was observed at 575 nm.

Selective catalytic oxidation of geraniol to citral with molecular oxygen in supercritical carbon dioxide - Dapurkar, Sudhir E.; Kawanami, Hajime; Chatterjee, Maya; Rode, Chandrasekhar V.; Yokoyama, Toshirou; Ikushima, Yutaka (Applied Catalysis A-General, 2011)
Selective catalytic oxidation of geraniol to citral with molecular oxygen in supercritical carbon dioxide (scCO(2)) has been investigated. The catalyst used was a chromium containing mesoporous molecular sieve catalyst viz. CrMCM-41. Comparison studies were performed with CoMCM-41. PtMCM-41 and PdMCM-41 catalysts. Among the various catalysts studied. CrMCM-41 showed a high conversion of geraniol and an excellent selectivity for citral. In contrast CoMCM-41, PtMCM-41 and PdMCM-41 catalysts exhibited low conversion of geraniol. However all three catalysts compared showed similar citral selectivity to CrMCM-41. The effect of CO(2) pressure and reaction temperature geraniol oxidation was studied with CrMCM-41. Supercritical CO(2) medium was found to enhance the conversion of geraniol and/or yield of citral. It was noticed that the catalyst can be recycled with negligible loss of conversion. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Citral; Geraniol; heterogeneous catalyst; Molecular oxygen; Selective oxidation; Supercritical carbon dioxide

Single nucleotide polymorphism in transcobalamin II (15V) induces structural changes in the protein as revealed by molecular modeling studies - Silla, Yumnam; Chandamouli, Balasubramanian; Maiti, Souvik; Sengupta, Shantanu (Biochemistry, 2011)
Cobalamin is an essential micronutrient in mammals. Deficiencies of this micronutrient have been implicated as risk factors for various complex diseases. Cobalamin is transported to the cells by the transport protein transcobalamin II (TCII), and hence genetic variations (like single nucleotide polymorphisms) in TCII could be perceived to affect the binding of cobalamin to TCII, thereby modulating the intracellular concentrations of cobalamin. To understand whether three nonsynonymous mutations in TCII (I5V, P241R, and R381Q) alter the structure of the protein which could potentially affect cobalamin binding, we performed molecular dynamics simulation in silico. Superimposition of active sites of the four simulated models (wild type and three variants) with the human TCII crystal structure revealed that the distance between the N epsilon nitrogen atom of His-173 and the cobalt ion of cobalamin deviated considerably in the I5V model as compared to wild type and other variants. His-173 directly coordinates with the cobalt ion of cobalamin. Further, from our dynamic cross-correlation and principal component analysis it appears that in the I5V model the beta-domain moves apart from the alpha-domain creating a wide gap between the two domains. This might facilitate the initial binding of cobalamin in the I5V model as cobalamin enters the binding site through the gap between the two domains. These observations were not found in the other variants. We thus speculate that binding of cobalamin will be more facile in the I5V variant.

Solvent-dependent aggregation behavior of a new Ru(ii)-polypyridyl based metallosurfactant - Mahato, Prasenjit; Saha, Sukdeb; Choudhury, Sipra; Das, Amitava (Chemical Communications, 2011)
Variation of the solvent polarity leads to the formation of vesicles and reverse vesicles of a newly synthesized amphiphilic Ru(II)-polypyridyl complex.

Solvent-free selective oxidation of primary alcohols-to-aldehydes and aldehydes-to-carboxylic acids by molecular oxygen over MgO-supported nano-gold catalyst - Choudhary, Vasant R.; Dumbre, Deepa K. (Catalysis Communications, 2011)
Magnesium oxide supported nano-gold catalyst (prepared by the homogeneous deposition precipitation technique) showed high activity/selectivity and excellent reusability in the oxidation of different primary alcohols and aldehydes to corresponding aldehydes and carboxylic acids, respectively, by molecular oxygen (under atmospheric pressure) in the absence of any solvent. Influence of the catalyst calcination temperature (400-900 degrees C), reaction temperature (50-120 degrees C) and use of different solvents (viz. toluene. p-xylene, DMF or DMSO) on the oxidation reaction has also been studied. (C) 2011 Published by Elsevier B.V.
Keywords: Alcohols; aldehydes; Au/MgO; Molecular oxygen; Solvent-free oxidation

Strong electric field modulation of transport in PVDF/MWCNT nanocomposite near the percolation threshold - Chanmal, Chetan; Deo, Meenal S.; Rana, Abhimanyu; Jog, Jyoti Prakash; Ogale, Satishchandra B. (Solid State Communications, 2011)
A nanocomposite comprising of multiwalled carbon nanotubes (MWCNT) embedded in ferroelectric Poly(vinylidene fluoride) PVDF polymer matrix is examined for electric field induced transport modulation. The pulsed laser deposition (PLD) grown thin films of the nanocomposite with different MWCNT content were characterized. When used as a channel layer in a field effect transistor configuration, a strong electric field modulation of the transport was realized just below the percolation threshold. We believe that this nanocomposite non-percolating channel concept can provide several opportunities for FET devices for organic electronics. (C) 2011 Elsevier Ltd. All rights reserved.
Keywords: Field effect device; pulsed laser deposition; PVDF; Scanning tunneling microscopy

Structural isomerism and effect of fluorination on gas adsorption in copper-tetrazolate based metal organic frameworks - Pachfule, Pradip; Chen, Yifei; Sahoo, Subash Chandra; Jiang, Jianwen; Banerjee, Rahul (Chemistry of Materials, 2011)
Synthesis, structure, and gas adsorption properties of three Metal Organic Frameworks (MOFs) synthesized from predesigned ligands 4-(1H-tetrazole-5-yl)benzoic acid (4-TBA) and 2-fluoro-4-(1H-tetrazole-5-yl)benzoic acid (2F-4-TBA) along with Cu(II) as an metal precursor has been reported. Among these MOFs, Cu-9(4-TBA)(10)(C2H5OH)(2) (Cu-TBA-1) and Cu-2(4-TBA)(2)(DMF)(C2H5OH) (Cu-TBA-2) are structural isomers. Whereas, Cu-2(4-TBA)(2)(DMF)(C2H5OH) (Cu-TBA-2) and Cu-2(2-F-4-TBA)(2)(DMF)(2) (Cu-TBA-2F) have similar crystal structure. N-2 adsorption isotherms of the activated sample of Cu-TBA-1 and -2 exhibit types-I sorption behavior with a Langmuir and Brunauer-Emmett-Teller (BET) surface area of 686, 402 m(2)/g and 616, 356 m(2)/g, respectively. It is noteworthy that Cu-TBA-1 and -2 adsorbs 1.16 and, 1.54 wt % H-2, while Cu-TBA-2F adsorbs 0.67 wt % at 77 K and 1 atm. On the other hand, Cu-TBA-1 and -2 adsorb 3.08 and 2.54 mmol/g, while Cu-TBA-2F adsorbs 1.27 mmol/g of CO2 at 298 K and 1 bar pressure. H-2 adsorption sites in Cu-TBA-2 and -2F have been analyzed by molecular simulation.
Keywords: CO2 adsorption; fluorination; Hydrogen storage; Metal-organic framework; structural isomerism

Structure-property of thermoplastic polyurethane-clay nanocomposite based on covalent and dual-modified laponite - Mishra, Ananta K.; Rajamohanan, P. R.; Nando, Golok B.; Chattopadhyay, Santanu (Journal of Computational and Theoretical Nanoscience, 2011)
Modification of surface of clay platelets by ionic and covalent modification techniques renders it to be easily dispersed in polymers like, Thermoplastic Polyurethane (TPU). Only ionic or covalent modification techniques in isolation are not sufficient to achieve uniform nanoscale dispersion of Laponite (synthetic hectorite nanoclay) in TPU. Hence, the dual modification of Laponite (both ionic and covalent) is performed and the effects of the modification on the morphology, thermal and rheological behaviors of the TPU-modified clay nanocomposites have been studied. The degree of exfoliation of clay platelet in TPU matrix is found to be higher for dual functionalized nanoclays compared to their singly modified counterparts. Interestingly, dual modified Laponite clays prepared by using two different techniques (ionic followed by covalent and covalent followed by ionic) exhibit different morphology and properties. The dual modified clays significantly alter the equilibrium morphology of TPU. The storage modulus of the dual modified Laponite-TPU nanocomposite in the glassy region (at -60 degrees C) land in the rubbery region (+98 degrees C) is improved by 172.8% and 85%, respectively as compared to the neat TPU. Similarly, the onset of degradation is found to be enhanced by 28.7 degrees C as compared to the neat TPU.
Keywords: Dual modification; Laponite Nanocomposite; Morphology; Structure-Property; Thermoplastic polyurethane

Surfactant tunable hierarchical nanostructures of CdIn2S4 and their photohydrogen production under solar light - Bhirud, Ashwini P.; Chaudhari, Nilima; Nikam, Latesh; Sonawane, Ravindra; Patil, Kashinath; Baeg, Jin-Ook; Kale, Bharat (International Journal of Hydrogen Energy, 2011)
The hierarchical nanostructures of CdIn2S4 were selectively prepared through hydrothermal process in the presence of different surfactants. Structural study demonstrated existence of cubic spinel structure and micro structural study shown a pretty marigold flower like morphology without any surfactant. The effect of surfactants on the morphology and microstructure of CdIn2S4 has been studied by using Polyvinyl pyrrolidone (PVP) and Cetyltrimethyl ammonium bromide (CTAB) as a surfactants. The CdIn2S4 bipyramids with length of 0.7-1 mu m have been obtained using PVP. Interestingly, the nanopetals (thin and transparent) of CdIn2S4 are self assembled into hollow spheres in the presence of CTAB. Considering the importance of these unique nanostructures, the growth mechanism has also been proposed. The optical properties demonstrated the band gap in the range of 2.12-2.29 eV which is well within the visible region. In this contest, photocatalytic activity for hydrogen production using the above nanostructures under visible light was also demonstrated. The prima-fascia observations shows that the bipyramidal CdIn2S4 exhibit excellent photocatalytic activity for hydrogen production (3238 mu molh(-1)) than other nanostructures. Being a nanostructured semiconductor chalcogenide with a good stability will also have potential applications in solar cells and LED. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
Keywords: Bipyramids; CdIn2S4; Hydrogen generation; hydrothermal; Self-assembled

Synthesis and characterization of chemically deposited nickel substituted CdSe thin film - Hankare, P. P.; Jadhav, B. V.; Chate, P. A.; Sathe, D. J.; Mulla, Imtiaz S. (Journal of Alloys and Compounds, 2011)
The technologically important Cd(0.5)Ni(0.5)Se thin film has been developed by solution growth technique on non-conducting glass substrate in tartarate bath containing Cd(+2), Ni(+2) ions and sodium selenosulphate in an aqueous alkaline medium at room temperature. Various preparative conditions of the thin films are outlined. The films were characterized by X-ray diffraction, scanning electron microscope, optical absorption and electrical measurements. The X-ray diffraction study indicates that the film is polycrystalline in nature with hexagonal phase. Scanning electron micrograph shows that the film is homogeneous with well-defined grains. The films have high optical absorption coefficient. Thermoelectric power measurement shows p-type conduction mechanism. (C) 2010 Elsevier B.V. All rights reserved.
Keywords: Chemical synthesis; Crystal growth; Electrical conductivity; thin film

Synthesis and characterization of cholesteric thermotropic liquid crystalline polyesters based on isosorbide - Chavan, Nayaku (Materials Sciences and Applications, 2011)
Generally main chain cholesteric thermotropic liquid crystalline polymers are prepared form chiral dia-cid or diol monomer. But these monomers are costly. Isosorbide is chiral cycloaliphatic diol accessible from renewable resources in the form of pure enantiomers. Thus it is used to synthesize main chain cholesteric thermotropic liquid crystalline polymers. Incorporation of phenyl hydroquinone into the backbone of the main chain frustrates chain pack-ing, thus lowering the crystallinity and depressing the melting point below the degradation temperature, also improves the solubility due to disruption of packing and maintains the mechanical and thermal performance. Results: Optical microscopy study reveals that more than 50% of isosorbide content with phenyl hydroquinone and terephthalic acid showed “yellow iridescent oily streaks” with a background of mosaic/marble texture. These are the typical textures of cholesteric liquid crystalline phase. Copolyesters based on phenyl hydroquinone, isosorbide and terephthalic acid are soluble in aprotic solvents like N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), and N-methyl-2-pyrrolidone (NMP). Solubility increases with the content of isosorbide percent. Thermal stabil-ity of all copolyesters was more than 300˚C on the basis of 10 wt% loss. Conclusions: It was found that main chain cholesteric thermotropic liquid crystalline polymers can be prepared form chiral cycloaliphatic diol such as isosorbide. Main chain cholesteric thermotropic liquid crystalline polyesters are prepared from phenyl hydroquinone, isosorbide and terephthalic acid showed thermal stability more than 300˚C. Main chain cholesteric thermotropic liquid crystalline polymers are soluble in aprotic solvents like DMAC, DMSO, DMF and NMP
Keywords: Cholesteric; Crystallinity; differential scanning calorimetry; Inherent Viscosity; Liquid Crystalline Polymers; Optical Microscopy; Solubility and Solution Polycondensation; Thermo Gravimetric Analysis; thermotropic; Wide Angle X-Ray Diffraction

Synthesis and drug-delivery behavior of chitosan-functionalized graphene oxide hybrid nanosheets - Rana, Vijay Kumar; Choi, Myeon-Cheon; Kong, Jin-Yeon; Kim, Gwang Yeon; Kim, Mi Ju; Kim, Sun-Hee; Mishra, Satyendra; Singh, Raj Pal; Ha, Chang-Sik (Macromolecular Materials and Engineering, 2011)
Chitosan-functionalized graphene oxides (FGOCs) were successfully synthesized. FGOCs were found to significantly improve the solubility of the GO in aqueous acidic media. The presence of organic groups was confirmed by means of XPS and TGA. Restoration of the sp(2) carbon network and exfoliation of graphene sheets were confirmed by Raman spectroscopy, UV-visible spectroscopy and WAXD. The SEM and AFM investigations of the resultant FGOCs showed that most of the graphene sheets were individual and few were layered. Controlled release behavior of Ibuprofen and 5-fluorouracil was then investigated. We found that FGOCs are a promising new material for biological and medical applications.
Keywords: Biocompatibility; Chitosan; drug delivery systems; functionalization of polymers; solution properties

Synthesis of single crystalline CdS nanocombs and their application in photo-sensitive field emission switches - Chavan, Padmakar G.; Badadhe, Satish S.; Mulla, Imtiaz S.; More, Mahendra A.; Joag, Dilip S. (Nanoscale, 2011)
Single crystalline CdS nanocombs were synthesized by a thermal evaporation route. The photo-sensitive field emission current shows a reproducible switching behavior, with a rise in current level of nearly five times the initial preset value of similar to 1 mu A. An ultra low turn-on field, required to draw an emission current density of similar to 0.1 mu A cm(-2) (100 nA), is found to be similar to 0.26 V mu m(-1) (260 V), which is much lower than the reported values for various other CdS nanostructures. Upon illumination with visible light the CdS nanocombs act as a photo field emission switch. At an applied field of similar to 0.65 V mu m(-1) the current densities are observed to be similar to 14.6 mu A cm(-2) and similar to 26.9 mu A cm(-2), without and with light illumination, respectively. The average emission current is seen to be stable over the duration of measurement for two preset values. The high sensitivity and fast response in the visible range indicates that the CdS nanocombs can be used as a photo-sensitive field emitting switch in device applications, and also in pulsed electron beam technology.

Thermally decomposed Ni-Fe-hydrotalcite: a highly active catalyst for the solvent-free N-acylation of different amines by acid chlorides - Choudhary, Vasant R.; Dumbre, Deepa K. (Catalysis Communications, 2011)
A composite Ni-Fe catalyst obtained from the thermal decomposition of Ni-Fe-hydrotalcite at 600 degrees C shows very high activity in the solvent-free N-acylation of amines by different acid chlorides with high product yields under very mild reaction conditions (viz, room temperature, short reaction period and small amount of catalyst). The catalyst also shows excellent reusability in the reaction. The crystalline phases present in the catalyst are mixed oxides and hydroxides of nickel and iron. The high catalytic activity of the decomposed Ni-Fe-hydrotalcite is attributed to the formation of uniformly distributed Ni-Fe metal oxides and hydroxides. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Acid chlorides; amines; Decomposition of Ni-Fe-hydrotalcite; N-acylation of amines; Ni-Fe-hydrotalcite derived catalyst

Transfer of technology (ToT) document of ethyl silicate-32 - Ponrathnam, Surendra; Chelanattukizhakkemadath, Raman Rajan; Dwivedi, Mayank; Chavan, Nayaku; Qureshi, Moham; Bhongale, Sunil Sitaram; Rao, Locanindi Hari Sarvothama; Dhanasekharan, Janakiraman; Mohan, S. Krishna; Deokar, Sarika Babasaheb; Momin, Mohasin Shamshuddin (Transfer of Technology (ToT)/ Technical Documents, 2011)

Transfer of technology (ToT) document of phenol-aniline-formaldehyde (sf-342a) resins - Ponrathnam, Surendra; Chelanattukizhakkemadath, Raman Rajan; Dwivedi, Mayank; Chavan, Nayaku; Qureshi, Moham; Bhongale, Sunil Sitaram; Rao, Locanindi Hari Sarvothama; Dhanasekharan, Janakiraman; Mohan, S. Krishna; Deokar, Sarika Babasaheb; Momin, Mohasin Shamshuddin (Transfer of technology (ToT) document, 2011)

Alkylation of benzene to cumene over mor zeolite catalysts - Vyawahare, Yogesh K.; Chumbhale, Vilas R.; Aswar, Anand S. (Revue Roumaine De Chimie, 2012)
The vapor phase alkylation of benzene to cumene (isopropyl benzene) is studied over MOR (mordenite) type zeolite at different process parameters. The reaction was also studied by adopting different methodologies (pyridine poisoning, passing of moist propylene, alkali dominant mordenite, use of coked catalyst and metal impregnated zeolite) to check the nature of product distribution and the extent of activity and selectivity to alkylated product IPB, DIPB (isopropyl benzene and diisopropyl benzene) and n-PB (n-propyl benzene). It is revealed that the adoption of different methodologies affects the activity and selectivity significantly by suppressing of alkylation / isomerisation reactions.
Keywords: Alkylation; cumene; isopropanol; MOR zeolite; propylene

Alpha-geminal dihydroxymethyl piperidine and pyrrolidine iminosugars: synthesis, conformational analysis, glycosidase inhibitory activity, and molecular docking studies - Pawar, Nitin J.; Parihar, Vijay Singh; Chavan, Sanjay T.; Joshi, Rakesh S.; Joshi, Pranaya V.; Sabharwal, Sushma G.; Puranik, Vedavati G.; Dhavale, Dilip D. (Journal of Organic Chemistry, 2012)
The Jocic-Reeve and Corey-Link type reaction of dichloromethyllithium with suitably protected 5-keto-hexofuranoses followed by treatment with sodium azide and sodium borohydride reduction gave 5-azido-5-hydroxylmethyl substituted hexofuranoses 7a-c with required geminal dihydroxymethyl group. Removal of protecting groups and converting the C-1 anomeric carbon into free hemiacetal followed by intramolecular reductive aminocyclization with in situ generated C5-amino functionality afforded corresponding 5C-dihydroxymethyl piperidine iminosugars 2a-c. Alternatively, removal of protecting groups in 7b and 7c and chopping of C1-anomeric carbon gave C2-aldehyde that on intramolecular reductive aminocyclization with CS-amino gave 4C-dihydroxyrnethyl pyrrolidine iminosugars 1b and 1c, respectively. On the basis of the H-1 NMR studies, the conformations of 2a/2b were assigned as C-4(1) and that of 2c as C-1(4). The glycosidase inhibitory activities of all five iminosugars were studied with various glycosidase enzymes and compared with natural o-g/uco-l-deoxynojirimycin (DNJ). All the five compounds were found to be potent inhibitors of rice alpha-glucosidase with K-i and IC50 values in the nanomolar concentration range. Iminosugars 2b and 1b were found to be more potent inhibitors than their parent iminosugar. These results were substantiated by in silico molecular docking studies.

Amino functionalized oligo polyimides with enhanced storage stability - Dwivedi, Mayank; Rao, Locanindi Hari Sarvothama; Mohan, Srinivasulu Reddy Krishna; Dhanasekharan, Janakiraman; Rao, Bevara Madhusudana; Kumar, Sriperambudur Rajesh; Ponrathnam, Surendra; Rajan, Chelanattukizhakkemadath Raman; Tayal, Rajiv Kumar; Shadbar, Qureshi Mohammed; Chavan, Nayaku; Deokar, Sarika Babasaheb; et al. (WO2012090055A1, 2012)
The invention relates to an improved process for the preparation of amino functionalized oligomeric monomeric reactant type polyimides having higher stability. More particularly it relates to a process for the preparation of soluble imide prepolymers, used as matrix resins that can be rapidly cured with multi-functional moieties such as diepoxy, dicarboxyl, anhydride, diisocyanates to form crosslinked structures having enhanced thermal stability and mechanical strength.

