Non-templated hydrothermal growth of anisotropic magnetite nanostructures using hexamine as the directing agent - Bhagwat, S. V.; Jouen, Samuel; Kundaliya, D. C.; Singh, H.; Jagadale, Tushar C.; Athawale, A. A.; Lofland, S. E.; Hannoyer, Beatrice; Ogale, Satishchandra B. (Journal of Nanoscience and Nanotechnology, 2009)
Anisotropic growth of magnetite (Fe(3)O(4)) nanoparticles is achieved in a hydrothermal growth process using hexamine to play a dual role of oxide forming and directing agent. The samples are characterized by X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, squid magnetometry, ferromagnetic resonance technique, diffuse reflectance spectroscopy and Mossbauer spectroscopy, which collectively establish the formation of Fe(3)O(4) phase. Anisotropic structures such as nanorods and nanotubules are revealed and these are shown to exhibit good humidity sensing properties.
Keywords: Anisotropic Nanostructures; Hexamine; hydrothermal; magnetite; Mossbauer

Novel electroless process for copper coating of flyash using titania/ultraviolet-radiation/metal catalyst-system - Shijitha, T.; Baiju, K. V.; Shukla, S.; Patil, K.; Warrier, K. G. K. (Applied Surface Science, 2009)
A novel electroless process has been demonstrated in this investigation to coat the surface of flyash particles with a conducting metal such as copper. The conventional electroless process has been modified for this purpose by replacing the tin-palladium catalyst-system with the titania/ultraviolet-radiation/metal catalyst-system, where the metal is either copper or silver as demonstrated here. The mechanism of copper coating of flyash particles in an electroless bath, using the novel methods of surface-sensitization and surface-activation, has been systematically studied by monitoring changes in the surface-morphology, surface-chemistry, and surface-structure of flyash particles using the scanning electron microscope, energy dispersive analysis of X-rays, X-ray photoelectron spectroscope, and X-ray diffraction. It has been revealed that the novel electroless method involves coating the flyash particles with titania photocatalyst via sol-gel, which acts as a surface-sensitizer under the ultraviolet-radiation exposure for the subsequent surface-activation with the copper- or silver-clusters. The latter in turn acts as surface-catalyst for the subsequent Cu-coating in an electroless bath. The proposed mechanism of surface-sensitization and surface-activation of flyash particles using the novel catalyst-system has been compared with that using the conventional catalyst-system. (C) 2009 Elsevier B. V. All rights reserved.
Keywords: Copper; Electroless; Flyash; Photocatalysis; sol-gel; titania

Novel/conceptual floating pulsatile system using high internal phase emulsion based porous material intended for chronotherapy - Sher, Praveen; Ingavle, Ganesh C.; Ponrathnam, Surendra; Benson, James R.; Li, Nai-Hong; Pawar, Atmaram P. (AAPS Pharmscitech, 2009)
The aim of the present study was to design a novel/conceptual delivery system using ibuprofen, anticipated for chronotherapy in arthritis with porous material to overcome the formulation limits (multiple steps, polymers, excipients) and to optimize drug loading for a desired release profile suitable for in vitro investigations. The objective of this delivery system lies in the availability of maximum drug amount for absorption in the wee hours as recommended. Drug loading using 3(2) factorial design on porous carrier, synthesized by high internal phase emulsion technique using styrene and divinylbenzene, was done via solvent evaporation using methanol and dichloromethane. The system was evaluated in vitro for drug loading, encapsulation efficiency, and surface characterization by scanning electron, atomic force microscopy, and customized drug release study. This study examined critical parameters such as solvent volume, drug amount, and solvent polarity on investigations related to drug adsorption and release mostly favoring low-polarity solvent dichloromethane. Overall release in all batches ranged 0.98-52% in acidic medium and 71-94% in basic medium. These results exhibit uniqueness in achieving the least drug release of 0.98%, an ideal one, without using any release modifiers, making it distinct from other approaches/technologies for time and controlled release and for chronotherapy.
Keywords: chronotherapy; floating pulsatile drug delivery system; high internal phase emulsion; ibuprofen; multiparticulate porous carriers

Oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide over nanogold supported on TiO2 and other transition and rare-earth metal oxides - Choudhary, Vasant R.; Dumbre, Deepa K.; Bhargava, Suresh Kumar (Industrial & Engineering Chemistry Research, 2009)
Liquid-phase oxidation of benzyl alcohol to benzaldehyde by tertiary butyl hydroperoxide (at 95 degrees C) over nanogold supported oil TiO2 and other transition-metal oxides (viz, MnO2, Fe2O3, CoOx, NiO, CuO, ZnO, and ZrO2) or rare-earth oxides (viz, La2O3, Sm2O3, Eu2O3, and Yb2O3) by the homogeneous deposition-precipitation (HDP) method has been investigated. The Au/TiO2 catalyst, prepared using the HDP method, showed high activity and selectivity in the reaction. The ZrO2-Supported nanogold catalyst (HDP) also showed very good performance. The Au/TiO2 catalyst that was prepared using the deposition-precipitation (DP) method, however, showed poor catalytic activity, mostly because of its much-lower gold loading and/or lower Au3+/Au-0 ratio. Irrespective of the catalyst preparation method, the catalytic activity increased as the gold loading increased. The gold deposition method strongly influenced the amount of gold that was deposited on TiO2, the gold particle size distribution, and also the surface Au3+/Au-0 ratio; using the HDP method, the gold deposition was much larger, the gold particle size was smaller, the gold particle size distribution was much narrower, and the Au3+/Au-0 ratio was higher. Both the metallic and ionic gold species (Au-0 and Au3+) are present in the Au/TiO2 catalyst. However, the Au3+ species are mostly responsible for the high catalytic activity in the oxidation process.

Pilot plant study of recovery of lactic acid from ethyl lactate - Barve, Prashant P.; Rahman, Imran; Kulkarni, Bhaskar D. (Organic Process Research & Development, 2009)
Purified lactic acid is used for production of biodegradable polymer. Esterification with ethanol and subsequent hydrolysis in distillation columns to produce purified lactic acid without catalyst has obvious advantages. In this paper, we present a pilot-plant study of ethyl lactate hydrolysis to produce 3.86 kg/h lactic acid (99.85% purity) using three distillation columns. Simulation of distillation columns at steady state has been carried out, and the results obtained tally with the experimental results of the pilot plant.

Polymeric ladderphanes - Chou, Chih-Ming; Lee, Shern-Long; Chen, Chih-Hsien; Biju, Akkattu T.; Wang, Hsian-Wen; Wu, Yi-Lin; Zhang, Guo-Fu; Yang, Kuang-Wei; Lim, Tsong-Shin; Huang, Min-Jie; Tsai, Po-Yu; Lin, Kin-Chuan; et al. (Journal of the American Chemical Society, 2009)
A new class of polymers, which have a double-stranded polybinorbornene skeleton with multilayer planar oligoaryl linkers, defined as polymeric ladderphanes, are synthesized. The structures of these ladderphanes are determined by spectroscopic means. Photophysical studies and time-resolved fluorescence spectroscopic investigations reveal that there is a strong interaction between the chromophore linkers. Thus, Soret band splitting in the absorption spectrum of the polymer with porphyrin linker (12e), significant fluorescence quenching with oligoaryl linkers (12b−d), and excimer emission with a terphenylene-diethynylene linker (12a) are characteristic photophysical properties of these polymers. Scanning tunneling microscopy shows that polymers 12b and d exhibit a ladder-like morphology and form a supramolecular assembly leading to a two-dimensional ordered array on a highly oriented pyrolytic graphite surface.