Analysis of AGE modified proteins and RAGE expression in HER2/neu negative invasive ductal carcinoma - Korwar, Arvind M.; Bhonsle, Hemangi S.; Chougale, Ashok D.; Kote, Sachin S.; Gawai, Kachru R.; Ghole, Vikram S.; Koppikar, Chaitanyananda B.; Kulkarni, Mahesh J. (Biochemical and Biophysical Research Communications, 2012)
Cancer is associated with increased glycolysis and carbonyl stress. In view of this, AGE modified proteins were identified from clinical breast cancer tissue using 2DE-immunoblot and mass-spectrometry. These proteins were identified to be serotransferrin, fibrinogen gamma chain, glycerol-3-phosphate dehydrogenase, lactate dehydrogenase, annexin II, prohibitin and peroxiredoxin 6, which have established role in cancer. Further, RAGE expression and its downstream signaling proteins NADPH oxidase and NF-kB were studied. Role of these AGE modified proteins and RAGE signaling in breast cancer is discussed. (C) 2012 Elsevier Inc. All rights reserved.
Keywords: advanced glycation end products; Breast cancer; RAGE

Anchored Pd-complexes in mesoporous supports: synthesis, characterization and catalysis studies for carbonylation reactions - Sarkar, Bibhas R.; Chaudhari, Raghunath V. (Catalysis Today, 2012)
Pd(pyca)(PPh3)(OTs) [pyca = 2-picolinate] complex is efficiently anchored inside different mesoporous matrices, such as MCM-41, MCM-48, SBA-15 using a molecular aminopropyl tether moiety employing different synthesis strategies. Thorough characterization of the materials using powder XRD, multinuclear (C-13, Si-29, P-31) CP-MAS NMR, XPS, SEM, N-2-sorption studies etc. confirmed the successful anchoring of the palladium complex to the walls of the support matrices thus establishing the synthesis protocols unambiguously. The catalysts were found to be highly active and selective for the carbonylation of different aryl olefins and alcohols. Consecutive recycling and successful reuse proved the stability and true heterogeneous nature of all the anchored catalysts, which is a substantial advancement over the existing heterogeneous catalysts for carbonylation. (C) 2012 Elsevier B. V. All rights reserved.
Keywords: Anchored catalysts; Carbonylation; Immobilization; mesoporous materials; Palladium complex

Asymmetric synthesis of a 12-membered macrolactone core and a 6-epi analogue of amphidinolide W from 4-pentenoic acid - Chatterjee, Bhaskar; Mondal, Dhananjoy; Bera, Smritilekha (Tetrahedron-Asymmetry, 2012)
A flexible and efficient asymmetric route to the synthesis of a 12-membered macrolactone core and a 6-epi analogue of amphidinolide W has been accomplished from commercially available 4-pentenoic acid. The successful generation of stereocenters was achieved by utilizing an Evans' chiral auxiliary-based alkylation and aldol reaction. Other key reactions such as a Julia-Kocienski olefination, Kita's macrolactonization, ring closing metathesis (RCM) reaction, and Yamaguchi's esterification were significant for the construction of the macrolactone cores. (c) 2012 Elsevier Ltd. All rights reserved.

Base promoted highly efficient copper fluorapatite catalyzed coupling of phenols with arylboronic acids under mild and ligand-free conditions - Mulla, Shafeek Abdul Rashid; Inamdar, Suleman M.; Pathan, Mohsinkhan Y.; Chavan, Santosh S. (RSC Advances, 2012)
A mild, general and highly efficient protocol has been developed for the synthesis of diaryl ethers in good to excellent yield under mild and ligand-free conditions. This is the first example in which a recyclable, heterogeneous copper fluorapatite catalyst is used for the arylation of phenols with arylboronic acids at room temperature in the presence of Cs2CO3 as a base and methanol as a solvent. The catalyst was recovered and reused several times without loss of catalytic activity.

Carbon dioxide capture by metal organic frameworks - Saha, Subhadeep; Chandra, Suman; Garai, Bikash; Banerjee, Rahul (Indian Journal of Chemistry Section A-Inorganic Bio-Inorganic Physical Theoretical & Analytical Chemistry, 2012)
The design and synthesis of functionalized metal organic framework materials (MOFs) for reversible physisorption of CO2 is discussed. This strategy of CO2 adsorption in MOFs requires less energy for regeneration than materials relying on chemisorption. As a result the MOFs have received considerable attention as sorbent materials for strategic gases such as CO2 and H,. In this review, we have discussed different MOFs and hybrid materials containing MOFs which can adsorb CO2 at room temperature. In order to achieve high adsorption capacity, fast CO2 adsorption-desorption and low energy requirement for regeneration are necessary. Several avenues for increasing the CO2 adsorption capacity of such materials, for instance, introduction of open metal sites and the use of ligand molecules with specific functionalities (like -OH or -NH2) have been described. It has been observed that CO2 loading capacity of MOFs increases with functionalization. Herein, we have discussed how N-containing and fluorinated MOFs are designed to achieve higher CO2 loading than their non-functionalized counterparts. Nanocarbons (e.g. carbon nanotubes, carbon nanofibres, etc.) are porous materials and a blend of these porous materials with porous MOFs or porous carbon derived from MOFs may act as a better adsorbate than even the pure materials. Enhancement of CO2 loading by nanocarbon-MOF hybrid material is also discussed.
Keywords: Carbon dioxide adsorbents; Carbon dioxide capture; hybrid materials; Metal organic frameworks; Nanocarbons; Porous nanocarbons

Carbon dioxide reforming of methane over ruthenium substituted strontium titanate perovskite catalysts - Gurav, Hanmant R.; Bobade, Richa; Das, Vineetha Lakshmi; Chilukuri, Satyanarayana V. (Indian Journal of Chemistry Section A-Inorganic Bio-Inorganic Physical Theoretical & Analytical Chemistry, 2012)
Strontium titanate (SrTiO3) doped with varying amounts of ruthenium (7.9, 15.6 and 31 wt%) have been prepared by the citrate gel synthesis method. Structural and textural characterizations reveal that at lower concentrations, a major part of Ru is incorporated in the lattice of SiTiO3. The content of surface Ru (outside lattice) increases with increasing amounts of the doped Ru. The surface Ru reduced at lower temperatures compared to Ru incorporated into the lattice. The reduction of the lattice substituted Ru occurs only at temperatures above the collapse of the perovskite structure. The catalyst sample with 7.9 wt% of Ru shows good conversions in the dry reforming of methane with CO2. The conversion of CO2 is in excess compared to methane under the studied reaction conditions. As a result, H-2/CO ratio of the product gases which should have been equivalent to unity is lower than the stoichiometric value. This ratio is particularly low when lower reaction temperatures (873-973 K) were used. Similar was the case when high space velocities were used. Low methane conversion and reverse water gas shift reaction are the causes for the low H-2/CO ratios.
Keywords: Carbon dioxide reforming; Catalysts; Citrate gel method; Doped catalysts; Dry reforming; Methane reforming; Perovskites; Reverse water gas shift; Ruthenium doped catalysts; Strontium titanate; Syngas

Ce-Ni mixed oxide as efficient catalyst for H-2 production and nanofibrous carbon material from ethanol in the presence of water - Fang, Wenhao; Pirez, Cyril; Capron, Mickael; Paul, Sebastien; Raja, Thirumalaiswamy; Dhepe, Paresh Laxmikant; Dumeignil, Franck; Jalowiecki-Duhamel, Louise (RSC Advances, 2012)
Hydrogen production from ethanol steam reforming (H2O/C2H5OH = 3) was studied over Ce-Ni based catalysts issued from different preparation methods (co-precipitation (CP), impregnation (IMP) and incipient wetness impregnation (IWI)). Catalysts prepared by the CP method exhibit higher activity and much better stability compared to the other two types of catalysts. The Ni1CeOY-CP catalyst is able to completely convert ethanol at 450 degrees C to H-2, CO2 and CH4 (almost no CO is observed), with a H-2 yield of 3 moles of hydrogen produced per mole of ethanol converted. A very high H-2 yield of 4.6 mol mol(EtOH)(-1) is achieved over the Ni1CeOY-CP mixed oxide at 650 degrees C. Correlations between the preparation method, catalytic activity and stability, and type of carbon deposition are discussed. The CP method forms very active small sized NiO (15 nm) and CeO2 (4 nm) nanoparticles, leading to the formation of a lower amount of carbon deposition in the form of nanofibrous carbon materials, the size of which depends on the Ni related nanoparticles. For CP catalysts, the graphitic filaments obtained correspond to carbon nanofibers (CNFs) and carbon nanotubes (CNTs) with a much smaller and homogenous size compared to the filamentous carbon formed over the catalysts issued from the other preparation methods, in relation to the active particles size. The catalytic stability is attributed to the type of carbon formed.

Chemical deposition of CuInSe2 thin films by photoelectrochemical applications - Hankare, P. P.; Rathod, K. C.; Chate, P. A.; Garadkar, K. M.; Sathe, D. J.; Mulla, Imtiaz S. (Journal of Alloys and Compounds, 2012)
Copper indium diselenide films have been synthesized by chemical bath deposition method. The configuration of fabricated cell is n-CuInSe2|NaOH (1 M) + S (1 M) + Na2S (1 M)|C-(graphite). The photoelectrochemical cell characterization of the films is carried out by studying current-voltage characteristics in dark, capacitance-voltage in dark, barrier height measurements, power output, photoresponse and spectral response. The study shows that CuInSe2 thin films are n-type conductivity. The junction ideality factor is found to be 3.81. The flat band potential is found to be 0.763 V. The barrier height value is found to be 0.232 eV. The study of power output characteristic shows open circuit voltage, short circuit current, fill factor and efficiency are found to be 310 mV, 20 mu A, 42.12% and 0.82%, respectively. Photoresponse shows lighted ideality factor which is 2.92. Spectral response shows the maximum current observed at 650 nm. (C) 2011 Published by Elsevier B.V.
Keywords: Chemical bath deposition; Flat band potential; Photo response; Power output; Spectral response

Cholesterol-tethered platinum II-based supramolecular nanoparticle increases antitumor efficacy and reduces nephrotoxicity - Sengupta, Poulomi; Basu, Sudipta; Soni, Shivani; Pandey, Ambarish; Roy, Bhaskar; Oh, Michael S.; Chin, Kenneth T.; Paraskar, Abhimanyu S.; Sarangi, Sasmit; Connor, Yamicia; Sabbisetti, Venkata S.; Kopparam, Jawahar; et al. (Proceedings of the National Academy of Sciences of the United States of America, 2012)
Nanoscale drug delivery vehicles have been harnessed extensively as carriers for cancer chemotherapeutics. However, traditional pharmaceutical approaches for nanoformulation have been a challenge with molecules that exhibit incompatible physicochemical properties, such as platinum-based chemotherapeutics. Here we propose a paradigm based on rational design of active molecules that facilitate supramolecular assembly in the nanoscale dimension. Using cisplatin as a template, we describe the synthesis of a unique platinum (II) tethered to a cholesterol backbone via a unique monocarboxylato and O -> Pt coordination environment that facilitates nanoparticle assembly with a fixed ratio of phosphatidylcholine and 1,2-distearoyl-sn-glycero-3-phosphoethanolamine- N-[amino (polyethylene glycol)-2000]. The nanoparticles formed exhibit lower IC50 values compared with carboplatin or cisplatin in vitro, and are active in cisplatin-resistant conditions. Additionally, the nanoparticles exhibit significantly enhanced in vivo antitumor efficacy in murine 4T1 breast cancer and in K-Ras(LSL/+/)Pten(fl/fl) ovarian cancer models with decreased systemic- and nephro-toxicity. Our results indicate that integrating rational drug design and supramolecular nanochemistry can emerge as a powerful strategy for drug development. Furthermore, given that platinum-based chemotherapeutics form the frontline therapy for a broad range of cancers, the increased efficacy and toxicity profile indicate the constructed nanostructure could translate into a nextgeneration platinum-based agent in the clinics.
Keywords: chemotherapy; nanomedicine

Comparative genomics of the apicomplexan parasites toxoplasma gondii and neospora caninum: coccidia differing in host range and transmission strategy - Reid, Adam James; Vermont, Sarah J.; Cotton, James A.; Harris, David; Hill-Cawthorne, Grant A.; Koenen-Waisman, Stephanie; Latham, Sophia M.; Mourier, Tobias; Norton, Rebecca; Quail, Michael A.; Sanders, Mandy; Shanmugam, Dhanasekaran; et al. (Plos Pathogens, 2012)
Toxoplasma gondii is a zoonotic protozoan parasite which infects nearly one third of the human population and is found in an extraordinary range of vertebrate hosts. Its epidemiology depends heavily on horizontal transmission, especially between rodents and its definitive host, the cat. Neospora caninum is a recently discovered close relative of Toxoplasma, whose definitive host is the dog. Both species are tissue-dwelling Coccidia and members of the phylum Apicomplexa; they share many common features, but Neospora neither infects humans nor shares the same wide host range as Toxoplasma, rather it shows a striking preference for highly efficient vertical transmission in cattle. These species therefore provide a remarkable opportunity to investigate mechanisms of host restriction, transmission strategies, virulence and zoonotic potential. We sequenced the genome of N. caninum and transcriptomes of the invasive stage of both species, undertaking an extensive comparative genomics and transcriptomics analysis. We estimate that these organisms diverged from their common ancestor around 28 million years ago and find that both genomes and gene expression are remarkably conserved. However, in N. caninum we identified an unexpected expansion of surface antigen gene families and the divergence of secreted virulence factors, including rhoptry kinases. Specifically we show that the rhoptry kinase ROP18 is pseudogenised in N. caninum and that, as a possible consequence, Neospora is unable to phosphorylate host immunity-related GTPases, as Toxoplasma does. This defense strategy is thought to be key to virulence in Toxoplasma. We conclude that the ecological niches occupied by these species are influenced by a relatively small number of gene products which operate at the host-parasite interface and that the dominance of vertical transmission in N. caninum may be associated with the evolution of reduced virulence in this species.

Competition between gelation and crystallisation of a peculiar multicomponent liquid system based on ammonium salts - Kapoor, Iti; Schoen, Eva-Maria; Bachl, Jurgen; Kuehbeck, Dennis; Cativiela, Carlos; Saha, Subhadeep; Banerjee, Rahul; Roelens, Stefano; Juan Marrero-Tellado, Jose; Diaz, David Diaz (Soft Matter, 2012)
An exemplar competition between gelation and crystallisation phenomena was examined with an unusual synergistic multicomponent (organo) gelator solution (MGS), which consists of a well-defined methanolic solution of (1R, 2R)-1,2-diaminocyclohexane L-tartrate containing 2.4 equiv. of concentrated hydrochloric acid. The optimal composition of the MGS was determined through meticulous solubility, gelation and structural studies, which support a transient gelation mechanism based on the kinetic self-assembly of the tartrate salt driven by hydrogen-bonding interactions, involving ammonium nitrogen donors and hydroxyl oxygen acceptors, and electrostatic interactions. The hydrochloric acid is involved in the solubilisation of the salt through an ionic dissociation-exchange process, which ends up with the formation-precipitation of (1R, 2R)-1,2-diaminocyclohexane dihydrochloride. As a consequence, an irreversible destruction of the gel takes place, which indicates the metastable nature of this phase that cannot be accessed from the thermodynamically equilibrated state. Gelation of a variety of oxygenated and nitrogenated solvents with moderate polarity occurred efficiently using extremely low MGS concentrations at low temperatures, and the gel phase was confirmed by dynamic rheological measurements. Several features make the described MGS unique: (1) it is a multicomponent solution where each component and its stoichiometry play a key role in the reproducible formation and stabilization of the gels; (2) it is formed by simple, small, and commercially available chiral building blocks (dissolved in a well-defined solvent system), which are easily amenable for further modifications; (3) the gelation phenomenon takes place efficiently at low temperature upon warming up the isotropic solution, conversely to the typical gel preparation protocol; and (4) the formed organogels are not thermoreversible despite the non-covalent interactions that characterize the 3D-network.

Conversion of cellulose to polyols over promoted nickel catalysts - Shrotri, Abhijit; Tanksale, Akshat; Beltramini, Jorge Norberto; Gurav, Hanmant; Chilukuri, Satyanarayana V. (Catalysis Science & Technology, 2012)
Sorbitol is one of the key platform chemicals that can be applied to several industrial applications, including bio-fuels and hydrogen production. Presently there is no commercial heterogeneous catalytic process to produce sorbitol from cellulose due to the low yield and high cost of noble metals required for the conversion. In this paper we describe an aqueous phase hydrolysis-hydrogenation process to convert cellulose to sorbitol using a cheap Ni based catalyst. Monometallic Ni catalysts showed little activity for the reaction, but with the addition of a small amount of Pt to the Ni catalyst (Ni : Pt = 22 : 1 atom ratio), the activity was greatly enhanced. Results showed that the bimetallic Ni-Pt catalysts supported on mesoporous alumina gave a hexitol (sorbitol + mannitol) yield of 32.4% compared to only 5% with a Ni catalyst. Moreover, Ni-Pt supported on a mesoporous beta zeolite support provided even higher yield of 36.6%. These results were obtained after only 6 hours of run at 200 degrees C and 50 bar H-2 pressure (at room temperature). The presence of a small amount of Pt promotes the protonation of water and hydrogen molecules, which spill over to Ni sites creating in situ acid sites to catalyse hydrolysis of cellulose.

Development and validation of a simple and sensitive RP-HPLC method for simultaneous estimation of drospirenone and ethinylestradiol in combined tablet dosage form - Warkad, Shrikant D.; Santhakumari, B.; Chandewar, A. V. (International Journal of Pharmacy and Pharmaceutical Sciences, 2012)

Effect of the A30P mutation on the structural dynamics of micelle-bound alpha synuclein released in water: a molecular dynamics study - Chatterjee, Prathit; Sengupta, Neelanjana (European Biophysics Journal With Biophysics Letters, 2012)
Atomistic molecular dynamics simulation has been used to probe the effect of the A30P mutation on the structural dynamics of micelle-bound, helical alpha Synuclein when released in an aqueous environment. On the timescales simulated, the effect of the mutation on the secondary structure is restricted to local changes close to the mutation site in the N-terminal helical domain. The changes are transient, and all residues except Lys23 recover their initial structure. The local behavior due to the mutation gives rise to a global difference in the A30P mutant in the form of a permanent kink in the N-terminal helical domain.
Keywords: A30P mutation; Alpha synuclein; Kink formation; molecular dynamics simulation; Structural persistence

Efficient, rapid synthesis of bis(indolyl)methane using ethyl ammonium nitrate as an ionic liquid - Mulla, Shafeek Abdul Rashid; Sudalai, A.; Pathan, Mohsinkhan Y.; Siddique, Shafi A.; Inamdar, Suleman M.; Chavan, Santosh S.; Reddy, R. Santosh (RSC Advances, 2012)
A simple and rapid protocol has been developed for an efficient synthesis of bis( indolyl)methane in excellent yields using ethyl ammonium nitrate (EAN) as reusable ionic liquid at room temperature. The protocol involves an electrophilic substitution reaction of indoles with several aldehydes.

Enantioselective synthesis of the essential oil and pheromonal component ar-himachalene by a chiral pool and chirality induction approach - Chavan, Subhash P.; Khatod, Harshali S. (Tetrahedron-Asymmetry, 2012)
The enantioselective synthesis of both isomers of ar-himachalene has been achieved starting from enantiomerically pure citronellal and p-methyl alpha-methyl styrene as an application of a chiral pool and chirality induction approach, respectively. The key reactions involved in the synthesis include the Sharpless asymmetric dihydroxylation for the induction of chirality at benzylic carbon bearing the methyl group and the use of a hypervalent iodine reagent or trimethylsilyldiazomethane (TMSCHN2) for the six to seven membered ring expansion. (C) 2012 Elsevier Ltd. All rights reserved.

Enhanced photocatalytic activity of multi-doped TiO2 for the degradation of methyl orange - Charanpahari, A.; Umare, S. S.; Gokhale, S. P.; Sudarsan, V.; Sreedhar, B.; Sasikala, R. (Applied Catalysis A-General, 2012)
We report the synergistic effect of dopants like Gd, N and Sin enhancing the photocatalytic activity of TiO2. Nanosized TiO2 doped at both cationic and anionic sites by Gd, N and S exhibited increased photocatalytic activity compared to TiO2 doped with either Gd or N and S. All the doped TiO2 existed as anatase phase and no separate phase due to Gd2O3 was seen up to a Gd concentration of 2%. The particle size as seen from the transmission electron micrograph was similar to 25 nm. The optical absorption property of TiO2 was improved by doping and redshift of the absorption edge is seen for all doped samples compared to pristine TiO2. The red shift of the absorption edge was the highest for the multiple ion-doped sample. Presence of bonded N and S in TiO2 was detected by X-ray photoelectron spectroscopy. Fluorescence lifetime studies indicated an enhanced lifetime for the charge carriers in the doped system compared to pristine TiO2. Photocatalytic activity study showed that the multi-doped sample has the highest activity for the degradation of methyl orange compared to Gd-TiO2, NS-TiO2 and pristine TiO2. The enhanced photocatalytic activity of the multi-doped TiO2 is attributed to factors such as improved optical absorption property and improved lifetime of the charge carriers. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Fluorescence lifetime; Gd N S doped TiO2; Methyl orange; Photocatalyst; Photodegradation

Enhancing the hydrogen storage capacity of Pd-functionalized multi-walled carbon nanotubes - Singh, Priyanka; Kulkarni, Mukta V.; Gokhale, Suresh P.; Chikkali, Samir H.; Kulkarni, Chandrashekhar V. (Applied Surface Science, 2012)
We demonstrate that the hydrogen storage capacity of multi-walled carbon nanotubes can be enhanced by polyvinylpyrrolidone functionalization. The polyvinylpyrrolidone acts as a stabilizing agent for Pd-nanoparticles, reduces their size and facilitates their uniform and enhanced loading onto multi-walled carbon nanotubes. According to sorption studies, the polyvinylpyrrolidone capping and consequent nanostructural modification enables 2.3 times more hydrogen adsorption than mere Pd-functionalization of multi-walled carbon nanotubes. Corresponding morphological changes before and after polyvinylpyrrolidone capping, characterized using Raman Spectroscopy, X-ray diffraction, TEM and thermal analysis techniques, are also presented. The results contribute towards increasing the efficiency of hydrogen based sustainable energy sources. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Hydrogen based energy sources; Hydrogen storage capacity; Multiwalled carbon nanotubes; Pd functionalization; PVP capping

Epitaxial magnetic oxide nanocrystals via phase decomposition of bismuth perovskite precursors - Bogle, Kashinath A.; Cheung, Jeffrey; Chen, Yong-Lun; Liao, Sheng-Chieh; Lai, Chih-Hung; Chu, Ying-Hao; Gregg, John M.; Ogale, Satishchandra B.; Valanoor, Nagarajan (Advanced Functional Materials, 2012)
The phase instability of bismuth perovskite (BiMO3), where M is a ferromagnetic cation, is exploited to create self-assembled magnetic oxide nanocrystal arrays on oxide supports. Conditions during pulsed laser deposition are tuned so as to induce complete breakdown of the perovskite precursor into bismuth oxide (Bi2O3) and metal oxide (M-Ox) pockets. Subsequent cooling in vacuum volatizes the Bi2O3 leaving behind an array of monodisperse nanocrystals. In situ reflective high energy electron diffraction beam is exploited to monitor the synthesis in real-time. Analysis of the patterns confirms the phase separation and volatization process. Successful synthesis of M-Ox, where M = Mn, Fe, Co, and Cr, is shown using this template-free facile approach. Detailed magnetic characterization of nanocrystals is carried out to reveal the functionalities such as magnetic anisotropy as well as larger than bulk moments, as expected in these oxide nanostructures.
Keywords: Bi2O3 evaporation; bismuth perovskites; epitaxial nanostructures; magnetic oxides; phase separation

Ethyl oligo-silicates with strong acid heterogeneous polymeric catalysts - Bevara, Madhusudana Rao; Bhongale, Sunil Sitaram; Bhosle, Sonali Madhavrao; Chavan, Nayaku; Chelanattukizhakkemadath, Raman Rajan; Deokar, Sarika Babasaheb; Dhoble, Deepa Arun; Dwivedi, Mayank; Ghorpade, Ravindra V.; Harikrishna, Reghunathan; Dhanasekharan, Janakiraman; John, Aruldoss; et al. (WO2012056290 A1, 2012)
The present invention provides a process for the synthesis of ethyl silicate with varying silica concentration, by hydrolysing ethyl silicate in varying water concentration in the presence of sulfonated catalysts having a styrene-divinyl benzene backbone. The present invention further relates to the preparation of beaded crosslinked polymers containing sulfonic acid moieties having an interconnected pore structure and surface area up to 400 m2 /g.

FeCl3/Montmorillonite K10 as an efficient catalyst for solvent-free aza-Michael reaction between amine and alpha,beta-unsaturated compounds - Choudhary, Vasant R.; Dumbre, Deepa K.; Patil, S. K. (RSC Advances, 2012)
A highly efficient, inexpensive and greener protocol for aza-Michael addition reaction of different aromatic and aliphatic/cyclic amines to alpha,beta-unsaturated compounds using a FeCl3/MontK10 catalyst under solvent-free conditions has been developed. The Michael addition products are obtained in good to excellent yields. The catalyst was insensitive to moisture and it also showed excellent reusability in the reaction. Its high activity is attributed mostly to redox properties of FeCl3.

Fluorinated metal-organic frameworks: advantageous for higher H-2 and CO2 adsorption or not? - Pachfule, Pradip; Chen, Yifei; Jiang, Jianwen; Banerjee, Rahul (Chemistry-A European Journal, 2012)
The synthesis, structure, and gas adsorption properties of three new metalorganic frameworks (MOFs) designed from isonicotinic acid (INA) and its fluorinated analogue 3-fluoroisonicotinic acid (FINA) along with CoII as the metal center have been reported. Co-INA-1 ([Co3(INA)4(O)(C2H5OH)3][NO3].C2H5OH.3?H2O; INA=isonicotinic acid) and Co-INA-2 ([Co(INA)2].DMF) are structural isomers as are Co-FINA-1 ([Co3(FINA)4(O)(C2H5OH)2].H2O; FINA=3-fluoroisonicotinic acid) and Co-FINA-2 ([Co(FINA)2].H2O), but the most important thing to note here is that Co-INA-1 and Co-FINA-1 are isostructural as are Co-INA-2 and Co-FINA-2. The effect of partial introduction of fluorine atoms into the framework on the gas uptake properties of MOFs having similar structures has been analyzed experimentally and computationally in isostructural MOFs.
Keywords: cobalt; fluorine; Hydrogen storage; metal-organic frameworks; microporous materials; X-ray diffraction

Formal synthesis of (-)-stemoamide using a useful epimerization at C-8 - Chavan, Subhash P.; Harale, Kishor R.; Puranik, Vedavati G.; Gawade, Rupesh L. (Tetrahedron Letters, 2012)
The formal synthesis of (-)-stemoamide was achieved starting from L-pyroglutamic acid. The key steps used are the allylation using BF3 center dot OEt2, ring closing metathesis, allylic oxidation and a novel epimerization at C8. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Allylation; Allylic oxidation; Pyroglutamic acid; Ring closing metathesis; Stemoamide

Geographic variation in the flavour volatiles of alphonso mango - Kulkarni, Ram S.; Chidley, Hemangi G.; Pujari, Keshav H.; Giri, Ashok P.; Gupta, Vidya S. (Food Chemistry, 2012)
Alphonso, one of the most popular cultivars of mango in India is known to exhibit geographic variation in the flavour of ripe fruits. To get chemical insight into this difference, volatiles were studied in the ripening fruits of Alphonso mangoes from three cultivation locations in India. Ripe fruits from Deogad had lower content of mono- and sesquiterpenes and higher content of lactones and furanones as compared to the fruits from Dapoli: whereas fruits from Vengurle had average quantities of these chemicals in comparison with Deogad and Dapoli fruits. This variation was clearly reflected as separate clustering of the localities in the Principal Component Analysis. The localities were indistinguishable from each other in terms of raw fruit volatiles. This study exemplifies a case of phenotypic plasticity; since the plants chosen were clonally propagated, such geographic variation in the volatiles can be attributed to varied abiotic conditions at these three localities. (C) 2011 Elsevier Ltd. All rights reserved.
Keywords: Mango; Phenotypic plasticity; Ripening; Volatiles

Heterocyclic tri-urea isocyanurate bridged groups modified periodic mesoporous organosilica synthesized for Fe(III) adsorption - Rana, Vijay Kumar; Selvaraj, M.; Parambadath, Surendran; Chu, Sang-Wook; Park, Sung Soo; Mishra, Satyendra; Singh, Raj Pal; Ha, Chang-Sik (Journal of Solid State Chemistry, 2012)
To achieve a high level of heavy metal adsorption, 1,1',1 `'-(1,3,5-triazine-2,4,6-triyl)tris(3-(3-(triethoxysilyl) propyl)urea) (TTPU) was synthesized as a novel melamine precursor and incorporated on the silica surface of periodic mesoporous organosilica (PMO). The melamine modified PMOs (MPMOs) were synthesized under acidic conditions using TTPU, tetraethylorthosilicate (TEOS) and Pluronic P123 as a template and the modified PMOs were characterized using the relevant instrumental techniques. The characteristic materials were used as adsorbents for the adsorption of Fe(III) ions. Fe(III) adsorption studies revealed MPMO-7.5 to be a good absorbent with higher adsorption efficiency than other MPMOs. (C) 2012 Elsevier Inc. All rights reserved.
Keywords: Adsorption efficiency; Fe(III) adsorption; Melamine; Periodic mesoporous organosilica (PMO)

Highly diastereoselective total synthesis of (+/-)-heritonin and (+/-)-heritol - Chavan, Subhash P.; Garai, Sumanta; Kalkote, Uttam R. (Tetrahedron, 2012)
A highly diastereoselective synthesis of heritol and heritonin by intramolecular cyclization on a preformed sensitive butenolide functionality is described. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Butenolide; cyclization; Dihydroxylation; Friedel-Crafts acylation; Tetralone

Hybrid molecules of carvacrol and benzoyl urea/thiourea with potential applications in agriculture and medicine - Pete, Umesh D.; Zade, Chetan M.; Bhosale, Jitendra D.; Tupe, Santosh G.; Chaudhary, Preeti M.; Dikundwar, Amol G.; Bendre, Ratnamala S. (Bioorganic & Medicinal Chemistry Letters, 2012)
Benzoyl phenyl urea, a class of insect growth regulator's acts by inhibiting chitin synthesis. Carvacrol, a naturally occurring monoterpenoid is an effective antifungal agent. We have structurally modified carvacrol (2-methyl-5-[1-methylethyl] phenol) by introducing benzoylphenyl urea linkage. Two series of benzoylcarvacryl thiourea (BCTU, 4a-f) and benzoylcarvacryl urea (BCU, 5a-f) derivatives were prepared and characterized by elemental analysis, IR, H-1 and C-13 NMR and Mass spectroscopy. Derivatives 4b, 4d, 4e, 4f and 5d, 5f showed comparable insecticidal activity with the standard BPU lufenuron against Dysdercus koenigii. BCTU derivatives 4c, 4e and BCU 5c showed good antifungal activity against phytopathogenic fungi viz. Magnaporthe grisae, Fusarium oxysporum, Dreschlera oryzae; food spoilage yeasts viz. Debaromyces hansenii, Pichia membranifaciens; and human pathogens viz. Candida albicans and Cryptococcus neoformans. Compounds 5d, 5e and 5f showed potent activity against human pathogens. Moderate and selective activity was observed for other compounds. All the synthesized compounds were non-haemolytic. These compounds have potential application in agriculture and medicine. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Antifungal agents; Benzoyl carvacryl urea; Benzoyl phenyl urea; Crop protection agents; Insect growth regulators

Identification of cholesterol binding sites in the serotonin(1A) receptor - Sengupta, Durba; Chattopadhyay, Amitabha (Journal of Physical Chemistry B, 2012)
The serotonin(1A) receptor is a representative member of the G protein-coupled receptor (GPCR) superfamily and serves as an important drug target in the development of therapeutic agents for neuropsychiatric disorders. Previous work has shown the requirement of membrane cholesterol in the organization, dynamics, and function of the serotonin(1A) receptor. We show here that membrane cholesterol binds preferentially to certain sites on the serotonin(1A) receptor by performing multiple, long time scale MARTINI coarse-grain molecular dynamics simulations. Interestingly, our results identify the highly conserved cholesterol recognition/interaction amino acid consensus (CRAC) motif on transmembrane helix V as one of the sites with high cholesterol occupancy, thereby confirming its role as a putative cholesterol binding motif. These results represent the first direct evidence for membrane cholesterol binding to specific sites on the serotonin(1A) receptor and represent an important step in our overall understanding of GPCR function in health and disease.

Immobilization of enantioselective lipase on soluble supports for kinetic resolution of drug intermediates - Chaubey, Asha; Parshad, Rajinder; Taneja, Subhash C.; Deokar, Sarika Babasaheb; Raman, Rajan C.; Ponrathnam, Surendra (Journal of Bioactive and Compatible Polymers, 2012)
The microbial lipase, Arthrobacter sp. lipase (MTCC 5125), from the Indian Institute of Integrative Medicine repository, is known as an effective catalyst for high enantioselective kinetic resolution of drug intermediates. The ABL was immobilized on water-soluble linear supports by covalently binding it to the epoxy groups on the N-vinyl pyrrolidone/allyl glycidyl ether and N-vinyl pyrrolidone/glycidyl methacrylate copolymers. The immobilized lipase, on different soluble supports, had 90-110 mg/g protein binding and 500-700 U/g hydrolysis activities for tributyrin substrate. These copolymers had soluble/insoluble characteristics in different pH ranges, which is an advantage over insoluble copolymers. A soluble polymer at neutral pH provided better accessibility to the immobilized enzyme, which was recovered by precipitation at pH 2-3 for reuse. Kinetic resolution of racemic acyl derivatives of chiral auxiliaries and drug intermediates, namely, phenyl ethanol, aminoalcohol, and fluoxetine intermediate resulted in a significant enhancement in enantioselectivity (99%).
Keywords: Arthrobacter sp lipase; Enantioselectivity; Immobilization; Kinetic resolution; N-vinylpyrrolidone; soluble polymer

Interfacial and film formation behavior of photoactive Ru(ii)bipyridyl based metallosurfactants and a rare example of a monolayer based logic gate approach - Mahato, Prasenjit; Saha, Sukdeb; Choudhury, Sipra; Das, Amitava (Chempluschem, 2012)
Three derivatives of tris(bipyridyl)–ruthenium(II) complexes with different alkyl-chain lengths (nC18H37 (1), nC14H29 (2) and nC10H21 (3)) were synthesised. All these complexes behaved as an amphiphile and their surface properties were studied at the air–water interface by measuring surface pressure–area (Π–A) isotherms. The surface morphology of the resulting films at the air–water interface was also studied by using Brewster angle microscopy. Mean molecular areas of these complexes were measured from the Π–A isotherms, which were approximately 200 Å2, thereby indicating a parallel arrangement of the Ru–bipyridyl moiety of the complexes. Mono- and multilayer Langmuir–Blodgett (LB) films were formed on different solid surfaces with transfer ratios close to one. Similarities in the absorption and fluorescence spectra of these amphiphiles in solution as well as in LB films deposited on a quartz surface confirmed the successful transfer of these films onto the substrates. The latter provided information about the arrangements of metallosurfactant molecules within the LB films. The two-dimensional concentrations of these films were calculated from the Lambert–Beer law as well as from the Π–A isotherm, which confirmed regular and reproducible transfer of the complex monolayers from the air–water interface onto the quartz surface. The surface morphology of these films on various substrates was characterised by atomic force microscopy. Furthermore, by oxidising the monolayer of complex 3, a one-input sequential logic gate was constructed.

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

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

Ligand free, highly efficient synthesis of diaryl ether over copper fluorapatite as heterogeneous reusable catalyst - Mulla, Shafeek Abdul Rashid; Inamdar, Suleman M.; Pathan, Mohsinkhan Y.; Chavan, Santosh S. (Tetrahedron Letters, 2012)
A novel ligand-free, highly efficient, and an inexpensive method has been developed by using ecofriendly, heterogeneous reusable copper fluorapatite (CuFAP) catalyst for the synthesis of diaryl ethers from the cross coupling reaction of the various substituted aryl halides (fluoride, chloride, bromide, and iodide) with the potassium salts of various substituted phenols in the presence of N-methyl 2-pyrrolidone (NMP) as a solvent at 120 degrees C. The protocol obtained the corresponding cross coupling products in good to excellent yield. The CuFAP catalyst was recovered by simple filtration from the reaction mixture and reused several times without the loss of catalytic activity. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Arylhalide; Copper fluorapatite; Diaryl ethers; phenol; Ullmann coupling

Ligand promoted and controlled palladium-catalyzed intramolecular Heck reaction of homoallyl alcohols: a facile synthesis of cyclopentaannulated quinolines - Singh, Radhey M.; Chandra, Atish; Sharma, Neha; Singh, Bhawana; Kumar, Ritush (Tetrahedron, 2012)
Bidentate phosphine ligands in palladium-catalyzed intramolecular Heck reactions of 2-chloroquinolin-3-yl-(1-homoallyl)alcohols are described to afford facile synthesis of 3-methylene-2,3-dihydro-1H-cy-clopenta[b]quinolines in improved yields. We further observed using bulky aromatic phosphine ligand in Pd-catalyzed intermolecular Heck coupling reaction at olefinic centers with iodobenzene also favored exclusively Heck products in excellent yield. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Heck cyclization; Homoallyl alcohol; Ligand promoted; Palladium-catalyzed; Quinoline

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

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

Molecular dynamics simulation of phosphoric acid doped monomer of polybenzimidazole: a potential component polymer electrolyte membrane of fuel cell - Pahari, Swagata; Choudhury, Chandan Kumar; Pandey, Prithvi Raj; More, Minal; Venkatnathan, Arun; Roy, Sudip (Journal of Physical Chemistry B, 2012)
Phosphoric acid doped polybenzimidazole is promising electrolyte membranes for high temperature (100 degrees C and above) fuel cells. Proton conduction is governed by the amount of phosphoric acid content in the polymer membrane. In this present work, we perform molecular dynamics simulations on phosphoric acid doped 2-phenyl-1H,1'H-5,5'-bibenzo[d]imidazole (monomer unit of polybenzimidazole) to characterize the structural and dynamical properties at varying phosphoric acid content and temperature. From the structural analysis, we have predicted the arrangement of the phosphoric acids, formation of H-bonds in the system, and the contribution of different atoms toward H-bonding. We have also examined the stacking of 2-phenyl-1H,1'H-5,5'-bibenzo[d]imidazole molecules and how their arrangement changes with the increasing amount of PA in the system with the help of cluster analysis. From the molecular dynamics simulation conducted at different temperatures and phosphoric acid doping level, we have predicted the diffusion of phosphoric acid and monomer. As a dynamic quantity, we have also calculated ring flipping of the imidazole ring of the monomer.

Multi-Hit action of membrane active peptides: towards understanding bacterial cell killing - Moiset, Gemma; Cirac, Anna D.; Mika, Jacek T.; Kocer, Armagan; Stuart, Marc C. A.; Sengupta, Durba; Marrink, Siewert-Jan; Poolman, Bert (Biophysical Journal, 2012)

NaIO4-NaN3-mediated diazidation of styrenes, alkenes, benzylic alcohols, and aryl ketones - Kamble, Dayanand A.; Karabal, Pratibha U.; Chouthaiwale, Pandurang V.; Sudalai, Arumugam (Tetrahedron Letters, 2012)
Sodium periodate and sodium azide combination has been found to be an excellent reagent system suitable for the direct diazidation of styrenes, alkenes, benzylic alcohols, and aryl ketones to produce the corresponding vicinal and geminal diazides respectively in high yields under mild reaction conditions. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: alkenes; Aryl ketones; Geminal diazides; Sodium periodate; Vicinal diazides

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

Noble metal ions incorporated in lattice points of perovskites - water gas shift activity of BaCe1-xPtxO3-d - Jijil, Chamundi P.; Rajarajan, A. K.; Devi, R. Nandini (56th DAE-Solid State Physics Symposium (SSPS), 2012)
Recently precious metals supported on oxides were reported to be very promising catalysts for the lower-temperature WGS reaction. Here we report the synthesis of platinum doped barium cerate and its use as catalysts for WGS reaction. It has been found that maximum CO conversion was obtained at 350 degrees C which enhanced after the first cycle. XPS analysis shows that after the first cycle more ionic Platinum species are present on the surface of the catalyst. Neutron diffraction at room temperature shows that the oxygen vacancies are in the O2 position and increases with increasing Pt substitution.
Keywords: BaCeO3; Neutron diffraction; Platinum catalysis; WGS reaction

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

Organization of cubic CeO2 nanoparticles on the edges of self assembled tapered ZnO nanorods via a template free one-pot synthesis: significant cathodoluminescence and field emission properties - Warule, Sambhaji S.; Chaudhari, Nilima S.; Kale, Bharat B.; Patil, Kashinath R.; Koinkar, Pankaj M.; More, Mahendra A.; Murakami, Ri-ichi (Journal of Materials Chemistry, 2012)
The present investigation explores the controlled architecture of a CeO2-ZnO nanocomposite via a template-free, low temperature, facile single step solvothermal approach. This complex architecture depicts cubic single crystalline CeO2 nanoparticles (size similar to 15 nm) grown on the edges of tapered ZnO nanorods with definite orientations and alignments. The formation of wurtzite ZnO, cubic CeO2 and the coexistence of Ce3+ and Ce4+ on the surface of the CeO2-ZnO nanocomposites are confirmed using various characterization tools. The finding of such unique nanostructures by a facile method is exemplified by a plausible growth mechanism. Surprisingly, the aqueous mediated ultrasonication reaction conferred the formation of crystalline ZnO nanotubes of diameter similar to 50 nm. Spatially resolved cathodoluminescence spectra are obtained by linearly scanning an individual CeO2-ZnO nanorod along its length, which reveals the size-dependent surface effects. Interestingly, such hybrid CeO2-ZnO nanoarchitecture is observed to exhibit enhanced field emission properties, demonstrating better current stability as compared to other ZnO nanostructures. This is attributed mainly to strong surface interactions between the Ce-ionic species and the ZnO nanorods. Herein, a soft-chemical approach is used for the first time to architect a binary oxide nanostructure, which is otherwise accomplished using high temperature techniques, as reported elsewhere. Also, the present work not only gives insight into understanding the hierarchical growth behaviour of the CeO2-ZnO nanocomposite in a solution phase synthetic system, but also provides an efficient route to enhance the field emission performance of ZnO nanostructures, which could be extended to other potential applications, such as chemical sensors, optoelectronic devices and photocatalysts.

Pd-catalyzed selective hydrosilylation of aryl ketones and aldehydes - Chouthaiwale, Pandurang V.; Rawat, Varun; Sudalai, Arumugam (Tetrahedron Letters, 2012)
Pd salts in combination with triethylsilane as hydride source and DMF as solvent has been found to be excellent catalytic combination that selectively reduces aryl ketones and aldehydes under mild conditions to afford triethylsilyloxy compounds in excellent yields. Product selectivity to the respective benzyl alcohols can however be achieved when the reaction was performed in DMF/H2O (4:1) as solvent system. (C) 2011 Elsevier Ltd. All rights reserved.
Keywords: aldehydes; Hydrosilylation; Ketones; Palladium; Triethylsilane

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

Polybenzimidazole mediated N-doping along the inner and outer surfaces of a carbon nanofiber and its oxygen reduction properties - Balan, Beena K.; Manissery, Aiswarya Padinhare; Chaudhari, Harshal D.; Kharul, Ulhas K.; Kurungot, Sreekumar (Journal of Materials Chemistry, 2012)
Nitrogen-doped (N-doped) hollow carbon nanofiber (CNF) was synthesized by incorporating a nitrogen containing polymer precursor, polybenzimidazole (PBI-BuI), in the inner cavity as well as on the outer walls of the CNF, followed by a high temperature treatment. PBI-BuI incorporation along the inner and outer surface of the CNF was accomplished by synthesizing a low molecular weight polymer by tuning the synthetic parameters. The solution concentration of the PBI-BuI is also varied to facilitate its entry into the CNF by capillary action. The high temperature treatment (700-1000 degrees C) of the resulting CNF-PBI material decomposes the polymer and induces N-doping along the inner and outer surfaces of the CNF. The initial PBI-BuI content and the annealing temperature are also systematically varied to choose the right combination of starting precursors and heat-treatment conditions. Detailed X-ray photoelectron spectroscopy analysis of the samples shows that pyridinic-type nitrogen is the major component in all the samples. Electrochemical characterizations of this material using cyclic voltammetry, rotating disc electrode studies and durability analysis demonstrated that this material can act as a metal-free oxygen reduction electrocatalyst with improved oxygen reduction kinetics and stability. It is also revealed that the onset potential, limiting current density, number of transferred electrons, etc. have a strong dependence on the annealing temperature.