Preparation of nearly monodisperse nickel nanoparticles by a facile solution based methodology and their ordered assemblies - Sidhaye, Deepti S.; Bala, Tanushree; Srinath, S.; Srikanth, H.; Poddar, Pankaj; Sastry, Murali; Bhagavatula L. V. Prasad (Journal of Physical Chemistry C, 2009)
Nickel nanoparticles have been synthesized by a simple wet chemical reduction technique in the presence of a surfactant sodium dodecyl sulfate (SDS) and a capping agent oleic acid. Varying the concentration of the surfactant and the capping agent has been found to critically govern the nature of the nanoparticles prepared. It is observed that at an optimum concentration of SDS and oleic acid, nearly monodisperse Ni nanoparticles are obtained that form highly ordered hexagonally close-packed structures on electron microscopy grids by a simple drop coating procedure. It is also shown that the presence of oleic acid is necessary for the stability of the Ni nanoparticles synthesized. Structural and magnetic characterizations of the nanoparticles are also presented.

Process for the preparation of polymeric absorbents - Lele, Ashish Kishor; Varghese, Shyni; Badiger, Manohar V.; Mashelkar, Raghunath Anant (2009)
The invention discloses a process for the preparation of polymeric absorbents useful for gelling organic liquids. The process comprises mixing one or more monomers with a cross-linking agent, a free radical initiator, an optional solvent, optionally in the presence of a transition metal source and subjecting the mixture so obtained to a conventional polymerisation method. The polymer is removed, crushed to obtain polymer powder, washed with solvent and dried by conventional methods to remove unreacted monomers, followed by swelling in alcohols to obtain the desired product.

Purification and characterization of acidic lipase from aspergillus niger NCIM 1207 - Mhetras, Nutan; Bastawade, Kulbhushan B.; Gokhale, D. V. (Bioresource Technology, 2009)
An extracellular lipase from Aspergillus niger NCIM 1207 has been purified to homogeneity using ammonium sulfate precipitation followed by phenyl sepharose and Sephacryl-100 gel chromatography. This protocol resulted in 149 fold purification with 54% final recovery. The purified enzyme showed a prominent single band on SDS-PAGE. The purified enzyme is a monomeric protein of 32.2 kDa molecular weight and exhibits optimal activity at 50 degrees C. One interesting feature of this enzyme is its highly acidic pH optimum. The isoelectric point (pl) of lipase was 8.5. The purified lipase appears to be unique since it cleaved triolein at only 3-position releasing 1,2-diolein. Chemical modification studies revealed that His, Ser, Carboxylate and Trp are involved in catalysis. (c) 2008 Elsevier Ltd. All rights reserved.
Keywords: Acidic lipase; Aspergillus niger; Positional specificity

Purification and characterization of putative alkaline [Ni-Fe] hydrogenase from unicellular marine green alga, tetraselmis kochinensis NCIM 1605 - Bhosale, Siddharth H.; Pant, A.; Khan, Mohammad Islam (Microbiological Research, 2009)
Hydrogenase enzyme from the unicellular marine green alga Tetraselmis kochinensis NCIM 1605 was purified 467 fold to homogeneity. The molecular weight was estimated to be similar to 89kDa by SDS-PAGE. This enzyme consists of two subunits with molecular masses of similar to 70 and similar to 19 kDa. The hydrogenase was found to contain 10 g atoms of Fe and 1 g of atom of Ni per mote of protein. The specific activity of hydrogen evolution was 50 mu mol H-2/mg/h of enzyme using reduced methyl viologen as an electron donor. This hydrogenase enzyme has pl value similar to 9.6 representing its alkaline nature. The absorption spectrum of the hydrogenase enzyme showed an absorption peak at 425 nm indicating that the enzyme had iron-sulfur clusters. The total of 16 cysteine residues were found per mote of enzyme under the denaturing condition and 20 cysteine residues in reduced denatured enzyme indicating that it has two disulfide bridges. (C) 2007 Published by Elsevier GmbH.
Keywords: Characterization; Chemical modification; Ni-Fe hydrogenase; Tetraselmis kochinensis; Unicellular green algae