Polymorphs, salts, and cocrystals: what's in a name? - Aitipamula, Srinivasulu; Banerjee, Rahul; Bansal, Arvind K.; Biradha, Kumar; Cheney, Miranda L.; Choudhury, Angshuman Roy; Desiraju, Gautam R.; Dikundwar, Amol G.; Dubey, Ritesh; Duggirala, Nagakiran; Ghogale, Preetam P.; Ghosh, Soumyajit; et al. (Crystal Growth & Design, 2012)
The December 2011 release of a draft United States Food and Drug Administration (FDA) guidance concerning regulatory classification of pharmaceutical cocrystals of active pharmaceutical ingredients (APIs) addressed two matters of topical interest to the crystal engineering and pharmaceutical science communities: (1) a proposed definition of cocrystals; (2) a proposed classification of pharmaceutical cocrystals as dissociable ``API-excipient'' molecular complexes. The Indo U.S. Bilateral Meeting sponsored by the Indo-U.S. Science and Technology Forum titled The Evolving Role of Solid State Chemistry in Pharmaceutical Science was held in Manesar near Delhi, India, from February 2-4, 2012. A session of the meeting was devoted to discussion of the FDA guidance draft. The debate generated strong consensus on the need to define cocrystals more broadly and to classify them like salts. It was also concluded that the diversity of API crystal forms makes it difficult to classify solid forms into three categories that are mutually exclusive. This perspective summarizes the discussion in the Indo-U.S. Bilateral Meeting and includes contributions from researchers who were not participants in the meeting.

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

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

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

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

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

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

Reply to comment on ``Reductive dechlorination of gamma-hexachlorocyclohexane using Fe-Pd bimetallic nanoparticles'', by C. Noubactep - Nagpal, Varima; Bokare, Alok D.; Chikate, Rajeev C.; Rode, Chandrashekhar V.; Paknikar, Kishore M. (Journal of Hazardous Materials, 2012)

Rhodamine-alginate conjugate as self-indicating gel beads for efficient detection and scavenging of Hg 2+ and Cr 3+ in aqueous media - Saha, Sukdeb; Chhatbar, Mahesh U.; Mahato, Prasenjit; Praveen, L.; Siddhanta, A. K.; Das, Amitava (Chemical Communications, 2012)
Effective extraction of Hg2+ and Cr3+ ions from aqueous media by novel rhodamine–alginate polymer-based highly fluorogenic, as well as colorimetric, chemosensor beads.

Selective oxidation of nonrefractory and refractory sulfides by cyclopentadienyl molybdenum acetylide complexes as efficient catalysts - Chandgude, Macchindra G.; Biradar, Ankush V.; Kotbagi, Trupti V.; Puranik, Vedavati G.; Dongare, Mohan K.; Shubhangi B. Umbarkar (Catalysis Letters, 2012)
{The synthesis and catalytic properties of molybdenum acetylide complexes CpMo(CO)(3)(-C CR)
Keywords: Homogeneous catalysis; Molybdenum acetylide; Oxo-peroxo species; Refractory sulfide oxidation

Selective recognition of fluoride and acetate by a newly designed ruthenium framework: experimental and theoretical investigations - Kundu, Tanaya; Chowdhury, Abhishek Dutta; De, Dipanwita; Mobin, Shaikh M.; Puranik, Vedavati G.; Datta, Anindya; Lahiri, Goutam Kumar (Dalton Transactions, 2012)
{An effective anion sensor, [Ru-II(bpy)(2)(H2L-)](+) (1(+)), based on a redox and photoactive {Ru-II(bpy)(2)} moiety and a new ligand (H3L = 5-(1H-benzo[d]imidazol-2-yl)-1H-imidazole-4-carboxylic acid), has been developed for selective recognition of fluoride (F-) and acetate (OAc-) ions. Crystal structures of the free ligand, H3L and [1](ClO4) reveal the existence of strong intramolecular and intermolecular hydrogen bonding interactions. The structure of [1](ClO4) shows that the benzimidazole N-H of H2L- is hydrogen bonded with the pendant carboxylate oxygen while the imidazole N-H remains free for possible hydrogen bonding interaction with the anions. The potential anion sensing features of 1(+) have been studied by different experimental and theoretical (DFT) investigations using a wide variety of anions, such as F-, Cl-, Br-, I-, HSO4-, H2PO4-, OAc- and SCN-. Cyclic voltammetry and differential pulse voltammetry established that 1(+) is an excellent electrochemical sensor for the selective recognition kof F- and OAc- anions. 1(+) is also found to be a selective colorimetric sensor for F- or OAc- anions where the MLCT band of the receptor at 498 nm is red shifted to 538 nm in the presence of one equivalent of F- or OAc- with a distinct change in colour from reddish-orange to pink. The binding constant between 1(+) and F- or OAc- has been determined to be logK = 7.61 or 7.88, respectively, based on spectrophotometric titration in CH3CN. The quenching of the emission band of 1(+) at 716 nm (lambda(ex) = 440 nm

Self–assembled histidine acid phosphate nanocapsules as templates for multifunctional hollow platinum nanospheres in ionic liquid [BMIM][BF 4 ] for drug delivery - Soni, Sarvesh Kumar; Sarkar, Sampa; Sarkar, Dhiman; Coloe, Peter J.; Bhargava, Suresh Kumar; Bansal, Vipul (Proceedings of Chemeca, 2012)
During the past few decades, the design and fabrication of nano drug delivery vehicle has received considerable attention for incorporating multi-functionality, emphasizing transportation of anticancer drugs to tumour sites. Protein-based nanoparticles hold significant promise in the development of anticancer drug delivery systems since they have remarkable superiority in biocompatibility, biodegradability and natural metabolism in physiologic systems. Ionic liquids (ILs) are a class of solvents that are composed solely of ions (ILs – commonly referred as room temperature molten salts or room temperature ionic liquids). They have recently emerged as green solvents or green reaction media, because of their reported unique physico-chemical properties. We report for the first time the controlled self-assembly of Histidine Acid phosphatase (HAP) enzyme in the IL 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF 4 ], leading to the formation of HAP nanocapsules as template for synthesis of platinum nanospheres. These HAP nano-containers were loaded with an anticancer drug curcumin. We further demonstrated in vitro drug release and synergistic anticancer effect of these systems on three different cell lines viz. hepatocellular carcinoma (HepG2), breast cancer (MCF-7) and human acute monocytes (THP-1). The present work can extend our theoretical understanding on nano-bio interfacial molecular self assembly and will facilitate the motivated insights of inorganic/organic hybrid nano-materials/ nano-particles/ nano-objects and ionic liquids based multi functional drug delivery vehicles with synergistic combination chemotherapy for potential application in tumor targeting. INTRODUCTION During the past few decades, the design and fabrication of drug delivery vehicle has received considerable attention for incorporating multi-functionality emphasizing transportation of anticancer drugs to tumour sites. These nano drug delivery vehicles have many advantages including prolonged circulation time of the drugs (Duncan, 2003, Kiick, 2007) , improved drug targeting and solubility (Duncan, 2003, Kiick, 2007), higher payloads (Duncan, 2003) and controlled release of the therapeutics into the blood stream or the targeted tumour tissues (Uhrich et al. 1999, Duncan, 2003).

Size-controlled flow synthesis of gold nanoparticles using a segmented flow microfluidic platform - Cabeza, Victor Sebastian; Kuhn, Simon; Kulkarni, Amol A.; Jensen, Klavs F. (Langmuir, 2012)
Segmented flow is often used in the synthesis of nanomaterials to achieve narrow particle size distribution. The narrowness of the distribution is commonly attributed to the reduced dispersion associated with segmented flows. On the basis of the analysis of flow fields and the resulting particle size distribution, we demonstrate that it is the slip velocity between the two fluids and internal mixing in the continuous-phase slugs that govern the nature of the particle size distribution. The reduction in the axial dispersion has less impact on particle growth and hence on the particle size distribution. Synthesis of gold nanoparticles from HAuCl4 with rapid reduction by NaBH4 serves as a model system. Rapid reduction yields gold nuclei, which grow by agglomeration, and it is controlled by the interaction of the nuclei with local flow. Thus, the difference in the physical properties of the two phases and the inlet flow rates ultimately control the particle growth. Hence, a careful choice of continuous and dispersed phases is necessary to control the nanoparticle size and size distribution.

Solvent-free one-pot synthesis of sulfonephthaleins from saccharin and phenols - Tillu, V. H.; Dumbre, Deepa K.; Borate, Hanumant B.; Wakharkar, R. D.; Choudhary, Vasant R. (Synthetic Communications, 2012)
Sulfonephthaleins can be synthesized in a single pot from saccharin and phenol via the in situ formation of 2-sulfobenzoic anhydride, followed by its reaction with phenol using H2SO4 as the condensing agent, in the absence of any solvent. This solvent-free synthesis is more economical and environmentally benign.
Keywords: H2SO4; Phenols; saccharin; sulfonephthalein

Solvent-free oxidation of aldehydes to acids by TBHP using environmental-friendly -exchanged Mg-Al hydrotalcite catalyst - Choudhary, Vasant R.; Dumbre, Deepa K.; Narkhede, Vijay S. (Journal of Chemical Sciences, 2012)
A number of hydrotalcite (Mg-Al, Mn-Al, Co-Al, Ni-Al, Mg-Fe, Mg-Cr and Cu-Al) catalysts, with or without MnO-exchange, were evaluated for their performance in the solvent-free oxidation of benzaldehyde to benzoic acid by tert-butyl hydroperoxide under reflux in the absence of any solvent. The MnO-exchanged Mg-Al-hydrotalcite (Mg/Al = 10) showed high activity in the oxidation of different aromatic and aliphatic aldehydes to their corresponding acids and also showed excellent reusability in the oxidation process which is environmental-friendly.
Keywords: acid; Aldehyde; MnO4-1-exchanged Mg-Al-hydrotalcite catalyst; Oxidation; TBHP

Structural, dynamical, and thermodynamical properties of carbon nanotube polycarbonate composites: a molecular dynamics study - Chakraborty, Souvik; Roy, Sudip (Journal of Physical Chemistry B, 2012)
All-atom molecular dynamics simulations are performed on pure monomer and trimer of polycarbonate and their mixtures with different molecular weight percentages of embedded single walled carbon nanotubes at different temperatures to study the structural and dynamical properties of the composite system. The diffusion behaviors of monomer, trimer of polycarbonate and carbon nanotubes in composite matrices are investigated and compared with pure matrices in details. Both structural and dynamical properties indicate the weak interaction between the nanotubes and matrix molecules. The high tendency of nanotubes to form bundles is observed during simulation. The bundle formation free energy has been calculated from the potential of mean force calculations. The mechanism and energetics of bundle formation is explored in the atomistic scale. The formation of the carbon nanotube bundle is a favorable process in the oligomeric polycarbonate matrix.

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

Synthesis of isomeric corniculatolides - Raut, Gajanan N.; Chakraborty, Kasturi; Verma, Priyanka; Gokhale, Rajesh S.; Reddy, D. Srinivasa (Tetrahedron Letters, 2012)
Synthesis of three natural macrolides 11-O-methylcorniculatolide A, 11-O-methylisocorniculatolide A and isocorniculatolide A is reported using a simple, straight forward and high-yielding route. The present synthesis confirms the assigned molecular structures and provides an access to sufficient quantities of the natural products for the biological evaluation. In addition, we have determined the anti-TB potential of the three natural compounds using Alamar-Blue assay (H(37)Rv) and found no significant inhibitory activity at 100 mu g/ml. Excellent yields, short sequence and useful SAR information are the highlights of the present work. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Diaryl ether; Isocorniculatolide; Macrocyclization; Mitsunobu reaction; Total synthesis

TDR Targets: a chemogenomics resource for neglected diseases - Magarinos, Maria P.; Carmona, Santiago J.; Crowther, Gregory J.; Ralph, Stuart A.; Roos, David S.; Shanmugam, Dhanasekaran; Van Voorhis, Wesley C. (Nucleic Acids Research, 2012)
The TDR Targets Database (http://tdrtargets.org) has been designed and developed as an online resource to facilitate the rapid identification and prioritization of molecular targets for drug development, focusing on pathogens responsible for neglected human diseases. The database integrates pathogen specific genomic information with functional data (e.g. expression, phylogeny, essentiality) for genes collected from various sources, including literature curation. This information can be browsed and queried using an extensive web interface with functionalities for combining, saving, exporting and sharing the query results. Target genes can be ranked and prioritized using numerical weights assigned to the criteria used for querying. In this report we describe recent updates to the TDR Targets database, including the addition of new genomes (specifically helminths), and integration of chemical structure, property and bioactivity information for biological ligands, drugs and inhibitors and cheminformatic tools for querying and visualizing these chemical data. These changes greatly facilitate exploration of linkages (both known and predicted) between genes and small molecules, yielding insight into whether particular proteins may be druggable, effectively allowing the navigation of chemical space in a genomics context.

Thermally decomposed Cu-Fe-hydrotalcite. a novel highly active catalyst for o-arylation of naphthol and phenols by aryl halides - Choudhary, Vasant R.; Dumbre, Deepa K.; Yadav, P. N.; Bhargava, Suresh Kumar (Catalysis Communications, 2012)
A novel, efficient and environmentally benign method has been reported for the synthesis of diaryl ethers by the o-arylation of napthol or phenols with aryl halides in dimethylformamide (as a solvent) under reflux, using a novel heterogeneous catalyst (having redox properties), obtained from thermal decomposition of Cu-Fe at 600 degrees C in the absence of externally added base. The catalyst comprises Cu(II) and Fe(III) species (oxides and hydroxides), which are uniformly distributed during the catalyst formation. The catalyst can be easily separated from the reaction mixture, simply by filtration and reused several times without a significant loss of its activity. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Aryl halides; C-O cross coupling reaction; Cu-Fe-hydrotalcite; Naphthol; o-Arylation; Phenols

Transesterification of diethyl oxalate with phenol over sol-gel MoO3/TiO2 catalysts - Kotbagi, Trupti; Duy Luan Nguyen; Lancelot, Christine; Lamonier, Carole; Thavornprasert, Kaew-Arpha; Zhu Wenli; Capron, Mickael; Jalowiecki-Duhamel, Louise; Shubhangi B. Umbarkar; Dongare, Mohan K.; Dumeignil, Franck (Chemsuschem, 2012)
The transesterification of diethyl oxalate (DEO) with phenol to form diphenyl oxalate (DPO) has been carried out in the liquid phase over very efficient MoO3/TiO2 solid-acid solgel catalysts. A selectivity of 100?% with a remarkable maximum yield of 88?% were obtained, which opens the route to downstream phosgene-free processes for the synthesis of polycarbonates. Interpretation of the results of various acidity measurements (NH3 and pyridine desorption, methanol oxidation as a probe reaction) allowed us to identify the catalytic sites as Lewis acid sites.
Keywords: heterogeneous catalysis; Lewis acids; Oxidation; sol-gel processes; transesterification

Transport of inorganic acids through polybenzimidazole (PBI) based membranes by chemo-dialysis - Chendake, Yogesh J.; Kharul, Ulhas K. (Desalination and Water Treatment, 2012)
A process of chemo-dialysis involving poly(benzimidazole) (PBI) as a chemically active membrane material is proposed for the transport of inorganic acids. These membranes possessing basic nature selectively bind acid molecules present in the feed solution due to acid-base interactions. They are transported across the membrane by concentration gradient as the driving force. The transported acid molecules are stripped away from other side of the membrane surface by a suitable stripping agent or water. Effects of nature of feed acid (pK(a), molecular size), its concentration in the feed solution and the nature of stripping agent (base or water) on acid transport properties are presented. Membranes showed appreciable transport rates for three acids, viz., H2SO4, HCl and HNO3. The fluxes for different acids varied from 16.1 to 140.7 g/m(2) h under different operating conditions. Most significantly, there was no transport of non-acidic solutes such as NaCl or glucose. This could be made possible since these solutes neither get sorbed in the membrane matrix, nor does the membrane exhibit any porosity for the transport to occur through pores. This resulted in practically infinite selectivity of transported acid over the non-acidic solutes. Use of water as the stripping agent allows recycling of the acid, making the process economically attractive. Moreover, possible recovery of acid and its reuse eliminated the requirement of acid neutralization and disposal; which is a routine practice followed today. Thus, this process of chemo-dialysis is economically attractive and environmentally benign.
Keywords: Acid transport; Chemical interaction; Chemo-dialysis; Inorganic acids; Membrane; Polybenzimidazole

Very practical and selective method for PMB protection of alcohols - Chavan, Subhash P.; Harale, Kishor R. (Tetrahedron Letters, 2012)
A very simple, practical and efficient one-step heterogeneous protocol for the PMB protection of alcohols using Amberlyst-15 has been developed. The stability and hazard issues regarding PMBCI and PMBBr are totally avoided by directly using anisyl alcohol for the protection. Alcohols are protected in very good yields. The selective mono-PMB protection of diols as well as di-PMB protection of diols was achieved in good yields, along with the demonstration of recyclability of the catalyst. (c) 2012 Elsevier Ltd. All rights reserved.
Keywords: 4-Methoxybenzyl alcohol; 4-Methoxybenzyl protection; Amberlyst-15; Di-PMB protection; Mono-PMB protection

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

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

Carbon nanofiber-RuO2-poly(benzimidazole) ternary hybrids for improved supercapacitor performance - Balan, Beena K.; Chaudhari, Harshal D.; Kharul, Ulhas K.; Kurungot, Sreekumar (RSC Advances, 2013)
Carbon nanofiber-RuO2-poly(benzimidazole) ternary hybrid electrode material which integrates dual wall decoration and interfacial area tuning for supercapacitor applications has been devised based on a simple approach. This is achieved by decorating RuO2 nanoparticles of size ca. 2-3 nm along the inner and outer walls of a hollow carbon nanofiber (CNF) support (F-20RuO(2)). In the next step, a proton conducting polymer, phosphoric acid doped polybenzimidazole (PBI-BuI), interface is created along the inner and outer surfaces of this material. A 103% increase in the specific capacitance is obtained for RuO2-PBI hybrid material as compared to that of F-20RuO(2) at the optimum level of the polymer wrapping. Apart from the high specific capacitance, the RuO2-PBI hybrid materials exhibit enhanced rate capability and excellent electrochemical stability of 98% retention in the capacitance. Such a remarkably high activity can be primarily attributed to the efficient dispersion of active sites achieved by properly utilizing inner and outer surfaces of CNF. Apart from this, the facile routes for ion transport created as a result of PBI incorporation coupled with excellent interfacial contact between the RuO2 and the electrolyte resulting in the improved utilization of the active material also contribute to the improved activity. In addition to this, the synergistic effects of pseudocapacitive contribution from both the PBI-BuI and RuO2 also contribute to the redefined performance characteristics.

Catalytic activity of ZIF-8 in the synthesis of styrene carbonate from CO2 and styrene oxide - Zhu, Minqi; Srinivas, Darbha; Bhogeswararao, Seemala; Ratnasamy, Paul; Carreon, Moises A. (Catalysis Communications, 2013)
The catalytic activity of ZIF-8 in the synthesis of styrene carbonate from carbon dioxide and styrene oxide is presented. ZIF-8 crystals displayed catalytic activity even at temperatures as low as 50 degrees C, with styrene carbonate yields as high as similar to 54% at 100 degrees C. In contrast to many prior-art catalysts, solvents or co-catalysts were not required. Pyridine and ammonia were used as probe molecules to estimate the type and density of acid sites in fresh and reused ZIF-8 catalysts. DRIFT spectroscopy of adsorbed pyridine revealed the presence of both Bronsted (B) and Lewis (L) acid sites. The B-sites have nearly vanished in the case of recycled ZIF-8 catalysts. The simultaneous presence of both the acid sites and the nitrogen basic moieties from the imidazole linker in ZIF-8 promoted the adsorption of the CO2 on the solid surface and its further conversion to the cyclic carbonate. The ZIF-8 catalysts could be recycled and reused without significant loss in catalytic activity. Published by Elsevier B.V.
Keywords: CO2 conversion; cyclic carbonates; Styrene carbonate; Zeolitic imidazolate frameworks; ZIF-8

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

Characterization of conformation and interaction of gene delivery vector polyethylenimine with phospholipid bilayer at different protonation state - Choudhury, Chandan Kumar; Kumar, Abhinaw; Roy, Sudip (Biomacromolecules, 2013)
Polyethylenimine (PEI) is a pH sensitive polymer possessing stretched and coiled conformation at low and high pH, respectively. It is an efficient gene delivery agent. Thus, the interaction of PEI with the biomembrane is very crucial to understand the gene delivery mechanism. In this report, we have investigated the structural properties of PEI and bilayer due to the interaction of PEI with lipid molecules. PEI has coil structure at high pH while at low pH it is elongated. The neutral PEI chain predominately settles itself at the bilayer water interface. We do not find any disruption or pore formation on the bilayer due to interaction of neutral PEI chain. PEI at low pH gets elongated due to electrostatic interaction between charges of the protonated sites. This protonated PEI chain interacts with bilayer membrane, which leads to formation of water/ion channel through the membrane. We have analyzed the structure of the channel and water dynamics along the channel.

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

Chemically stable multilayered covalent organic nanosheets from covalent organic frameworks via mechanical delamination - Chandra, Suman; Kandambeth, Sharath; Biswal, Bishnu P.; Lukose, Binit; Kunjir, Shrikant M.; Chaudhary, Minakshi V.; BabaRao, Ravichandar; Heine, Thomas; Banerjee, Rahul (Journal of the American Chemical Society, 2013)
A series of five thermally and chemically stable functionalized covalent organic frameworks (COFs), namely, TpPa-NO2, TpPa-F-4, TpBD-(NO2)(2), TpBD-Me-2, and TpBD-(OMe)(2) were synthesized by employing the solvothermal aldehyde-amine Schiff base condensation reaction. In order to complete the series, previously reported TpPa-1, TpPa-2, and TpBD have also been synthesized, and altogether, eight COFs were fully characterized through powder X-ray diffraction (PXRD), Fourier transform IR (FT-IR) spectroscopy, C-13 solid-state NMR spectroscopy, and thermogravimetric analysis. These COFs are crystalline, permanently porous, and stable in boiling water, acid (9 N HCl), and base (3 N NaOH). The. synthesized COFs (all eight) were successfully delaminated using a simple, safe, and environmentally friendly mechanical grinding route to transform into covalent organic nanosheets (CONs) and were well characterized via transmission electron microscopy and atomic force microscopy. Further PXRD and FT-IR analyses confirm that these CONs retain their structural integrity throughout the delamination process and also remain stable in aqueous, acidic, and basic media like the parent COFs. These exfoliated CONs have graphene-like layered morphology (delaminated layers), unlike the COFs from which they were synthesized.

Chitin synthase inhibitors as antifungal agents - Chaudhary, Preeti M.; Tupe, Santosh G.; Deshpande, Mukund V. (Mini-Reviews in Medicinal Chemistry, 2013)
Increased risk of fungal diseases in immunocompromised patients, emerging fungal pathogens, limited repertoire of antifungal drugs and resistance development against the drugs demands for development of new and effective antifungal agents. With greater knowledge of fungal metabolism efforts are being made to inhibit specific enzymes involved in different biochemical pathways for the development of antifungal drugs. Chitin synthase is one such promising target as it is absent in plants and mammals. Nikkomycin Z, a chitin synthase inhibitor is under clinical development. Chitin synthesis in fungi, chitin synthase as a target for antifungal agent development, different chitin synthase inhibitors isolated from natural sources, randomly synthesized and modified from nikkomycin and polyoxin are discussed in this review.
Keywords: Antifungal agents; Chitin synthase; Chitin synthase inhibitors; Nikkomycin; Peptidyl nucleoside antibiotics; Polyoxin

Chitinolytic enzymes: an appraisal as a product of commercial potential - Chavan, S. B.; Deshpande, Mukund V. (Biotechnology Progress, 2013)
Chitin, its deacetylated form, chitosan and chitinolytic enzymes viz. endo-chitinase, N-acetylglucosaminidase, chitosanase, chitin deacetylase (CDA) are gaining importance for their biotechnological applications. Presently, chitin degrading enzymes constitute high-cost low-volume products in human health care and associated research. Indeed chitinases and CDA-chitosanase complex possesss tremendous potential in agriculture to control plant pathogenic fungi and insects. The success in exploring chitinases especially for agriculture, i.e. as a high-volume low-cost product, depends on the availability of highly active preparations with a reasonable cost. Therefore, a reconsideration in terms of understanding the roles of chitinolytic enzymes in applications, e.g. host-pathogen interaction for biocontrol, different mechanisms of chitin degradation, and identification of new enzymes with varying specificities, may make them more useful in a variety of commercial processes in the near future. The possible issues and challenges encountered in the translation of proof of concept into a commercial product will be appraised in this review. (c) 2013 American Institute of Chemical Engineers Biotechnol. Prog., 29:833-846, 2013
Keywords: chitin deacetylase; chitinase; chitosanase; high-cost low-volume product; high-volume low-cost product

Controlled synthesis of aligned Bi2S3 nanowires, sharp apex nanowires and nanobelts with its morphology dependent field emission investigations - Warule, Sambhaji S.; Chaudhari, Nilima S.; Kale, Bharat B.; Pandiraj, S.; Khare, Ruchita T.; More, Mahendra A. (Crystengcomm, 2013)
Well-aligned ultra-long Bi2S3 nanowire arrays with three kinds of apex morphology - abruptly sharpened apex, thin belt and flat - have been systematically fabricated on tungsten (W) foil by a facile hydrothermal method. The structural and morphological studies reveal formation of distinct tip morphologies, possessing high aspect ratio, single crystalline nature and growth along the orthorhombic [001] axis. A plausible growth mechanism has been proposed on the basis of observed experimental results. The field emission properties of Bi2S3 nanowires and sharp apex Bi2S3 nanowires are investigated. From the field emission studies, the values of the turn-on field, required to draw emission current density of similar to 0.1 mu A cm(-2), are observed to be similar to 2.01 and 1.21 V mu m(-1) for nanowires and sharp apex nanowires, respectively. Furthermore, ultra-long Bi2S3 nanowires are also grown on the W microtip (brush-like) from which very high emission current density similar to 11 mA cm(-2) has been drawn. These results are helpful for the design, fabrication and optimization of integrated field emitters using 1D nanostructures as cold cathode material.

Dehydration of fructose to 5-hydroxymethyl furfural over ordered AlSBA-15 catalysts - Lucas, Nishita; Kokate, Ganesh; Nagpure, Atul; Chilukuri, Satyanarayana V. (Microporous and Mesoporous Materials, 2013)
5-Hydroxymethyl furfural is an important platform chemical. It is successfully synthesized from renewable carbohydrates using mesoporous AlSBA-15 catalysts under biphasic conditions. Fine tuning of the catalyst acidity is important to drive the reaction to give good yields of furan compound. Al-SBA-15 catalysts with different Si/Al ratios were prepared and characterized by XRD, Al-27 MASNMR, SEM, TEM, N-2 sorption, ICP-OES and TPD of ammonia. Results show that part of aluminium is substituted into tetrahedral positions. The catalyst with lower acid site density but medium to strong acid strength favours selective formation of HMF. Under the optimized conditions, HMF selectivity was as high as 88% at 59 mol% conversion of fructose. Leaching of part of aluminium occurs under hydrothermal conditions, if solvent mixtures containing water are used, while activity can be retained if DMSO is used as solvent. (c) 2013 Elsevier Inc. All rights reserved.
Keywords: Acidity; AlSBA-15; dehydration; fructose; Hydroxymethyl furfural

Design, synthesis, structural characterization by IR, 1H, 13C, 15N, 2D-NMR, X-ray diffraction and evaluation of a new class of phenylaminoacetic acid benzylidene hydrazines as pfENR inhibitors - Samal, Ramanuj P.; Khedkar, Vijay M.; Pissurlenkar, Raghuvir R. S.; Bwalya, Angela Gono; Tasdemir, Deniz; Joshi, Ramesh A.; Rajamohanan, P. R.; Puranik, Vedavati G.; Coutinho, Evans C. (Chemical Biology & Drug Design, 2013)
Recent studies have revealed that plasmodial enoyl-ACP reductase (pfENR, FabI), one of the crucial enzymes in the plasmodial type II fatty acid synthesis II (FAS II) pathway, is a promising target for liver stage malaria infections. Hence, pfENR inhibitors have the potential to be used as causal malarial prophylactic agents. In this study, we report the design, synthesis, structural characterization and evaluation of a new class of pfENR inhibitors. The search for inhibitors began with a virtual screen of the iResearch database by molecular docking. Hits obtained from the virtual screen were ranked according to their Glide score. One hit was selected as a lead and modified to improve its binding to pfENR; from this, a series of phenylamino acetic acid benzylidene hydrazides were designed and synthesized. These molecules were thoroughly characterized by IR, 1H, 13C, 15N, 2D-NMR (COSY, NOESY, 1H-13C, 1H-15N HSQC and HMBC), and X-ray diffraction. NMR studies revealed the existence of conformational/configurational isomers around the amide and imine functionalities. The major species in DMSO solution is the E, E form, which is in dynamic equilibrium with the Z, E isomer. In the solid state, the molecule has a completely extended conformation and forms helical structures that are stabilized by strong hydrogen bond interactions, forming a helical structure stabilized by N-H...O interactions, a feature unique to this class of compounds. Furthermore, detailed investigation of the NMR spectra indicated the presence of a minor impurity in most compounds. The structure of this impurity was deduced as an imidazoline-4-one derivative based on 1H-13C and 1H-15H HMBC spectra and was confirmed from the NOESY spectra. The molecules were screened for in vitro activity against recombinant pfENR enzyme by a spectrophotometric assay. Four molecules, viz. 17, 7, 10, and 12 were found to be active at 7, 8, 10, and 12m concentration, respectively, showing promising pfENR inhibitory potential. A classification model was derived based on a binary QSAR approach termed recursive partitioning (RP) to highlight structural characteristics that could be tuned to improve activity.
Keywords: ADMET; docking; enoyl-ACP reductase; FabI; hydrogen bonding; NMR; phenylaminoacetic acid benzylidene hydrazine; Plasmodium falciparum; Plasmodium falciparum enoyl-ACP reductase; QSAR; recursive partitioning; X-ray diffraction

Desymmetrization approach to the enantiopure syn/anti-1,5-diols via hydrolytic kinetic resolution (hkr) of functionalized meso-bis-epoxides: further elaboration to syn/syn-1,3,5-triols and application to the formal synthesis of cryptocarya diacetate - Kumar, Pradeep; Chowdhury, Partha Sarathi; Pandey, Menaka (Advanced Synthesis & Catalysis, 2013)
A new approach has been developed for the synthesis of enantiopure syn/anti-1,5-diols by desymmetrization of functionalized meso-bis-epoxides using hydrolytic kinetic resolution (HKR). The usage of this protocol was demonstrated by converting syn-1,5-diols into syn/syn-1,3,5-triols and its subseqent application to the formal synthesis of cryptocarya diacetate.
Keywords: bis-epoxides; cryptocarya diacetate; desymmetrization; stereoselective reduction; synthetic methods

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

Draft genome of ochrobactrum intermedium strain M86 isolated from non-ulcer dyspeptic individual from India - Kulkarni, Girish; Dhotre, Dhiraj; Dharne, Mahesh S.; Shetty, Sudarshan; Chowdhury, Somak; Misra, Vatsala; Misra, Sriprakash; Patole, Milind; Shouche, Yogesh (GUT Pathogens, 2013)
Background: Ochrobactrum intermedium is an emerging opportunistic pathogen of humans that is closely related to members of the genus Brucella. Earlier, we reported the case of an Indian subject with non-ulcer dyspeptic symptoms whose urease positive gastric biopsy revealed the presence of Helicobacter pylori along with non-Helicobacter like bacteria, eventually cultured and identified as O. intermedium strain M86. Results: Here, we describe the unclosed draft genome of the strain M86 with a length of 5,188,688 bp and mean G+C content of 57.9%. We have also identified many putative gene clusters that might be responsible for its persistence in the gastric mucosa. Comparative analysis of genomic features of Ochrobactrum intermedium strain M86 and Ochrobactrum intermedium LMG 3301(T) was also done. Conclusions: This paper attempts to gain whole-genome based insights into the putative gene determinants of O. intermedium for survival in the highly acidic stomach lumen environment. Identification of genes putatively involved in the various metabolic pathways may lead to a better understanding of the survival of O. intermdedium in acidic condition.

Drug targets and biomarker identification from computational study of human notch signaling pathway - Chowdhury, Saikat; Sarkar, Ram Rup (Clinical and Experimental Pharmacology and Physiology, 2013)
Notch signaling pathway is widely implicated in controlling various cellular functions, cell fate determination, and stem cell renewal in human but aberrant activity in cancer stem cells may cause different types of cancers. Understanding the complexity of this pathway to identify important targets for cancer therapy and to suppress the pathway activity without affecting the normal functions is of utmost importance to clinical and experimental pharmacologists. For developing therapeutic strategy, non availability of detailed molecular interactions, complex regulations and cross talks with other pathways pose a serious challenge to get a coherent understanding of this pathway. This motivated us to reconstruct the largest human cell specific Notch pathway with more number of molecules and interactions available from literatures and databases. To identify probable drug targets and biomarkers for cancer prognosis, we also performed computational study of the pathway using structural and logical analysis and identified important hub proteins, cross talks and feedback mechanisms. The model simulation is validated using reported mRNA expression profile in Glioblastoma cell line and the predictions not only show significant accuracy but also able to identify the undetermined expressions. From our simulation, to identify novel combinations of drug targetable proteins and better substitute for GAMMA SECRETASE inhibition, we proposed two alternative scenarios: partial suppression of Notch target proteins by NICD1 & HIF1A; and complete suppression by NICD1 & MAML, in Glioblastoma cell line. This reconstructed Notch signaling pathway and the computational analysis for identifying new biomarkers and combinatory drug targets will be useful for future in-vitro and in-vivo analysis to control different cancers

Dual action of BPC194: a membrane active peptide killing bacterial cells - Moiset, Gemma; Cirac, Anna D.; Stuart, Marc C. A.; Marrink, Siewert-Jan; Sengupta, Durba; Poolman, Bert (Plos One, 2013)
Membrane active peptides can perturb the lipid bilayer in several ways, such as poration and fusion of the target cell membrane, and thereby efficiently kill bacterial cells. We probe here the mechanistic basis of membrane poration and fusion caused by membrane-active, antimicrobial peptides. We show that the cyclic antimicrobial peptide, BPC194, inhibits growth of Gram-negative bacteria and ruptures the outer and inner membrane at the onset of killing, suggesting that not just poration is taking place at the cell envelope. To simplify the system and to better understand the mechanism of action, we performed Forster resonance energy transfer and cryogenic transmission electron microscopy studies in model membranes and show that the BPC194 causes fusion of vesicles. The fusogenic action is accompanied by leakage as probed by dual-color fluorescence burst analysis at a single liposome level. Atomistic molecular dynamics simulations reveal how the peptides are able to simultaneously perturb the membrane towards porated and fused states. We show that the cyclic antimicrobial peptides trigger both fusion and pore formation and that such large membrane perturbations have a similar mechanistic basis.

Effect of clay and of electrospinning on the polymorphism, structure and morphology of poly(vinylidene fluoride) - Neppalli, Ramesh; Wanjale, Santosh; Birajdar, Mallinath S.; Causin, Valerio (European Polymer Journal, 2013)
Electrospun poly(vinylidene fluoride) (PVDF) fibers, containing different amounts of montmorillonite clay were produced, in order to study the effect of clay and of the electrospinning process on the polymorphism, structure and morphology of the PVDF matrix, Clay acted as a processing aid agent, avoiding the formation of beads and improving the quality of the fibers. Clay and the electrospinning process acted synergically on the chain mobility, favoring the formation of beta phase of PVDF, the most valuable for its piezoelectric properties, and shaping its semicrystalline morphology. Electrospinning did not significantly aid the dispersion of clay within the matrix. The interplay of formulation and processing in these composites allowed to obtain PVDF-based materials with varying polymorphism, structure and morphology, offering the possibility to ultimately control their functional properties. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Composite; electrospinning; Poly(vinylidene fluoride); Polymer; polymorphism; SAXS

Effect of the viscosity of poly(benzimidazole) on the performance of a multifunctional electrocatalyst with an ideal interfacial structure - Balan, Beena K.; Unni, Bipinlal; Chaudhari, Harshal D.; Kharul, Ulhas K.; Kurungot, Sreekumar (Journal of Materials Chemistry A, 2013)
A novel electrocatalyst system with unique multifunctional characteristics, originated by the presence of a proton conducting polybenzimidazole (PBI-BuI) bound layer and electron conducting hollow carbon nanofibers (CNF) with catalytically active Pt nanoparticles, has been devised based on a simple strategy. This was achieved by decorating Pt nanoparticles along the inner cavity, as well as on the outer walls of the hollow CNF support (F-Pt). In a further extension, a low molecular weight PBI, synthesized by optimizing the experimental parameters, was incorporated into the inner cavity and along the outer surfaces of F-Pt. Excellent dispersion of the Pt nanoparticles was achieved by properly utilizing the available carbon surface results in improved electrocatalytic activity, while the CNF backbone ensures high electron conductivity as well. The polymer binder coverage formed along the inner and outer wall surfaces provides an efficient triple phase boundary (TPB) around the Pt nanoparticles to facilitate the electrode reactions. The amount and the viscosity of the PBI-BuI in the electrode material were systematically varied to study the influence on the electrochemical performance. Transmission electron microscopy analysis confirms PBI insertion into the tubular cavity of CNF. Pore size distribution analysis implies that both the viscosity and the amount of PBI-BuI have a pivotal role in defining the microstructure of the electrode. Electrochemical studies using cyclic voltammetry (CV) and rotating disc electrode (RDE) reveal the exceptionally high activity of this hybrid material with an improved electrochemically active area. The significant improvement for the oxygen reduction reaction is further confirmed by the single cell analysis also. The high power density displayed by the PBI-BuI based system, as compared to the Nafion based system, validates the conceptualization of the well controlled triple-phase boundary in the system. These results demonstrate that PBI-BuI has a constructive effect in tuning the electrochemical activity at an optimum amount and at a favourable viscosity of the proton conducting polymer.

Enhanced field-emission behavior of layered MoS2 sheets - Kashid, Ranjit V.; Late, Dattatray J.; Chou, Stanley S.; Huang, Yi-Kai; De, Mrinmoy; Joag, Dilip S.; More, Mahendra A.; Dravid, Vinayak P. (Small, 2013)
Field emission studies are reported for the first time on layered MoS2 sheets at the base pressure of approximate to 1 x 10(-8) mbar. The turn-on field required to draw a field emission current density of 10 A/cm(2) is found to be 3.5 V/m for MoS2 sheets. The turn-on values are found to be significantly lower than the reported MoS2 nanoflowers, graphene, and carbon nanotube-based field emitters due to the high field enhancement factor (approximate to 1138) associated with nanometric sharp edges of MoS2 sheet emitter surface. The emission current-time plots show good stability over a period of 3 h. Owing to the low turn-on field and planar (sheetlike) structure, the MoS2 could be utilized for future vacuum microelectronics/nanoelectronic and flat panel display applications.

Epoxidation of styrene by t-butyl hydroperoxide over gold nanoparticles supported on Yb2O3: effect of gold deposition method, gold loading, and calcination temperature of the catalyst on its surface properties and catalytic performance - Choudhary, Vasant R.; Dumbre, Deepa K.; Patil, N. S.; Uphade, B. S.; Bhargava, Suresh Kumar (Journal of Catalysis, 2013)
Surface properties and epoxidation performance of Au/Yb2O3 catalyst are influenced by the method of gold deposition [viz. deposition-precipitation (DP), homogeneous deposition-precipitation (HDP) or impregnation], gold loading (0.9-6.6 wt%), and the catalyst calcination temperature (400-900 degrees C)]. The catalyst showed the best epoxidation performance when it was prepared by the HDP method and calcined at 500 degrees C. The Au/Yb2O3 catalyst even after calcination at 900 degrees C showed good activity and epoxide selectivity. Both Au-0 and Au3+ surface species were found in the catalyst calcined at 800 degrees C, but only Au-0 species were observed at the lower calcination temperatures (<600 degrees C). The selectivity for styrene oxide increased continuously with the reaction temperature (from 75 degrees C to 97 degrees C) and time (1-5 h), indicating that styrene oxide did not undergo secondary reactions under these conditions. (C) 2013 Elsevier Inc. All rights reserved.
Keywords: Au/Yb2O3 catalyst; Epoxidation of styrene; gold nanoparticles; Styrene oxide; tert-Butyl hydroperoxide

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

Highly concise and practical route to clavaminols, sphinganine and (+)-spisulosine via indium mediated allylation of alpha-hydrazino aldehyde and a theoretical insight into the stereochemical aspects of the reaction - Pandey, Menaka; Chowdhury, Partha Sarathi; Dutta, Achintya Kumar; Kumar, Pradeep; Pal, Sourav (RSC Advances, 2013)
A conceptually different approach has been employed for the synthesis of 1,2-amino alcohols by proline-catalyzed alpha-amination of aldehyde and one-pot indium mediated allylation of the crude alpha-hydrazino aldehydes. DFT based quantum chemical calculations have been performed to obtain a quantitative explanation of the stereoselectivity of the reaction.

Highly efficient catalyst derived from Ni-Fe-hydrotalcite for solvent-free O- or S-acetylation of alcohols, phenols and thiols at room temperature - Choudhary, Vasant R. (Proceedings of the National Academy of Sciences India Section A-Physical Sciences, 2013)
Solvent-free O-acetylation of alcohols (including secondary and tertiary alcohols) and phenols and S- acetylation of thiols by acetyl chloride with high product yields at room temperature in a very short reaction period can be easily accomplished using a small amount of solid catalyst obtained from the decomposition (at 600 A degrees C) of Ni-Fe-hydrotalcite. Both the reactions are carried out at room temperature under solvent-free conditions. The catalyst can be easily separated from the reaction mixture, simply by filtration and reused several times without a significant loss of its activity.
Keywords: Acetyl chloride; Alcohols; Ni-Fe- ht derived catalyst; O- and S-acetylation; Phenols; Solvent-free

Hollow nanogold/meso-magnetite composite: pulsed laser synthesis, properties, and biosensing application - Chaudhari, Nilima; Warule, Sambhaji; Agrawal, Shailaja; Thakare, Vishal; Jouen, Samuel; Hannoyer, Beatrice; Kale, Bharat; Paknikar, Kishore; Ogale, Satishchandra B. (Journal of Nanoparticle Research, 2013)
A facile and template-free UV (Excimer) laser photolysis process is demonstrated to transform a Fe-complex into unique hollow Fe3O4 nanosphere morphology with each sphere having nanometric pores and an opening. Depending on the Fe-complex concentration and processing time interesting configurations are seen to evolve. When an identical process is applied to a mixture of Fe-complex and chloroauric acid an enthrallingly decorated Au-Fe3O4 nanostructure evolves, with Au nanoparticles surface-loaded on mesospheric Fe3O4. This room temperature process implemented under normal laboratory conditions is clearly versatile and applicable to heterojunction nanomaterials synthesis in a single-step process. The potential application of these gold-decorated magnetic nanostructures was also investigated for immuno-magnetic capture of E. coli in biosensing and these were found to be sensitive even below 1,000 cfu/ml. The test results demonstrate linear sensing response in the range of 10(3)-10(5) cfu/ml. We also show that these nanostructures can be used for simple electrical conductivity-based biosensing since they show dramatic conductivity change in a simple drop-cast test. A new laser-based approach to the synthesis of unique hollow sphere morphology of magnetite (Fe3O4) without and with Au nanoparticle decoration is presented. The potential application of these gold-decorated magnetic nanostructures was also investigated for immuno-magnetic capture of E. coli in biosensing and these were found to be sensitive even below 1,000 cfu/ml.
Keywords: E. coli cells; Fe-complex; Meso-magnetite; Nanobiotechnology; Nanocomposite; Pulse laser irradiation

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

Interplay between crystallization and glass transition in binary lennard-Jones mixtures (vol 139, 104501, 2013) - Banerjee, Atreyee; Chakraborty, Suman; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2013)

Interplay between crystallization and glass transition in binary Lennard-Jones mixtures - Banerjee, Atreyee; Chakrabarty, Suman; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2013)
In this work we explore the interplay between crystallization and glass transition in different binary mixtures by changing their inter-species interaction length and also the composition. We find that only those systems which form bcc crystal in the equimolar mixture and whose global structure for larger x(A) (x(A) = 0.6, where x(A) is the mole fraction of the bigger particles) is a mixed fcc + bcc phase, do not crystallize at this higher composition. However, the systems whose equimolar structure is a variant of fcc (NaCl type crystal) and whose global structure at larger xA is a mixed NaCl + fcc phase, crystallize easily to this mixed structure. We find that the stability against crystallization of this ``bcc zone'' is due to the frustration between the locally preferred structure (LPS) and the mixed bcc + fcc crystal. Our study suggests that when the global structure is a mixed crystal where a single species contributes to both the crystal forms and where the two crystal forms have large difference in some order parameter related to that species then this induces frustration between the LPS and the global structure. This frustration makes the systems good glass former. When x(A) is further increased (0.70 <= x(A) < 0.90) the systems show a tendency towards mixed fcc crystal formation. However, the ``bcc zone'' even for this higher composition is found to be sitting at the bottom of a V shaped phase diagram formed by two different variants of the fcc crystal structure, leading to its stability against crystallization. (C) 2013 AIP Publishing LLC.