Reactions of morita-baylis-hillman acetates with huisgen zwitterions: a novel strategy for the synthesis of ?-amino acid derivatives - Jose, Anu; Paul, Rony Rajan; Mohan, Resmi; Mathew, Smitha C.; Biju, Akkattu T.; Eringathodi, Suresh; Nair, Vijay (Synthesis, 2009)
The reaction of Huisgen Zwitterion with Morita–Baylis– Hillman acetates afforded b-amino acid derivatives.
Keywords: b-amino acid; Huisgen zwitterion; Morita–Baylis–Hillman acetate

Reactive extrusion of poly(L-Lactic Acid) with glycidol - Deenadayalan, E.; Lele, Ashish K.; Balasubramanian, M. (Journal of Applied Polymer Science, 2009)
Glycidol modified polylactic acid (PLLA) polymers have been prepared by reactive extrusion. Influences of residence time and the concentration of glycidol on the extent of reaction with different weight average molecular weight (45,000, 65,000, and 100,000) PLLA's were studied. Structure-property relationship has been established by measuring molecular, mesoscopic, and macroscopic properties. Under reactive extrusion conditions glycidol reacted with the end groups of PLLA to initiate chain extension. Low-molecular weight PLLA reacted with glycidol faster than the medium molecular weight PLLA, whereas high-molecular weight PLLA did not show significant reactions. The glass transition temperature, melting temperature, crystallization temperature, and heat of fusion were measured for unmodified and modified PLLA's. Chain extended PLLA had higher T(g) and T(m) than the unmodified samples. Time sweep rheological experiments were performed to test the melt stability of PLLA. Chain extended PLLA's were found to retain viscoelastic properties for much longer time than the unreacted samples. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 1391-1398, 2009
Keywords: biodegradable; reactive extrusion; Rheology; structure-property relations; Thermal properties

Selective N-alkylation of aniline with methanol over a heteropolyacid on montmorillonite K10 - Nehate, Manoj; Bokade, Vijay V. (Applied Clay Science, 2009)
N-methylaniline is an industrially important product in the manufacture of paper, textile dyes, drugs, perfumes and explosives. The vapour phase alkylation of aniline with methanol forming N-methylaniline is advantageous over liquid phase alkylation. In present study, vapour phase methylation of aniline over dodecatungestophosphoric acid supported on K10 montmorillonite was systematically studied and optimization of process parameters was carried out. The 20% m/m DTPA/K10 was found to be optimum with 79% aniline conversion and 99% N-methylaniline selectivity. The reaction required milder operating conditions than reported for commercial catalysts. We also studied the feasibility of 20% m/m DTPA/K10 as a catalyst for the alkylation of aniline with other alcohols like ethanol, n-propanol, iso-propanol and n-butanol. The activity of 20% m/m DTPA/K10 decreased with increasing carbon number. (C) 2009 Elsevier B.V. All rights reserved.
Keywords: Alkylation; Aniline; Heteropolyacid; montmorillonite K10; N-methylaniline

Selective oxidation of aromatic primary alcohols to aldehydes using molybdenum acetylide oxo-peroxo complex as catalyst - Biradar, Ankush V.; Dongare, Mohan K.; Shubhangi B. Umbarkar (Tetrahedron Letters, 2009)
Selective oxidation of various aromatic alcohols to aldehydes has been carried out with very high conversion (90%) and selectivity (90%) for aldehydes using cyclopentadienyl molybdenum acetylide complex, CpMo(CO)(3)(C CPh) (1) as catalyst and hydrogen peroxide as environmentally benign oxidant, Water-soluble Mo acetylide oxo-peroxo species is formed in situ after reaction of I with aqueous hydrogen peroxide during the Course of reaction as catalytically active species. Interestingly even though the catalyst is homogeneous it Could be recycled very easily by separating the products in organic phase and catalyst in aqueous phase using separating funnel. Even after five recycles no appreciable loss in alcohol conversion and aldehyde selectivity was observed. (C) 2009 Elsevier Ltd. All rights reserved.
Keywords: Homogenous catalyst; Hydrogen peroxide; Molybdenum complex; Oxidation; Oxo-peroxo; Primary aromatic alcohol

Selective synthesis of cumene by isopropylation of benzene using catalytic membrane reactor - Bokade, Vijay V.; Kharul, Ulhas K. (Chemical Engineering Journal, 2009)
Selective isopropylation of benzene to cumene is demonstrated using catalytic membrane reactor (CMR), to our knowledge for the first time and the performance was evaluated against conventional plug flow reactor (PFR). Almost complete elimination of byproducts like polyalkylated benzene and higher aromatics could be made possible by using CMR. These are present in significant amount when reaction is carried out with PFR. The cumene selectivity increased up to a maximum of 97.25% by CMR as against 90.05% with conventional PFR. The effect of reaction parameters that can greatly influence the process economics, such as liquid hourly space velocity (LHSV), reactant mole ratio and catalyst/reactor volume ratio were investigated. Changes in these parameters made for CMR are industrially advantageous. The process by CMR is more economical and ecofriendly than PFR as far as milder process parameters (higher LHSV, lower reactant feed mole ratio, less catalyst require, etc.) and process intensification (reaction and separation in single reactor) are concerned. The study provides new insights for benzene isopropylation reaction. (C) 2008 Elsevier B.V. All rights reserved.
Keywords: Benzene; Catalytic membrane reactor; cumene; Diisopropyl benzene; Friedel-Craft alkylation

Self assembled hydrophobic nanoclusters of poly(methylmethcrylate) embedded into polyvinyl alcohol based hydrophilic matrix: preparation and water sorption study - Shukla, Sandeep Kumar; Shaikh, A. Wasif; Gunari, Nikhil; Bajpai, A. K.; Kulkarni, R. A. (Journal of Applied Polymer Science, 2009)
Hydrophilic matrices containing nanosized Clusters of hydrophilic moieties have demonstrated potential applications in biomedical field. A novel hydrogel containing nanosized domains (20-35 nm) of hydrophobic moieties of poly(methyl methacrylate) (PMMA) was prepared by grafting crosslinked p ly(acrylic acid-co-methyl-methacrylate) chains onto polyvinyl alcohol (PVA) backbone using an efficient redox system. The graft copolymerization process was investigated to observe the influence of gel components on the kinetic parameters of grafting such as rate of grafting (R(g)), grafting yield (G(y)) and grafting efficiency (G(e)). The prepared graft nanohydrogel was evaluated for its water sorption potential under varying chemical composition of the gel and changing pH, temperature, and ionic strength of the swelling bath. The swelling process was also examined mechanistically and diffusion constants (D) of water molecules through the swellable nanohydrogel were also evaluated. (c) 2008 Wiley Periodicals, Inc. J ppl Polym Sci 111: 1300-1310, 2009
Keywords: graft copolymers; hydrophilic polymers; Nanocomposites; swelling

Short synthesis of 3,6-disubstituted N-2-thienyl/aryl-indoles - Borate, Hanumant B.; Sawargave, Sangmeshwer P.; Maujan, Suleman R. (Tetrahedron Letters, 2009)
A short synthetic strategy for 3,6-disubstituted-N-2-thienyl/aryl-indoles, involving reaction of substituted 2,4-difluoro/dichloro-styrene epoxide with substituted 2-formylaminothiophenes or substitued N-formylanilins in the presence of a base followed by treatment with an acid, has been developed The method was applied for the synthesis of a number of indoles with a variety of substitutents at 1, 3, and 6 positions of the indole moiety. (C) 2009 Elsevier Ltd All rights reserved.
Keywords: Formylaminothiophene; Gewald synthesis; Indole; Styrene epoxide