Mechanism of action of novel synthetic dodecapeptides against Candida albicans - Maurya, Indresh Kumar; Thota, Chaitanya Kumar; Sharma, Jyotsna; Tupe, Santosh Genba; Chaudhary, Preeti; Singh, Manoj Kumar; Thakur, Indu Shekhar; Deshpande, Mukund V.; Prasad, Rajendra; Chauhan, Virander Singh (Biochimica Et Biophysica Acta-General Subjects, 2013)
Background: Three de novo designed low molecular weight cationic peptides (IJ2, IJ3 and IJ4) containing an unnatural amino acid alpha,beta-didehydrophenylalanine (APhe) exhibited potent antifungal activity against fluconazole (FLC) sensitive and resistant clinical isolates of Candida albicans as well as non-albi cans and other yeast and filamentous pathogenic fungi. In the present study, their synthesis, susceptibility of different fungi and the mechanism of anti-candidal action have been elucidated. Methods: The antimicrobial peptides (AMPs) were synthesized by solid-phase method and checked for antifungal activity against different yeasts and fungi by broth microdilution method. Anti-candidal mode of action of the peptides was investigated through detecting membrane permeabilization by confocal microscopy, Reactive Oxygen Species (ROS) generation by fluorometry, apoptosis and necrosis by flow cytometry and cell wall damage using Scanning and Transmission Electron Microscopy. Results and conclusions: The MIC of the peptides against C. albicans and other yeast and filamentous fungal pathogens ranged between 3.91 and 250 mu M. All three peptides exhibited effect on multiple targets in C. albi cans including disruption of cell wall structures, compromised cell membrane permeability leading to their enhanced entry into the cells, accumulation of ROS and induction of apoptosis. The peptides also showed synergistic effect when used in combination with fluconazole (FLC) and caspofungin (CAS) against C. albi cans. General significance: The study suggests that the AMPs alone or in combination with conventional antifungals hold promise for the control of fungal pathogens, and need to be further explored for treatment of fungal infections. (C) 2013 Elsevier By. All rights reserved.
Keywords: Antifungal peptide; Antimicrobial peptide (AMP); Apoptosis; Candida albicans; Reactive Oxygen Species (ROS)

Mechanochemical synthesis of chemically stable isoreticular covalent organic frameworks - Biswal, Bishnu P.; Chandra, Suman; Kandambeth, Sharath; Lukose, Binit; Heine, Thomas; Banerjeet, Rahul (Journal of the American Chemical Society, 2013)
Three thermally and chemically stable isoreticular covalent organic frameworks (COFs) were synthesized via room-temperature solvent-free mechanochemical grinding. These COFs were successfully compared with their solvothermally synthesized counterparts in all aspects. These solvent-free mechanochemically synthesized COFs have moderate crystallinity with remarkable stability in boiling water, acid (9 N HCl), and base [TpBD (MC) in 3 N NaOH and TpPa-2 (MC) in 9 N NaOH]. Exfoliation of COF layers was simultaneously observed with COF formation during mechanochemical synthesis. The structures thus obtained seemed to have a graphene-like layered morphology (exfoliated layers), unlike the parent COFs synthesized solvothermally.

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

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

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

Morphology and dynamics of carbon nanotube in polycarbonate carbon nanotube composite from dissipative particle dynamics simulation - Chakraborty, Souvik; Choudhury, Chandan Kumar; Roy, Sudip (Macromolecules, 2013)
Morphology and dynamics of carbon nanotube (CNT) in polycarbonate matrix with different mixing ratios are studied in mesoscale by using dissipative particle dynamics (DPD). We have used atomistic simulation to derive necessary interaction parameter for mesoscale DPD simulation for polycarbonate nanotube composite using Flory-Huggins theory. The diffusion and morphology of nanotubes in different concentrations (2%, 5%, 10%) are investigated. Diffusivity of nano tubes in polymer matrices is explored at different temporal regimes of simulation. Diffusion of nanotubes becomes significantly slow when bundling of nanotubes takes place. The bundle formation of nanotubes is observed in all of three mixtures with varying degrees of assembling and alignment Bundle size analysis is performed to study the extent of bundling affinity of CNTs in different filler concentrations. Size of the bundles of nanotubes is more in higher nanotube concentrations. In the 10% mixture percolation network is found to be formed by bundles of nanotubes.

Noble metal promoted CeO2-ZrO2-supported ni catalysts for liquid-phase hydrogenation of cinnamaldehyde - Bhogeswararao, Seemala; Kumar, V. Pavan; Chary, K. V. R.; Srinivas, D. (Catalysis Letters, 2013)
Pd or Pt promoted CeO2-ZrO2-supported Ni catalysts exhibited superior catalytic activity to the hitherto known Ni catalysts for liquid-phase hydrogenation of cinnamaldehyde at moderate conditions. Under similar experimental conditions, the unpromoted catalyst was selective for hydrocinnamaldehyde product (C=C hydrogenation) whereas the promoted catalyst yielded 3-phenyl propanol (C=C and C=O hydrogenation product). Enhanced dispersion of Ni was the cause for higher activity of the promoted Ni catalysts.
Keywords: Ceria-zirconia; Cinnamaldehyde; Noble metal promoted catalyst; Selective hydrogenation; Supported Ni catalyst

Novel and efficient synthesis of azaarene-substituted 3-hydroxy-2-oxindoles via sp(3) C-H functionalization of 2-methyl azaarenes and (2-azaaryl)methanes over a heterogeneous, reusable silica-supported dodecatungstophosphoric acid catalyst - Mulla, Shafeek Abdul Rashid; Pathan, Mohsinkhan Y.; Chavan, Santosh S. (RSC Advances, 2013)
A novel and efficient protocol has been developed for the synthesis of azaarene-substituted 3-hydroxy-2-oxindoles via sp(3) C-H functionalization of 2-methyl azaarenes and (2-azaaryl)methanes with isatin in good to excellent yield. This is the first example in which heterogeneous, reusable silica supported dodecatungstophosphoric acid (DTP/SiO2) catalyzed sp(3) C-H functionalization of 2-substituted azaarenes and (2-azaaryl)methanes.

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

Novel mechanism for antiglycative action of limonene through stabilization of protein conformation - Joglekar, Madhav M.; Panaskar, Shrimant N.; Chougale, Ashok D.; Kulkarni, Mahesh J.; Arvindekar, Akalpita U. (Molecular Biosystems, 2013)
Inhibition of protein glycation is known to ameliorate secondary complications in diabetes. In the present study antiglycative properties of limonene, a natural product, were evaluated using BSA as a model protein. AMG (aminoguanidine) was used as a positive control. Measurement of total AGEs (Advanced Glycation End-products) and specific AGEs revealed that limonene could inhibit protein glycation to the extent of 56.3% and 75.1% respectively at 50 mu M concentration as against 54.4% and 82.2% by AMG at 1 mM. Congo red binding and CD (Circular Dichroism) analysis revealed inhibition of alpha-helix to beta-sheet transition wherein 18.5% beta-sheet structures were observed in glycated BSA (bovine serum albumin) as against 4.9% with limonene. Glycation of protein in the presence of urea was enhanced by 18%, while in the presence of limonene it was reduced by 23% revealing the stabilizing effect of limonene. Electrophoretic mobility was similar to the normal control and a zeta potential value of -12.1 mV as against -15.1 mV in diabetic control was observed. Inhibition of glycation in limonene treated samples was confirmed through LC-MS analysis wherein AGEs such as pentosidine, CML (N-epsilon-(carboxymethyl)lysine), CEL (N-epsilon-(carboxyethyl) lysine), MOLD (methylglyoxal-lysine dimer) and imidazolone observed in glycated samples were absent in limonene treated samples. PatchDock studies revealed that limonene could bind to the major glycation sites IB, IIA and IIB sub domains and AMG to the IIIA sub domain. Thus limonene is a potent protein glycation inhibitor that prevents protein glycation through a novel mechanism of stabilization of protein structure through hydrophobic interactions.

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

One-pot migration-formylation of benzyl aryl ethers under duff reaction condition - Chavan, Subhash P.; Lasonkar, Pradeep B. (Tetrahedron Letters, 2013)
A one-pot migration-formylation of benzyl aryl ethers under Duff reaction condition is described. The reaction was performed with HMTA (hexamethylene tetramine) and TFA (trifluoroacetic acid). Under the optimal reaction conditions, a variety of Bn and PMB ethers underwent ortho rearrangement. (C) 2013 Elsevier Ltd. All rights reserved.
Keywords: Benzyl aryl ethers; Duff reaction; Hexamethylene tetramine; One-pot; ortho Rearrangement

One-pot synthesis of gold nanoparticle/molybdenum cluster/graphene oxide nanocomposite and its photocatalytic activity - Barras, Alexandre; Das, Manash R.; Devarapalli, Rami Reddy; Shelke, Manjusha V.; Cordier, Stephane; Szunerits, Sabine; Boukherroub, Rabah (Applied Catalysis B-Environmental, 2013)
The paper reports on a facile one-pot synthesis of a tri-component gold nanoparticle/molybdenum cluster/graphene oxide (AuNPs@Mo-GO) nanohybrid composite. The synthetic methodology consists on direct UV irradiation of an aqueous solution containing graphene oxide (GO), Na-2[Mo6Br8(N-3)(6)], HAuCl4 center dot 3H(2)O and isopropanol at room temperature in air using a UV fiber lamp. The composite material exhibits very high photocatalytic activity for the degradation of rhodamine B under visible light irradation. The resulting nanohybrid material was characterized using Raman spectroscopy, UV-vis spectrometry, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). (c) 2012 Elsevier B.V. All rights reserved.
Keywords: gold nanoparticles; graphene oxide; Nanohybrid; Photodegradation; Rhodamine B; visible light; [Mo6Br8(N-3)(6)](2-)cluster

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

Organophotocatalysis in nanostructured soft gel materials as tunable reaction vessels: comparison with homogeneous and micellar solutions - Bachl, Jurgen; Hohenleutner, Andreas; Dhar, Basab Bijayi; Cativiela, Carlos; Maitra, Uday; Koenig, Burkhard; Diaz, David Diaz (Journal of Materials Chemistry A, 2013)
Riboflavin tetraacetate-catalyzed aerobic photooxidation of 1-(4-methoxyphenyl)ethanol was investigated as a model reaction under blue visible light in different soft gel materials, aiming to establish their potential as reaction vessels for photochemical transformations. Three strategies involving different degrees of organization of the catalyst within the gel network were explored, and the results compared to those obtained in homogeneous and micellar solutions. In general, physical entrapment of both the catalyst and the substrate under optimized concentrations into several hydrogel matrices (including low-molecular-weight and biopolymer-based gels) allowed the photooxidation with conversions between 55 and 100% within 120 min (TOF similar to 0.045-0.08 min(-1); k(obs) similar to 0.011-0.028 min(-1)), albeit with first-order rates ca. 1-3-fold lower than in solution under comparable non-stirred conditions. Remarkably, the organogel made of a cyclohexane-based bisamide gelator in CH3CN not only prevented the photodegradation of the catalyst but also afforded full conversion in less than 60 min (TOF similar to 0.167 min(-1); k(obs) similar to 0.073 min(-1)) without the need of additional proton transfer mediators (e. g., thiourea) as it occurs in CH3CN solutions. In general, the gelators could be recycled without detriment to their gelation ability and reaction rates. Moreover, kinetics could be fine-tuned according to the characteristics of the gel media. For instance, entangled fibrillar networks with relatively high mechanical strength were usually associated with lower reaction rates, whereas wrinkled laminated morphologies seemed to favor the reaction. In addition, the kinetics results showed in most cases a good correlation with the aeration efficiency of the gel media.

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

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

Proteomic study reveals downregulation of apolipoprotein A1 in plasma of poorly controlled diabetes: a pilot study - Bhonsle, Hemangi S.; Korwar, Arvind M.; Chougale, Ashok D.; Kote, Sachin S.; Dhande, Nitin L.; Shelgikar, Kishore M.; Kulkarni, Mahesh J. (Molecular Medicine Reports, 2013)
Proteomic approaches aid in gaining a better understanding of the pathophysiology of diabetic complications. In view of this, differential protein expression in diabetic plasma samples was studied by a combination of proteomic and western blot analyses. Diabetic plasma samples were categorized based on glycated haemoglobin levels as controlled diabetes (CD; 7-8%), poorly controlled diabetes (PCD; >8%) and non-diabetic control (ND;<6.4%). Two-dimensional electrophoresis and liquid chromatography-mass spectrometry revealed differential expression of proteins including upregulation of fibrinogen and haptoglobin and downregulation of vitamin D binding protein, alpha-1-antitrypsin, transthyretin and apolipoprotein A1 (Apo A1) in diabetic compared with non-diabetic plasma samples. Amongst these proteins, Apo A1 downregulation was prominent in PCD. Downregulation of Apo A1 may serve as an early predictive marker of diabetic complications.
Keywords: biomarker; HbA1c; proteomics

Proton-conducting supramolecular metallogels from the lowest molecular weight assembler ligand: a quote for simplicity - Saha, Subhadeep; Schoen, Eva-Maria; Cativiela, Carlos; Diaz, David Diaz; Banerjee, Rahul (Chemistry-A European Journal, 2013)
Oxalic acid has been proven to be the lowest molecular weight organic ligand able to form robust supramolecular metallogel networks in the presence of metal salts. In particular, two novel multifunctional metallogels were readily prepared at room temperature by simple mixing of stock solutions of Cu-II acetate monohydrate or Cu-II perchlorate hexahydrate and oxalic acid dihydrate. Formation of different polymorphs and unprecedented proton conduction under anhydrous conditions were also demonstrated with some of these materials.
Keywords: Copper; low-molecular-weight ligands; metallogels; proton conductivity; supramolecular chemistry

Quantifying the mechanism of phosphate monoester hydrolysis in aqueous solution by evaluating the relevant Ab initio QM/MM free-energy surfaces - Plotnikoy, Nikolay V.; Prasad, B. Ram; Chakrabarty, Suman; Chu, Zhen T.; Warshel, Arieh (Journal of Physical Chemistry B, 2013)
Understanding the nature of the free-energy surfaces for phosphate hydrolysis is a prerequisite for understanding the corresponding key chemical reactions in biology. Here, the challenge has been to move to careful ab initio QM/MM (QM(ai)/MM) free-energy calculations, where obtaining converging results is very demanding and computationally expensive. This work describes such calculations, focusing on the free-energy surface for the hydrolysis of phosphate monoesters, paying special attention to the comparison between the one water (1W) and two water (2W) paths for the proton-transfer (PT) step. This issue has been explored before by energy minimization with implicit solvent models and by nonsystematic QM/MM energy minimization, as well as by nonsystematic free-energy mapping. However, no study has provided the needed reliable 2D (3D) surfaces that are necessary for reaching concrete conclusions. Here we report a systematic evaluation of the 2D (3D) free-energy maps for several relevant systems, comparing the results of QM(ai)/MM and QM(ai)/implicit solvent surfaces, and provide an advanced description of the relevant energetics. It is found that the 1W path for the hydrolysis of the methyl diphosphate (MDP) trianion is 6-9 kcal/mol higher than that the 2W path. This difference becomes slightly larger in the presence of the Mg2+ ion because this ion reduces the plc of the conjugated acid form of the phosphate oxygen that accepts the proton. Interestingly, the BLYP approach (which has been used extensively in some studies) gives a much smaller difference between the 1W and 2W activation barriers. At any rate, it is worth pointing out that the 2W transition state for the PT is not much higher that the common plateau that serves as the starting point of both the 1W and 2W PT paths. Thus, the calculated catalytic effects of proteins based on the 2W PT mechanistic model are not expected to be different from the catalytic effects predicted using the 1W PT mechanistic model, which was calibrated on the observed barrier in solution and in which the TS charge distribution was similar to the that of the plateau (as was done in all of our previous EVB studies).

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

Seasonal prediction of Indian summer monsoon in NCEP coupled and uncoupled model - Chaudhari, Hemantkumar S.; Pokhrel, Samir; Mohanty, Sachiko; Saha, Subodh K. (Theoretical and Applied Climatology, 2013)
This study has identified probable factors that govern ISMR predictability. Furthermore, extensive analysis has been performed to evaluate factors leading to the predictability aspect of Indian Summer Monsoon Rainfall (ISMR) using uncoupled and coupled version of National Centers for Environmental Prediction Coupled Forecast System (CFS). It has been found that the coupled version (CFS) has outperformed the uncoupled version [Global Forecast System (GFS)] of the model in terms of prediction of rainfall over Indian land points. Even the spatial distribution of rainfall is much better represented in the CFS as compared to that of GFS. Even though these model skills are inadequate for the reliable forecasting of monsoon, it imparts the capacious knowledge about the model fidelity. The mean monsoon features and its evolution in terms of rainfall and large-scale circulation along with the zonal and meridional shear of winds, which govern the strength of the monsoon, are relatively closer to the observation in the CFS as compared to the GFS. Furthermore, sea surface temperature-rainfall relation is fairly realistic and intense in the coupled version of the model (CFS). It is found that the CFS is able to capture El Nio Southern Oscillation ISMR (ENSO-ISMR) teleconnections much strongly as compared to GFS; however, in the case of Indian Ocean Dipole ISMR teleconnections, GFS has the larger say. Coupled models have to be fine-tuned for the prediction of the transition of El Nio as well as the strength of the mature phase has to be improved. Thus, to sum up, CFS tends to have better predictive skill on account of following three factors: (a) better ability to replicate mean features, (b) comparatively better representation of air-sea interactions, and (c) much better portrayal of ENSO-ISMR teleconnections. This study clearly brings out that coupled model is the only way forward for improving the ISMR prediction skill. However, coupled model's spurious representation of SST variability and mean model bias are detrimental in seasonal prediction.

Selective imaging of quorum sensing receptors in bacteria using fluorescent Au nanocluster probes surface functionalized with signal molecules - Mukherji, Ruchira; Samanta, Anupam; Illathvalappil, Rajith; Chowdhury, Somak; Prabhune, Asmita; Devi, R. Nandini (ACS Applied Materials & Interfaces, 2013)
Fluorescent ultrasmall gold clusters decorated with bacterial quorum sensing signal molecules, acyl homoserine lactone, are synthesized. These fluorescent probes are found to have emission in the near-infrared spectral region advantageous for bioimaging. Imaging studies using different. strains of bacteria with and without acyl homoserine lactone receptors with the aid of confocal microscopy have shown that the probe interacts preferentially with cells possessing these receptors. This indicates that, with appropriate surface functionalization, the Au clusters can be used for receptor specific detection with enhanced selectivity.
Keywords: Au nanoclusters; Biosensor; fluorescence imaging; quorum sensing

Sensing behavior of atomically thin-layered MoS2 transistors - Late, Dattatray J.; Huang, Yi-Kai; Liu, Bin; Acharya, Jagaran; Shirodkar, Sharmila N.; Luo, Jiajun; Yan, Aiming; Charles, Daniel; Waghmare, Umesh V.; Dravid, Vinayak P.; Rao, C. N. R. (ACS Nano, 2013)
Most of recent research on layered chalcogenides is understandably focused on single atomic layers. However, it is unclear if single-layer units are the most ideal structures for enhanced gas solid interactions. To probe this issue further, we have prepared large-area MoS2 sheets ranging from single to multiple layers on 300 nm SiO2/Si substrates using the micromechanical exfoliation method. The thickness and layering of the sheets were identified by optical microscope, invoking recently reported specific optical color contrast, and further confirmed by AFM and Raman spectroscopy. The MoS2 transistors with different thicknesses were assessed for gas-sensing performances with exposure to NO2, NH3, and humidity in different conditions such as gate bias and light Irradiation. The results show that, compared to the single-layer counterpart, transistors of few MoS2 layers exhibit excellent sensitivity, recovery, and ability to be manipulated by gate bias and green light. Further, our ab initio DFT calculations on single-layer and bilayer MoS2 show that the charge transfer is the reason for the decrease in resistance in the presence of applied field.

Short synthesis of (2S,3S)-3-hydroxypipecolic acid - Chavan, Subhash P.; Harale, Kishor R.; Pawar, Kailash P. (Tetrahedron Letters, 2013)
A convenient synthesis of (2S,3S)-3-hydroxypipecolic acid starting from cheap and abundant L-(+)-tartaric acid has been achieved. The strategy employs selective ester reduction and reductive lactamization as key steps. (C) 2013 Elsevier Ltd. All rights reserved.
Keywords: Reductive lactamization; Selective deprotection; Wittig reaction

Simple synthesis of the novel antihistaminic drug olopatadine hydrochloride - Chavan, Subhash P.; Lasonkar, Pradeep B. (Synthesis-Stuttgart, 2013)
A new alternative route for the synthesis of olopatadine is described. The present strategy involves a Lewis acid mediated ring opening of a cyclic ether to introduce 3-(dimethylamino)propylidene group as the side chain.
Keywords: antihistaminic drugs; chelates; Lewis acids; spiro compounds; zinc

Solvent-free, highly efficient one-pot multi-component synthesis of 1-amido- and 1-carbamato-alkyl naphthols/phenols catalyzed by ethylammonium nitrate as reusable ionic liquid under neat reaction condition at ambient temperature - Mulla, Shafeek Abdul Rashid; Salama, Tarek A.; Pathan, Mohsinkhan Y.; Inamdar, Suleman M.; Chavan, Santosh S. (Tetrahedron Letters, 2013)
A solvent-free, environmentally clean, mild, and simple one-pot multi-component protocol has been developed for the efficient synthesis of 1-amido- and 1-carbamato-alkyl naphthols/phenols in excellent yields via one-pot three-component condensation of various aldehydes, amides/carbamates/urea, and naphthols/phenols using ethylammonium nitrate (EAN) as a reusable ionic liquid catalyst under neat reaction condition at ambient temperature. (c) 2012 Elsevier Ltd. All rights reserved.
Keywords: Aldehyde; amide; Carbamate Phenol; Ethylammonium nitrate (EAN); Urea

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

Structural and dynamical properties of polyethylenimine in explicit water at different protonation states: a molecular dynamics study - Choudhury, Chandan Kumar; Roy, Sudip (Soft Matter, 2013)
PEI is a pH sensitive polymer which acts as a proton sponge in acidic conditions. Despite many experimental and theoretical efforts, a fundamental understanding of the structure and dynamics of linear PEI chains on the atomistic level at different protonation states in dilute solutions remains a topic of discussion. This report analyses the structural properties of PEI at different protonation states, which are representative of different pH, using all atomistic molecular dynamic simulations. The structural properties revealed that the polymer at high pH (basic medium) is highly coiled, while at low pH (strong acidic conditions) the chains are elongated. We studied the dynamics and ordering of water molecules that are part of the solvation shells of the PEI chains at different protonation states. We observe that the water molecules are ordered along the polymer backbone for a completely protonated PEI chain (i.e. in the case of acidic pH) and hop to the neighbouring solvation shell. The residence time and the self-diffusion of water molecules in the solvation shells and their activation barriers were also calculated and analysed further. We concluded the study by correlating the solvation shell water dynamics and the structure of the PEI chain at different protonation states.