Simple and efficient enzymatic transglycosylation of stevioside by beta-cyclodextrin glucanotransferase from Bacillus firmus - Jaitak, V.; Kaul, V. Kumar; Bandna; Kumar, N.; Singh, B.; Savergave, L. S.; Jogdand, Vitthal V.; Nene, S. (Biotechnology Letters, 2009)
Stevioside was subjected to 1,4-intermolecular transglycosylation using beta-cyclodextrin glucanotransferase (beta-CGtase) produced from an alkalophilic strain of Bacillus firmus. The reaction was carried out by traditional, ultrasound-assisted and microwave-assisted techniques. Reaction under microwave conditions was faster and was completed in 1 min yielding two 1,4 transglycosylated products, 4'-O-alpha-d-glycosyl stevioside (I) and 4''-O-alpha-d-maltosyl stevioside (II) in 66% and 24%, respectively. The optimum transglycosylation occurred by using stevioside (1.24 mmol), beta-CD (1.76 mmol) and beta-CGtase (2 U/g) under microwave assisted reaction (MAR) in 5 ml sodium phosphate buffer (pH 7) at 50A degrees C and 80 W power. MAR is therefore potentially a useful and economical method for faster transglycosylation of stevioside.
Keywords: beta-cyclodextrin; beta-Cyclodextrin glucanotransferase; Microwave-assisted reaction; Stevia rebaudiana; Stevioside; Transglycosylation

Solubilization and conformational behavior of zein in aqueous solution of dodecyldimethylethylammonium bromide (DDAB) - Mehta, S. K.; Bhawna; Bhasin, K. K.; Kumar, Anil (Colloids and Surfaces A-Physicochemical and Engineering Aspects, 2009)
The solubilization and conformational behavior of Zein in the presence of cationic surfactant, dodecyldimethylethylammonium bromide (DDAB) have been studied. The colloidal properties of DDAB in the absence and presence of Zein have also been investigated using physico-chemical and spectroscopy methods. The surfactant appears to bind to Zein at concentrations below the critical micelle concentration (cmc) and the binding becomes weaker at concentrations above the cmc. The interaction between DDAB and Zein depends on the chemical structure and molecular parameters (conformation, molar mass, charge) of the protein. The schematic sketches of the molecular mechanisms of the complex formation between like-charged proteins and surfactants have been proposed. (C) 2009 Elsevier B.V. All rights reserved.
Keywords: Absorbance spectroscopy; Aggregation number; conductivity; DDAB; FT-IR; Surface tension; viscosity; Zein

Some mechanistic insights into the gelation of regenerated silk fibroin sol - Nagarkar, Shailesh; Patil, Avinash; Lele, Ashish K.; Bhat, Suresh K.; Bellare, Jayesh R.; Mashelkar, Raghunath Anant (Industrial & Engineering Chemistry Research, 2009)
We provide some new insights into the kinetics and mechanism of sol-gel transition as it pertains to regenerated silk fibroin, which is the principle structural protein of silkworm silk fiber. Silk fibroin was dissolved in lithium bromide and dialyzed against deionized water to prepare a regenerated fibroin solution. This solution was found to be unstable at lower pH and transformed into a colloidal gel. The kinetics and mechanism of the sol-gel transition were investigated using rheology and light scattering. We show that gelation proceeds in two steps. In the first step, a weak gel is formed almost immediately upon lowering the pH, while in the second step further gelation proceeds rapidly after a long induction time to form a self-similar structure.