Structural and logical analysis of a comprehensive hedgehog signaling pathway to identify alternative drug targets for glioma, colon and pancreatic cancer - Chowdhury, Saikat; Pradhan, Rachana N.; Sarkar, Ram Rup (Plos One, 2013)
Hedgehog is an evolutionarily conserved developmental pathway, widely implicated in controlling various cellular responses such as cellular proliferation and stem cell renewal in human and other organisms, through external stimuli. Aberrant activation of this pathway in human adult stem cell line may cause different types of cancers. Hence, targeting this pathway in cancer therapy has become indispensable, but the non availability of detailed molecular interactions, complex regulations by extra- and intra-cellular proteins and cross talks with other pathways pose a serious challenge to get a coherent understanding of this signaling pathway for making therapeutic strategy. This motivated us to perform a computational study of the pathway and to identify probable drug targets. In this work, from available databases and literature, we reconstructed a complete hedgehog pathway which reports the largest number of molecules and interactions to date. Using recently developed computational techniques, we further performed structural and logical analysis of this pathway. In structural analysis, the connectivity and centrality parameters were calculated to identify the important proteins from the network. To capture the regulations of the molecules, we developed a master Boolean model of all the interactions between the proteins and created different cancer scenarios, such as Glioma, Colon and Pancreatic. We performed perturbation analysis on these cancer conditions to identify the important and minimal combinations of proteins that can be used as drug targets. From our study we observed the under expressions of various oncoproteins in Hedgehog pathway while perturbing at a time the combinations of the proteins GLI1, GLI2 and SMO in Glioma; SMO, HFU, ULK3 and RAS in Colon cancer; SMO, HFU, ULK3, RAS and ERK12 in Pancreatic cancer. This reconstructed Hedgehog signaling pathway and the computational analysis for identifying new combinatory drug targets will be useful for future in-vitro and in-vivo analysis to control different cancers.

Structure-property relationship of different types of polyester industrial yarns - Samui, Barun Kumar; Prakasan, Manikanda Priya; Ramesh, C.; Chakrabarty, Debabrata; Mukhopadhyay, R. (Journal of the Textile Institute, 2013)
Four major types of polyester industrial yarns (1000 Denier) which are used commercially were studied for their key structural parameters. An attempt has been made to establish a relationship between morphology and properties of these yarns. High tenacity (HT) polyester yarn has the highest birefringence, amorphous orientation, and long period but is relatively less crystalline. High shrinkage characteristic of HT polyester yarn can be accounted for its higher amorphous orientation. High modulus low shrinkage (HMLS) polyester yarn has higher crystallinity and crystal size compared to HT yarn. Fraction of tie molecules of these yarns has been calculated and found that low shrinkage (LS) and super low shrinkage (SLS) yarns have lesser tie molecules. These LS and SLS yarns are tailor-made to achieve lower shrinkage and at the same time maintaining a good level of tenacity. This is achieved with lower amorphous orientation in the final drawn yarn structure. Amorphous orientation was found to have stronger influence than any other structural parameter on the key yarn properties like modulus, tenacity, elongation, and shrinkage.
Keywords: modulus; orientation; polyester; shrinkage; structure

Surfactant-free synthesis of anisotropic gold nanostructures: can dicarboxylic acids alone act as shape directing agents? - Kumar, D. V. Ravi; Kumavat, S. R.; Chamundeswari, V. N.; Patra, Partha Pratim; Kulkarni, A. A.; Bhagavatula L. V. Prasad (RSC Advances, 2013)
The present study describes the synthesis of gold nanostructures using different dicarboxylic (viz. oxalic, malonic, succinic, glutaric and adipic) acids as reducing agents in the absence of any other additives or surfactants. Various anisotropic structures such as kites, tadpoles, triangular/hexagonal plates, and twinned particles were seen to evolve depending on the molar ratio of dicarboxylic acid to HAuCl4 used. It was also demonstrated that gold nanostructure formation is hampered as the chain length/distance between two carboxylic acid groups increases. Among the various structures obtained the kite like structures displayed the largest surface enhanced Raman enhancement factors.

Suzuki-Miyaura cross-coupling reaction between aryl halides and phenylboronic acids over gold nano-particles supported on MgO (or CaO) and other metal oxides - Dumbre, Deepa K.; Yadav, P. N.; Bhargava, Suresh Kumar; Choudhary, Vasant R. (Journal of Catalysis, 2013)
Gold nano-particles-supported alkaline earth metal oxides, particularly MgO or CaO, show high catalytic activity in the Suzuki-Miyaura cross-coupling reaction in the presence of K2CO3 and DMF (as a solvent). The catalytic activity is strongly influenced by the nature or type of metal oxide support (viz, alkaline earth oxide, Group IIIA metal oxide, transition metal oxide, or rare earth oxide actinide oxide). It is also strongly influenced by the nature of aryl halide (aryl iodide, bromide, chloride, or fluoride), amount of K2CO3 in the reaction mixture and catalyst calcination temperature. Influence of reaction parameters viz, temperature and time and different substituents in aryl halides and/or phenylboronic acids on the biphenyl product yield in the reaction over Au/MgO catalyst has also been investigated. The catalyst showed excellent reusability in the reaction. Moreover, it is ligand-free and also has much lower cost than the commonly used homogeneous and heterogeneous Pd catalysts. (C) 2013 Elsevier Inc. All rights reserved.
Keywords: Aryl halides; Au/MgO (or CaO) catalyst; Biphenyls; Gold nano-particles; phenylboronic acids; Suzuki-Miyaura coupling reaction

Synthesis, structure, and H-2/CO2 adsorption in a three-dimensional 4-connected triorganotin coordination polymer with a sqc topology - Chandrasekhar, Vadapalli; Mohapatra, Chandrajeet; Banerjee, Rahul; Mallick, Arijit (Inorganic Chemistry, 2013)
A 4-connected triorganotin 3D coordination polymer in a sqc topology has been shown to possess 1D microchannels along its crystallographic a axis. This main-group-element-containing framework structure shows selective gas adsorption, preferring CO2 and H-2 over N-2.

Thermoresponsive and biodegradable dextran based microgels: synthesis and structural investigation - Ghugare, Shivkumar V.; Chiessi, Ester; Sakai, Victoria Garcia; Telling, Mark T. F.; Wadgaonkar, Prakash P.; Paradossi, Gaio (Macromolecular Symposia, 2013)
Nanostructured objects, often ranging from hundreds of nanometers to few microns, support a number of functions directly linked to their structural features. They are, or they will be, protagonists in biomedical applications where miniaturized activities are required. These include the interface with living systems as tissues and cells, where targeted release of drug molecules occurs, or molecular imaging methods monitoring the drug trafficking in specific cell districts. The potentials of such devices, far to be fully understood, will be assessed only when a close correlation of their functions with their structure will be established. In this contribution we present a dextran based microdevice responsive to temperature and biodegradable. Both thermoresponsivity and biodegradability are of relevance for the potential use as drug carrier and controlled release device. The temperature behaviour, overall structure and internal architectures have been addressed with different methods.
Keywords: Biomaterials; colloids; dynamic light scattering; hydrogels; p(NiPAAm)

Total synthesis of umuravumbolide and hyptolide through silicon-tethered ring-closing metathesis - Chowdhury, Partha Sarathi; Kumar, Pradeep (European Journal of Organic Chemistry, 2013)
The total synthesis of umuravumbolide and hyptolide has been achieved in a efficient manner by using temporary silicon-tethered ring-closing metathesis and cross-coupling reactions as key steps. The stereogenic centres were generated by means of proline-catalysed -aminoxylation of aldehydes and Brown's asymmetric allylation method.
Keywords: lactones; Metathesis; Silanes; synthetic methods; Total synthesis; Wittig reactions

9-Fluorenemethanol: an internal electron donor to fine tune olefin polymerization activity - Gnanakumar, Edwin S.; Chokkapu, Eswara Rao; Kunjir, Shrikant; Ajithkumar, Thalasseril G.; Rajamohanan, P. R.; Chakraborty, Debashis; Gopinath, Chinnakonda S. (Dalton Transactions, 2014)
A new MgCl2 based molecular adduct has been synthesized with 9-fluorenemethanol (9FM) as a novel internal electron donor (IED), along with ethanol (EtOH) (MgCl2 center dot n9FM center dot xEtOH). The above molecular adduct has been subjected to a variety of structural, spectroscopic and morphological characterization techniques. The results of the solid state C-13 CPMAS NMR technique suggests the coordination of 9FM to MgCl2. Observation of a low angle diffraction peak at 2 theta = 5.7 degrees (d = 15.5 angstrom) underscores the coordination of 9FM along the z-axis, and ethanol in the molecular adduct. Active Ziegler-Natta catalysts were prepared by two different synthesis methods; the conventional method to obtain a high surface area active catalyst, and other one with 9FM as an integral part of the active catalyst in order to study the influence of 9FM as an IED over the active sites. The active catalysts were also characterized thoroughly with different analytical tools. The XRD results show (003) facets of delta-MgCl2 (alpha-MgCl2) for the conventional (non-conventional) titanated catalyst. Results of the ethylene polymerization activity study reveals that the conventionally prepared highly porous active catalyst shows 1.7-2.5 times higher activity than the non-conventional prepared catalyst; however, the latter shows a low molecular weight distribution and confirms the role of the Lewis base as an IED.

Additive induced capture of elusive polymorphs of conformationally flexible Sulfonamides/Sulfoesters - Shaikh, Samir Rashid; Gawade, Rupesh L.; Chakravarty, Debamitra K.; Puranik, Vedavati G.; Gonnade, Rajesh (Acta Crystallographica A‐Foundation and Advances, 2014)
Keywords: additive induced polymorphism; intermolecular interactions; phase transition

Antifungal activity and mechanism of action of carvacrol and thymol against vineyard and wine spoilage yeasts - Chavan, Pradnya S.; Tupe, Santosh G. (Food Control, 2014)
Antimicrobial activity of carvacrol and thymol against natural yeast flora of the grapes and yeasts known to cause wine spoilage was examined. Carvacrol and thymol exhibited comparable or better antifungal activity than potassium metabisulphite, commercially used wine preservative, against the natural yeast flora and spoilage yeasts. The antifungal activity for both the compounds was better at pH 3.5 than pH 6.5. Addition of carvacrol and thymol (64 mu g/mL) in red wine resulted in inhibition of growth of the spoilage yeasts. Carvacrol and thymol exerted their antimicrobial action through membrane damage, leakage of cytoplasmic content and ergosterol depletion. In conclusion, carvacrol and thymol holds promise as a potential natural preservative for the control of wine spoilage. (C) 2014 Elsevier Ltd. All rights reserved.
Keywords: antifungal; Carvacrol; Thymol; Wine spoilage

Antifungal dimeric chalcone derivative kamalachalcone E from Mallotus philippinensis - Kulkarni, Roshan R.; Tupe, Santosh G.; Gample, Suvarna P.; Chandgude, Macchindra G.; Sarkar, Dhiman; Deshpande, Mukund V.; Joshi, Swati P. (Natural Product Research, 2014)
From the red coloured extract (Kamala) prepared through acetone extraction of the fresh whole uncrushed fruits of Mallotus philippinensis, one new dimeric chalcone (1) along with three known compounds 1-(5,7-dihydroxy-2,2,6-trimethyl-2H-1-benzopyran-8-yl)-3-phenyl-2-propen -1-one (2), rottlerin (3) and 4 `-hydroxyrottlerin (4) were isolated. The structure of compound 1 was elucidated by 1D and 2D NMR analyses that included HSQC, HMBC, COSY and ROESY experiments along with the literature comparison. Compounds 1-4 were evaluated for antifungal activity against different human pathogenic yeasts and filamentous fungi. The antiproliferative activity of the compounds was evaluated against Thp-1 cell lines. Compounds 1 and 2 both exhibited IC50 of 8, 4 and 16 mu g/mL against Cryptococcus neoformans PRL518, C. neoformans ATCC32045 and Aspergillus fumigatus, respectively. Compound 4, at 100 mu g/mL, showed 54% growth inhibition of Thp-1 cell lines.
Keywords: 4 `-hydroxyrottlerin; antifungal; dimeric chalcone; kamalachalcone E; Mallotus philippinensis; rottlerin

Antimicrobial activity of a new series of Bis(isoxazoline),Bis(isoxazole)and their derivatives - Gajbhiye, Jayant M.; Chopade, A. U. (International Journal of Chemical and Physical Sciences, 2014)
A series of 1,1-bis [2-hydroxy-3-(5’-aryl-isoxazoline-3-yl)-5-methyl phenyl] methane and 1,1-bis [2-hydroxy-3-(5’-aryl-isoxazol-3-yl)-5-methyl phenyl] methane derivatives were evaluated for their antimicrobial activity against some selected pathogenic micro-organisms such as Gram-positive bacteria, Staphylococcus aureus, Citrobacter frundii, Bacillus megatherium and Gram-negative bacteria Staphyloccus aureus, Escherichia coli, Proteus mirabilis, Pseudomonas aeruginosa, Enterobacter aerogenes, Salmonella typhi, Proteus vulgaris.

Antimicrobial and SEM studies of sophorolipids synthesized using lauryl alcohol - Dengle-Pulate, Vrushali; Chandorkar, Parul; Bhagwat, Sunil S.; Prabhune, Asmita Ashutosh (Journal of Surfactants and Detergents, 2014)
In recent years, researchers have developed biosurfactants for industrial, pharmaceutical and medical applications revealing the promising biological activities of these biomolecules. One of the best studied microbial surfactants are glycolipids, especially sophorolipids (SLs) produced by selected non-pathogenic yeast species of Candida. They are biodegradable, non-toxic and are environmentally friendly. Sophorolipid production was carried out using glucose as the hydrophilic source and lauryl alcohol C12-14, as the hydrophobic source using Candida bombicola ATCC 22214. Primary characterization of the SL obtained using lauryl alcohol (SLLA) was done by FTIR which depicted the presence of alkyl sophorosides/SLs. Antimicrobial activity testing revealed that SLLA showed complete inhibition against gram negative bacteria, Escherichia coli (ATCC 8739) Pseudomonas aeruginosa (ATCC 9027) at 30 and 1 mu g/ml at a contact time of 2 and 4 h respectively. Whereas for gram positive bacteria Staphylococcus aureus (ATCC 6358), Bacillus subtilis (ATCC 6633), complete inhibition was observed at 6 and 1 mu g/ml respectively at a contact time of 4 h. The formed SLLA showed noteworthy inhibition against the pathogenic yeast Candida albicans (ATCC 2091) at 50 mu g/ml with a contact time of 4 h. These values are remarkably low compared to reported values of oleic acid SLs and linolenic acid SLs which were studied for antimicrobial properties. Scanning electron microscopy analysis of the treated cells revealed the changes in morphology and topography of the microorganisms.
Keywords: Antimicrobial property; Biosurfactants; Candida bombicola; Lauryl alcohol; sophorolipids

Artificial intelligence-based modeling of high ash coal gasification in a pilot plant scale fluidized bed gasifier - Patil-Shinde, Veena; Kukarni, Tejas; Kulkarni, Rahul; Chavan, Prakash D.; Sharma, Tripurari; Sharma, Bijay Kumar; Tambe, Sanjeey S.; Kulkarni, B. D. (Industrial & Engineering Chemistry Research, 2014)
The quality of coalespecially its high ash contentsignificantly affects the performance of coal-based processes. Coal gasification is a cleaner and an efficient alternative to the coal combustion for producing the syngas. The high-ash coals are found in a number of countries, and they form an important source for the gasification. Accordingly, in this study, extensive gasification experiments were conducted in a pilot-plant scale fluidized-bed coal gasifier (FBCG) using high-ash coals from India. Specifically, the effects of eight coal and gasifier process related parameters on the four gasification performance variables, namely CO+H-2 generation rate, syngas production rate, carbon conversion, and heating value of the syngas, were rigorously studied. The data collected from these experiments were used in the FBCG modeling, which was conducted by utilizing two artificial intelligence (AI) strategies namely genetic programming (GP) and artificial neural networks (ANNs). The novelty of the GP formalism is that it searches and optimizes both the form and parameters of an appropriate linear/nonlinear function that best fits the given process data. The original eight-dimensional input space of the FBCG models was reduced to three-dimensional space using the principal component analysis (PCA) and the PCA-transformed three variables were used in the AI-based FBCG modeling. A comparison of the GP and ANN-based models reveals that their output prediction accuracies and the generalization performance vary from good to excellent as indicated by the high training and test set correlation coefficient magnitudes lying between 0.92 and 0.996. This study also presents results of the sensitivity analysis performed to identify those coal and process related parameters, which significantly affect the FBCG process performance.

Calcium oxide supported gold nanoparticles as catalysts for the selective epoxidation of styrene by t-butyl hydroperoxide - Dumbre, Deepa K.; Choudhary, Vasant R.; Patil, Nilesh S.; Uphade, Balu S.; Bhargava, Suresh Kumar (Journal of Colloid and Interface Science, 2014)
Gold nanoparticles are deposited on basic CaO supports as catalysts for the selective conversion of styrene into styrene oxide. Synthetic methods, gold loading and calcination temperatures are varied to permit an understanding of their influence on gold nanoparticle size, the presence of cationic gold species and the nature of interaction between the gold nanoparticles and the CaO support. Based on these studies, optimal conditions are designed to make the Au/CaO catalyst efficient for the selective epoxidation of styrene. (C) 2013 Elsevier Inc. All rights reserved.
Keywords: Au/CaO; Epoxidation of styrene; gold nanoparticles; Homogenous deposition precipitation method; Styrene oxide

CdS nanowires: ultra-long growth and enhanced field emission properties - Chavan, Padmakar G.; Kashid, Ranjit V.; Badhade, Satish S.; Mulla, Imtiaz S.; More, Mahendra A.; Joag, Dilip S. (Vaccum, 2014)
Here, we report the synthesis of ultra-long CdS nanowires with aspect ratio similar to 8 x 10(4) by simple route of thermal evaporation technique. A change in the vertical arrangement of quartz boats leads in to the synthesis of ultra-long CdS nanovvires via high degree of condensation. This technique is seen to be cost effective and easy. The growth of the nanowires is found to be increased very rapidly from few micrometers to few millimeters. The possible reason for the growth of the ultra-long CdS nanowires is discussed in detail. The turn-on field defined for the current density of similar to 0.1 mu A/cm(2) has been found to be similar to 1.4, 1.45, 1 and 0.17 V/mu m for specimen A, B, C and D (specimens A-D, synthesized by variation in synthesis parameters) respectively. The turn-on field of the specimen D (similar to 0.17 V/mu m) is found to be quite superior than the value reported for other CdS nanoforms which is very remarkable. Simple way of bulk fabrication leads to the low turn-on value which indicates a possible use of the present emitter in the micro/nanoelectronics devices. (C) 2013 Elsevier Ltd. All rights reserved.
Keywords: Current stability; field emission; synthesis

Cellulose supported cuprous iodide nanoparticles (Cell-CuI NPs): a new heterogeneous and recyclable catalyst for the one pot synthesis of 1,4-disubstituted-1,2,3-triazoles in water - Chavan, Pramod V.; Pandit, Kapil S.; Desai, Uday V.; Kulkarni, Makarand A.; Wadgaonkar, Prakash P. (RSC Advances, 2014)
Cellulose supported cuprous iodide nanoparticles (Cell-CuI NPs) have been demonstrated for the first time as an efficient heterogeneous catalyst in the click synthesis of 1,4-disubstituted 1,2,3-triazoles by a one-pot three component reaction between aralkyl/alkyl bromides, alkynes and sodium azide in water. The catalyst has been characterized by XRD, HRTEM, SEM, ICP-AES, EDS as well as IR spectroscopy. It was found to be reusable for five consecutive runs without significant loss of activity.

CH3NH3PbI(3-x)(BF4)(x): molecular ion substituted hybrid perovskite - Nagane, Satyawan; Bansode, Umesh P.; Game, Onkar S.; Chhatre, Shraddha; Ogale, Satishchandra (Chemical Communications, 2014)
A molecular ion (BF4-) substituted hybrid perovskite CH3NH3PbI(3-x)(BF4)(x) is synthesized. The substituted perovskite shows significant enhancement in electrical conductivity at low frequencies and improved photoresponse under AM1.5 illumination as compared to the perovskite (CH3NH3PbI3).