Stereo-controlled approach to pyrrolidine iminosugar C-glycosides and 1,4-dideoxy-1,4-imino-L-allitol using a D-mannose-derived cyclic nitrone - Bande, Omprakash P.; Jadhav, Vrushali H.; Puranik, Vedavati G.; Dhavale, Dilip D.; Lombardo, Marco (Tetrahedron Letters, 2009)
Intramolecular N-alkylation of 2,3-O-isopropylidene-5-O-methanesulfonyl-6-O-t-butyldimethylsilyl-D-mann ofuranose-oxime 7 afforded a five-membered cyclic nitrone 9, which on N-O bond reductive cleavage followed by deprotection of -OTBS and acetonide functionalities gave 1,4-dideoxy-1,4-imino-L-allitol (DIA) 3. Addition of allylmagnesium chloride to nitrone 9 afforded alpha-allylated product 10a in high diastereoselectivity providing an easy entry to N-hydroxy-C1-alpha-allyl-substituted pyrrolidine iminosugar 4a after removal of protecting group, while N-O bond reductive cleavage in 10a afforded C1-alpha-allyl-pyrrolidine iminosugar 4b. (C) 2009 Elsevier Ltd. All rights reserved.
Keywords: Cyclic nitrone; Enzyme inhibitors; Iminosugars; pyrrolidine

Strain improvement and up scaling of phytase production by aspergillus niger NCIM 563 under submerged fermentation conditions - Shah, P.; Bhavsar, Kavita P.; Soni, S. K.; Khire, Jayant Malhar (Journal of Industrial Microbiology & Biotechnology, 2009)
Combination of physical and chemical mutagenesis was used to isolate hyper secretory strains of Aspergillus niger NCIM 563 for phytase production. Phytase activity of mutant N-1 and N-79 was about 17 and 47% higher than the parent strain. In shake flask the productivity of phytase in parent, mutant N-1 and N-79 was 6,181, 7,619 and 9,523 IU/L per day, respectively. Up scaling of the fermentation from shake flask to 3 and 14 L New Brunswick fermenter was studied. After optimizing various fermentation parameters like aeration, agitation and carbon source in fermentation medium the fermentation time to achieve highest phytase activity was reduced considerably from 14 days in shake flask to 8 days in 14 L fermenter. Highest phytase activity of 80 IU/ml was obtained in 1% rice bran-3.5% glucose containing medium with aeration 0.2 vvm and agitation 550 rpm at room temperature on 8th day of fermentation. Addition of either bavistin (0.1%), penicillin (0.1%), formalin (0.2%) and sodium chloride (10%) in fermented broth were effective in retaining 100% phytase activity for 8 days at room temperature while these reagents along with methanol (50%) and ethanol (50%) confer 100% stability of phytase activity at 4A degrees C till 20 days. Among various carriers used for application of phytase in feed, wheat bran and rice bran were superior to silica and calcium carbonate. Thermo stabilization studies indicate 100% protection of phytase activity in presence of 12% skim milk at 70A degrees C, which will be useful for its spray drying.
Keywords: Agriculture residue; Aspergillus niger; Phytase; phytate degradation; Poultry feed supplement; Submerged fermentation

Susceptibility of aedes aegypti and culex quinquefasciatus larvae to gedunin-related limonoids - Gurulingappa, Hallur; Tare, Vrushali; Pawar, Pushpa; Tungikar, Vijay; Jorapur, Yogesh R.; Madhavi, Sriram; Bhat, Sujata V. (Chemistry & Biodiversity, 2009)
The major non-azadirachtin limonoids such as gedunin (1), epoxyazadiradione (3), nimbocinol (4), and nimolicinol (5) from Azadirachta indica A. Juss ('neem') and their derivatives were evaluated for their toxic action against fourth instar larvae of Aedes aegypti L. and Culex quinquefasciatus SAY. Gedunin exhibited 100% toxic action against both the mosquito larvae at 50 and 10 ppm. Epoxyazadiradione and epoxynimolicinol also showed significant toxicities (>= 50%) against larvae of both mosquito species at 50 ppm. These neem limonoids can have benefits in mosquito-control programs.