Chemoselective deprotection of N-allylic amines using DDQ - Kumar, Pradeep; Cherian, Shijo K.; Jain, Ruchi; Show, Krishanu (Tetrahedron Letters, 2014)
A highly chemoselective and simple method for the deprotection of N-allylic amines using DDQ has been developed. The use of DDQ in dichloromethane-water provides a mild and efficient one-step deallylation of a wide variety of orthogonally protected tertiary amine derivatives. (C) 2014 Elsevier Ltd. All rights reserved.
Keywords: Chemoselective deprotection; DDQ; N-Allylic amines; Orthogonally protected tertiary amines

Chiron approach to formal synthesis of both antipodes of cis 3-hydroxypipecolic acid - Chavan, Subhash P.; Khairnar, Lalit B.; Chavan, Prakash N.; Dumare, Nilesh B.; Kalbhor, Dinesh B.; Gonnade, Rajesh G. (Tetrahedron Letters, 2014)
The efficient and practical formal syntheses of both enantiomers of cis 3-hydroxypipecolic acid were accomplished from cis aziridine-2-carboxylate as the common synthetic precursor. The key steps involved are stereo and regioselective aziridine ring opening, reductive cyclization and selective N-debenzylation over O-debenzylation reactions. (C) 2014 Elsevier Ltd. All rights reserved.
Keywords: 3-Hydroxypipecolic acid; Aziridine ring opening; Aziridine-2-carboxylate; Piperidine alkaloids; Selective debenzylation

Chitosan and chitosan-co-poly(epsilon-caprolactone) grafted multiwalled carbon nanotube transducers for vapor sensing - Rana, Vijay Kumar; Akhtar, Shamim; Chatterjee, Sudipta; Mishra, Satyendra; Singh, Raj Pal; Ha, Chang-Sik (Journal of Nanoscience and Nanotechnology, 2014)
Vapor sensitive transducer films consisting of chitosan grafted (CNT-CS) and chitosan-co-polycaprolactone grafted (CNT-CS-PCL) multiwalled carbon nanotubes were prepared using a spray layer-by-layer technique. The synthesized materials (CNT-CS and CNT-CS-PCL) were characterized by Fourier transform infrared spectroscopy, C-13 CP/MAS solid state nuclear magnetic resonance spectroscopy and thermogravimetric analysis. Both CNT-CS and CNT-CS-PCL transducers were analyzed for the response of volatile organic compounds and toluene vapors. The ranking of the relative resistance (A(r)) for both chitosan based transducers were as follows: toluene < chloroform < ethanol < methanol. The CNT transducer (CNT-CS) was correlated selectively with an exponential law to the inverse of Flory-Huggins interaction parameters, chi(12). Dosing the films on the interdigitated electrodes with methanol, ethanol, chloroform and toluene vapors increased the film resistance of CNT-CS but decreased the resistance of CNT-CS-PCL compared to that of the reported transducers.
Keywords: Biocompatibility; Chitosan; MWCNTs; Poly(epsilon-caprolactone); Vapour Sensing

Cholesterol depletion by methyl-beta-cyclodextrin augments tamoxifen induced cell death by enhancing its uptake in melanoma - Mohammad, Naoshad; Malvi, Parmanand; Meena, Avtar Singh; Singh, Shivendra Vikram; Chaube, Balkrishna; Vannuruswamy, Garikapati; Kulkarni, Mahesh J.; Bhat, Manoj Kumar (Molecular Cancer, 2014)
Background: Despite modern advances in treatment, skin cancer is still one of the most common causes of death in the western countries. Chemotherapy plays an important role in melanoma management. Tamoxifen has been used either alone or in-combination with other chemotherapeutic agents to treat melanoma. However, response rate of tamoxifen as a single agent has been comparatively low. In the present study, we investigated whether treatment with methyl-beta-cyclodextrin (MCD), a cholesterol depleting agent, increases the efficacy of tamoxifen in melanoma cells. Methods: This was a two-part study that incorporated in vitro effects of tamoxifen and MCD combination by analyzing cell survival, apoptosis and cell cycle analysis and in vivo antitumor efficacy on tumor isografts in C57BL/6J mice. Results: MCD potentiated tamoxifen induced anticancer effects by causing cell cycle arrest and induction of apoptosis. Sensitization to tamoxifen was associated with down regulation of antiapoptotic protein Bcl-2, up-regulation of proapoptotic protein Bax, reduced caveolin-1 (Cav-1) and decreased pAkt/pERK levels. Co-administration of tamoxifen and MCD caused significant reduction in tumor volume and tumor weight in mice due to enhancement of drug uptake in the tumor. Supplementation with cholesterol abrogated combined effect of tamoxifen and MCD. Conclusion: Our results emphasize a potential synergistic effect of tamoxifen with MCD, and therefore, may provide a unique therapeutic window for improvement in melanoma treatment.
Keywords: Caveolin-1; Cholesterol; Methyl beta-cyclodextrin; Tamoxifen

Cholesterol modulates the dimer interface of the beta(2)-adrenergic receptor via cholesterol occupancy sites - Prasanna, Xavier; Chattopadhyay, Amitabha; Sengupta, Durba (Biophysical Journal, 2014)
The beta(2)-adrenergic receptor is an important member of the G-protein-coupled receptor (GPCR) superfamily, whose stability and function are modulated by membrane cholesterol. The recent high-resolution crystal structure of the beta(2)-adrenergic receptor revealed the presence of possible cholesterol-binding sites in the receptor. However, the functional relevance of cholesterol binding to the receptor remains unexplored. We used MARTINI coarse-grained molecular-dynamics simulations to explore dimerization of the beta(2)-adrenergic receptor in lipid bilayers containing cholesterol. A novel (to our knowledge) aspect of our results is that receptor dimerization is modulated by membrane cholesterol. We show that cholesterol binds to transmembrane helix IV, and cholesterol occupancy at this site restricts its involvement at the dimer interface. With increasing cholesterol concentration, an increased presence of transmembrane helices I and II, but a reduced presence of transmembrane helix IV, is observed at the dimer interface. To our knowledge, this study is one of the first to explore the correlation between cholesterol occupancy and GPCR organization. Our results indicate that dimer plasticity is relevant not just as an organizational principle but also as a subtle regulatory principle for GPCR function. We believe these results constitute an important step toward designing better drugs for GPCR dimer targets.

Combined gasification of lignite coal: thermodynamic and application study - Kale, Ganesh R.; Kulkarni, Bhaskar D.; Chavan, Rank N. (Journal of the Taiwan Institute of Chemical Engineers, 2014)
Combined gasification (a combination of steam gasification and CO2 gasification) without air is an important process for research in coal gasification to reduce the steam generation energy in the gasification system and also to enhance the slow CO2 gasification reaction. A thermodynamic study involving the effect of temperature, pressure and feed CO2 and steam ratios in gasification of lignite coal was studied in this paper. The product generation trends of syngas and methane with carbon (in coal) conversion were studied in detail. The carbon (in lignite coal) was converted completely at a lower temperature than pure carbon in the combined gasification. Some applications of the gasifier product gas were also studied. Combined gasification offers great advantages to produce syngas of exact ratio in one step for use in petrochemical manufacture and fuel cell systems. The complete carbon (in coal) conversion occurred beyond the thermoneutral gasification temperature in the study. The combined gasification process was a useful way for CO2 utilization reducing the net CO2 emission to the atmosphere. (C) 2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: CO2 utilization; Coal gasification; Coal to syngas; Combined gasification; Thermodynamic study

Concise enantioselective syntheses of (+)-L-733,060 and (2S,3S)-3-hydroxypipecolicw acid by cobalt(III)(salen)-catalyzed two-stereocenter hydrolytic kinetic resolution of racemic azido epoxides - Devalankar, Dattatray A.; Chouthaiwale, Pandurang V.; Sudalai, Arumugam (Synlett, 2014)
An efficient synthesis of the 2,3-disubstituted piperidines (+)-L-733,060 and (2S,3S)-3-hydroxypipecolic acid (99% ee) in high optical purity from commercially available starting materials is described. The strategy involves a cobalt-catalyzed hydrolytic kinetic resolution of a racemic azido epoxide with two stereocenters and an intramolecular reductive cyclization as key reactions.
Keywords: azides; cyclizations; epoxides; piperidines; stereoselective synthesis; Wittig reactions

Concise synthetic approach toward tamiflu (oseltamivir phosphate): cis-aziridine as the key synthon and RCM - Chavan, S. P.; Chavan, P. N.; Khairnar, L. B. (RSC Advances, 2014)
A synthesis of oseltamivir (Tamiflu) was achieved starting from D-mannitol. A unique feature of the synthetic route is that an acyclic precursor was constructed, which was then cyclized in an intramolecular aldol reaction to form the Tamiflu skeleton. Throughout the synthesis, well-established, highly efficient reactions were employed, and no protection/deprotection sequence was needed.

Contemporary avenues in catalytic P-H bond addition reaction: a case study of hydrophosphination - Koshti, Vijay; Gaikwad, Shahaji R.; Chikkali, Samir H. (Coordination Chemistry Reviews, 2014)
Remarkable advances and current state-of-the-art developments in catalytic hydrophosphination of alkenes and alkynes are reviewed. The challenges in constructing a C P bond with a special emphasis on metal catalysed (asymmetric) hydrophosphination are highlighted. Only those systems that unambiguously proceed via P H bond addition across a C-C/X (X = O, N, S) multiple bond have been covered in this overview. Reviewed examples support the assumption that either strongly chelating ligands or reaction products that act as ligands, enhance the rate of hydrophosphination. The asymmetric variant of this transformation allows installation of p-chiral [enantiomeric excess (ee) up to 82%] as well as C-chiral (ee up to 99%) centres. The limited spectroscopic, mechanistic data and OFT calculations point at two distinctly different mechanisms. In case of hydrophosphination, the metal undergoes oxidative addition and reductive elimination steps (in general), thus changing the oxidation state from M(0) to M(II) and back to M(0). Whereas in asymmetric hydrophosphination it is proposed that the oxidation state of the metal remains unaltered throughout the catalytic cycle. The examples described in this overview showcase the real power of catalytic hydrophosphination in constructing various phosphorus compounds, which may initiate a new era in organo-phosphorus chemistry. (C) 2014 Elsevier B.V. All rights reserved.
Keywords: Alkynes; Asymmetric hydrophosphination; Hydrophosphination; Metal catalyzed hydrophosphination; Olefins; P-H bond addition

Cross dimerization of amyloid-beta and alpha synuclein proteins in aqueous environment: a molecular dynamics simulations study - Jose, Jaya C.; Chatterjee, Prathit; Sengupta, Neelanjana (Plos One, 2014)
Self-assembly of the intrinsically unstructured proteins, amyloid beta (A beta) and alpha synclein (alpha Syn), are associated with Alzheimer's Disease, and Parkinson's and Lewy Body Diseases, respectively. Importantly, pathological overlaps between these neurodegenerative diseases, and the possibilities of interactions between A beta and alpha Syn in biological milieu emerge from several recent clinical reports and in vitro studies. Nevertheless, there are very few molecular level studies that have probed the nature of spontaneous interactions between these two sequentially dissimilar proteins and key characteristics of the resulting cross complexes. In this study, we have used atomistic molecular dynamics simulations to probe the possibility of cross dimerization between alpha Syn(1-95) and A beta(1-42), and thereby gain insights into their plausible early assembly pathways in aqueous environment. Our analyses indicate a strong probability of association between the two sequences, with inter-protein attractive electrostatic interactions playing dominant roles. Principal component analysis revealed significant heterogeneity in the strength and nature of the associations in the key interaction modes. In most, the interactions of repeating Lys residues, mainly in the imperfect repeats `KTKEGV' present in alpha Syn(1-95) were found to be essential for cross interactions and formation of inter-protein salt bridges. Additionally, a hydrophobicity driven interaction mode devoid of salt bridges, where the non-amyloid component (NAC) region of alpha Syn(1-95) came in contact with the hydrophobic core of A beta(1-42) was observed. The existence of such hetero complexes, and therefore hetero assembly pathways may lead to polymorphic aggregates with variations in pathological attributes. Our results provide a perspective on development of therapeutic strategies for preventing pathogenic interactions between these proteins.

Culturable bacterial phylogeny from a shallow water hydrothermal vent of espalamaca (Faial, Azores) reveals a variety of novel taxa - Rajasabapathy, Raju; Mohandass, Chellandi; Colaco, Ana; Dastager, Syed Gulam; Santos, Ricardo Serrao; Meena, Ram Murti (Current Science, 2014)
Phylogenetic diversity of the 16S rRNA gene associated with the domain bacteria was examined at the level of operational taxonomic units (OTUs) using the rarefaction analysis from a newly identified shallow water hydrothermal vent, Espalamaca in the Azorean Island Faial (Horta), North Atlantic Ocean. Diluted sea water nutrient agar amended with metals manganese, lead, iron and element sulphur, could help in retrieving highest OTUs (95) from the vent and 39 OTUs from nonvent. Molecular tools implemented on bacterial census indicated the occupancy of gamma-Proteobacteria by 55.78%, alpha-Proteobacteria by 21.05% and 12.63% of Bacteroidetes in the total population. Occurrence of novel species maximized with alpha-Proteobacteria (11/20) followed by Bacteroidetes (5/12) signified the necessity of studying these groups to strengthen the biodiversity database. Shannon index (H') and the Chao I richness estimator illustrated a strong bacterial community in the venting area. The current study confers many bacterial genera which were not reported earlier in any of the shallow water vents and adds 33 new taxa to the database.
Keywords: Bacterial phylogeny; metals; novel taxa; rarefaction analysis; shallow vent

Design and synthesis of 3D porous diamondoid frameworks by cocrystallization - Tothadi, Srinu; Little, Marc A.; Hasell, Tom; Briggs, Michel E.; Chong, Samantha Y.; Cooper, Andrew I. (Acta Crystallographica A‐Foundation and Advances, 2014)
Keywords: cocrystals; crystal engineering; Porous Organic Cages

Determination of optimum values of descriptors to set filters for synthetic tri-pyrrole derivatives (prodiginines) against multi drug resistant strain of plasmodium falciparum - Masand, Vijay H.; Mahajan, Devidas T.; Pourbasheer, Eslam; Hadda, Taibi Ben; Chauhan, Harsh; Gajbhiye, Jayant M.; Alafeefy, A. M. (Current Research in Drug Discovery, 2014)
Abstract: In the present study, we have carried out extensive non-linear Quantitative-Structure Activity Relationship (QSAR) analysis to correlate in vitro anti-malarial activity against multi drug resistant strain of Plasmodium falciparum. Forty-three synthetic prodiginines with different structural features were used for their potential antimalarial activity. Linear, bilinear, biexponential and parabolic equations were developed. These equations were compared to determine the optimum values of descriptors for very useful and easily interpretable descriptors. The optimum values of these descriptors could be helpful in finding and optimizing a good lead compound. Obtained correlations reveal that various factors like lipophilicity, molecular weight and number of bonds have non-linear relation with the anti-malarial activity. Keywords: Prodiginines, Anti-Malarial Activity, Optimum/Desirability Values, Hybrid Inverse-QSAR

Dimorphism and hydrocarbon metabolism in Yarrowia lipolytica var. indica - Palande, A. S.; Kulkarni, S. V.; Leon-Ramirez, C.; Campos-Gongora, E.; Ruiz-Herrera, J.; Deshpande, Mukund V. (Archives of Microbiology, 2014)
Yarrowia lipolytica is able to metabolize high Mr hydrophobic natural compounds such as fatty acids and hydrocarbons. Characteristically, strains of Y. lipolytica can grow as populations with variable proportions of yeast and filamentous forms. In the present study, we describe the dimorphic characteristics of a variant designated as Y. lipolytica var. indica isolated from petroleum contaminated sea water and the effect of cell morphology on hydrocarbon metabolism. The variant behaved as a yeast monomorphic strain, under conditions at which terrestrial Y. lipolytica strain W29 and its derived strains, grow as almost uniform populations of mycelial cells. Using organic nitrogen sources and N-acetylglucosamine as carbon source, var. indica was able to form mycelial cells, the proportion of which increased when incubated under semi-anaerobic conditions. The cell surface characteristics of var. indica and W29 were found to be different with respect to contact angle and percent hydrophobicity. For instance, percent hydrophobicity of var. indica was 89.93 +/- A 1.95 while that of W29 was 70.78 +/- A 1.1. Furthermore, while all tested strains metabolize hydrocarbons, only var. indica was able to use it as a carbon source. Yeast cells of var. indica metabolized hexadecane with higher efficiency than the mycelial form, whereas the mycelial form of the terrestrial strain metabolized the hydrocarbon more efficiently, as occurred with the mycelial monomorphic mutant AC11, compared to the yeast monomorphic mutant AC1.
Keywords: Hexadecane metabolism; Yarrowia lipolytica; Yeast-mycelium transition

Easy access to alpha-aryl substituted gamma-ketophosphonates: lewis acid mediated reactions of 1,3-diketones with alpha-hydroxyphosphonates and tandem regioselective C-C bond cleavage - Pallikonda, Gangaram; Chakravarty, Manab; Sahoo, Manoj Kumar (Organic & Biomolecular Chemistry, 2014)
A range of alpha-aryl substituted gamma-ketophosphonates is synthesised by Lewis acid mediated reactions of 1,3-diketones and easily accessible, inexpensive benzylic alpha-hydroxyphosphonates in an operationally simple method under solvent-free conditions without exclusion of air/moisture. A regioselective C-C bond cleavage for 1,3-diketones in a tandem fashion has also been demonstrated. Synthesis of a gamma-ketophosphonate with phenol functionality at the a-position (structural analogue of raspberry ketone, a natural product) has also been presented.

Efficient and mild method for preparation of allylic amines from aziridine-2-alcohols using PPh3/I-2/imidazole - Chavan, Subhash P.; Khairnar, Lalit B.; Chavan, Prakash N. (Tetrahedron Letters, 2014)
Allylic amines are synthesized in good to excellent yields by treatment of aziridine-2-alcohols with PPh3/I-2/imidazole in THF as solvent under mild conditions. (C) 2014 Elsevier Ltd. All rights reserved.
Keywords: Chiral allylic amine; Chiral aziridine-2-alcohols; PPh3/iodine/imidazole; Reductive elimination

Efficient synthesis of 1,5-benzodiazepines catalyzed by bismuth nitrate - Bhattacharya, Asish K.; Dange, Santoshkumar S.; Polanki, Innaiah K.; Chand, Hemender R. (Indian Journal of Chemistry Section B-Organic Chemistry including Medicinal Chemistry, 2014)
An efficient method has been developed for the synthesis of biologically active 1,5-benzodiazepines in one-pot by reacting o-phenylenediamine and ketones catalyzed by bismuth nitrate pentahydrate at room temperature or under microwave irradiation.
Keywords: 1; 5-benzodiazepines; bismuth nitrate pentahydrate; o-Phenylenediamine; synthetic methods

Efficient synthesis of O-aryloxime ethers by copper fiuorapatite catalyzed cross-coupling of aryloximes with arylboronic acids - Mulla, Shafeek Abdul Rashid; Chavan, Santosh S.; Inamdar, Suleman M.; Pathari, Mohsinkhan Y.; Shaikh, Taufeekaslam M. Y. (Tetrahedron Letters, 2014)
A novel, highly efficient, and mild protocol has been developed for the synthesis of O-aryloxime ethers in good to excellent yields at ambient reaction conditions. This is the first report in which =N-O-Ar linkage was achieved with ecofriendly, recyclable, heterogeneous copper fluorapatite (CuFAP) catalyst via C-O cross coupling of aryloxime with arylboronic acid in the presence of Cs2CO3 as base and methanol as solvent. (C) 2014 Elsevier Ltd. All rights reserved.
Keywords: Arylboronic acid; Aryloxime; Copper fluorapatite; O-Aryloxime ethers

Enhancement in the field emission behavior of graphene in N-2/O-2 high vacuum ambience - Suryawanshi, S. R.; Kolhe, Pankaj S.; Gavhane, D. S.; Patil, S. S.; Chavan, P. G.; More, Mahendra A.; Late, Dattatray J. (2014 27th International Vacuum Nanoelectronics Conference (IVNC), 2014)
Herein we report, pressure dependent field emission (FE) behaviour of a few-layer graphene emitter. Gas dependent FE properties have been investigated in ultra high vacuum (UHV), as well as in N-2 and O-2 ambience at base pressure similar to 1x10(-6) torr. Interestingly, the graphene emitter when operated in N-2/O-2 ambience exhibits lower turn-on field and higher emission current density, as compared to the UHV conditions. The emission current stability investigated at preset value of similar to 1 mu A over the period of more than 2 hrs is found better in the N2 ambience and is characterized by fewer fluctuations, in contrast to the behaviour in the O-2 ambience. The observed enhanced electron emission behavior in N-2/O-2 ambience is attributed to modulation of the work function of graphene emitter.
Keywords: graphene; Pressure Dependent Field Emission

Facile and convenient synthesis of (+/-)-Biotin via MgCl2/Et3N-mediated C-C coupling and mitsunobu reaction - Chavan, Subhash P.; Chavan, Prakash N.; Lasonkar, Pradeep B.; Khairnar, Lalit B.; Kadam, Appasaheb L. (Synlett, 2014)
A synthesis of (+/-)-biotin is described starting from simple starting materials viz. cyclohexanone and amino malonic acid ester. The key steps involved are MgCl2/Et3N coupling of amino malonic acid ester derivative and acid chloride, Mitsunobu reaction, ozonolysis, Staudinger reduction, novel urea formation, and subsequent dibenzylation. This approach is economical and involves high-yielding steps and simple reaction conditions.
Keywords: Appel reaction; biotin; Mitsunobu reaction; Ozonolysis; Staudinger reduction

Ferromagnetic tetranuclear Cu(II) complex: catecholase and phenoxazinone synthase activities - Mitra, Merry; Kundu, Tanay; Kaur, Gurpreet; Sharma, Gyaneswar; Choudhury, Angshuman Roy; Singh, Yogesh; Ghosh, Rajarshi (Acta Crystallographica A‐Foundation and Advances, 2014)
Keywords: catalysis; Ferromagnetic; Tetranuclear copper

Field emission properties of ZnO nanosheet arrays - Naik, Kusha Kumar; Khare, Ruchita T.; Chakravarty, Disha; More, Mahendra A.; Thapa, Ranjit; Late, Dattatray J.; Rout, Chandra Sekhar (Applied Physics Letters, 2014)
{Electron emission properties of electrodeposited ZnO nanosheet arrays grown on Indium tin oxide coated glass substrates have been studied. Influence of oxygen vacancies on electronic structures and field emission properties of ZnO nanosheets are investigated using density functional theory. The oxygen vacancies produce unshared d electrons which form an impurity energy state; this causes shifting of Fermi level towards the vacuum, and so the barrier energy for electron extraction reduces. The ZnO nanosheet arrays exhibit a low turn-on field of 2.4 V/mu m at 0.1 mu A/cm(2) and current density of 50.1 mu A/cm(2) at an applied field of 6.4 V/mu m with field enhancement factor