Switching the electron-donor properties of n-heterocyclic carbenes by a facile deprotonation strategy - Biju, Akkattu T.; Hirano, Keiichi; Frohlich, Roland; Glorius, Frank (Chemistry an Asian Journal, 2009)
Flip the switch! The facile and distinct variation of the electronic properties of an N-heterocyclic carbene (NHC) ligand is reported. In this process, a simple deprotonation/protonation strategy can render the NHC to be an electron-poor or an electron-rich NHC ligand: one ligand, two electronic natures.
Keywords: carbenes; electronic properties; enolates; heterocycles; ligand design

Synthesis and antifungal activity of 1,2,3-triazole containing fluconazole analogues - Aher, Nilkanth G.; Pore, Vandana S.; Mishra, Nripendra N.; Kumar, Awanit; Shukla, Praveen K.; Sharma, Aanchal; Bhat, Manoj K. (Bioorganic & Medicinal Chemistry Letters, 2009)
Fluconazole based novel mimics containing 1,2,3-triazole were designed and synthesized as antifungal agents. Their antifungal activities were evaluated in vitro by measuring the minimal inhibitory concentrations (MICs). Compounds 12, 15, and 16 were found to be more potent against Candida fungal pathogens than control drugs fluconazole and amphotericin B. The studies presented here provide structural modi. cation of fluconazole to give 1,2,3-trazole containing molecules. Furthermore, these molecules were evaluated in vivo against Candida albicans intravenous challenge in Swiss mice and antiproliferative activities were tested against human hepatocellular carcinoma Hep3B and human epithelial carcinoma A431. It was found that compound 12 resulted in 97.4% reduction in fungal load in mice and did not show any profound proliferative effect at lower dose (0.001 mg/ml). (C) 2008 Elsevier Ltd. All rights reserved.
Keywords: 1; 2; 3-Triazole; Antifungal agent; bile acid; Conjugates; Fluconazole

Synthesis and conformational study of chiral oxepines: the baylis-hillman reaction and RCM approach with sugar aldehyde - Jadhav, Vrushali H.; Bande, Omprakash P.; Pinjari, Rahul V.; Gejji, Shridhar P.; Puranik, Vedavati G.; Dhavale, Dilip D. (Journal of Organic Chemistry, 2009)
The Baylis-Hillman reaction of 3-O-allyl-alpha-D-xylo-pentodialdo-1,4-furanose 3 afforded a diastereomeric mixture of D-gluco- and L-ido-configured alpha-methylene-beta-hydroxy esters 4a and 4b, respectively, in a ratio of 2:3. Reduction of the ester functionality in 4a/4b gave alcohols 5a/5b. The diene thus formed in 5a/5b was subjected to ring-closing metathesis (Grubbs' second-generation catalyst) to afford oxa-bicyclic ring system 6a/6b in high yield. Further manipulation of the aectonide functionality in 6a and 6b afforded new polyhydroxylated oxepines 1a/2a and 1b/2b, respectively. The (1)H NMR of oxepines 1a and 1b in D(2)O showed doubling of signals indicating their existence in two different rotamers/conformers. This fact was substantiated by calculating energetics of 1 and 2 conformers using the density functional theory and correlating the calculated (1)H NMR chemical shift pattern with that of the experimental spectra.

Synthesis and in vitro study of 14-aryl-14H-dibenzo[a.j]xanthenes as cytotoxic agents - Bhattacharya, Asish K.; Rana, Kalpeshkumar C.; Mujahid, Mohammad; Sehar, Irum; Saxena, Ajit K. (Bioorganic & Medicinal Chemistry Letters, 2009)
A simple and expedient method for the synthesis of a series of 14-aryl-14H-dibenzo[a.j]xanthenes is described through a one-pot condensation of beta-naphthol with aryl aldehydes catalysed by TaCl(5) under solvent-free conventional heating. The major advantages of the present method are: high yields, less reaction time, solvent-free condition and easy purification of the products. The synthesized 14-aryl-14H-dibenzo[a.j]xanthenes were evaluated against a panel of six human cancer lines of different tissues. Synthesized compound 30 showed IC(50) of 37.9 and 41.3 mu M against Colo-205 and 502713, respectively, whereas 3g showed IC(50) of 41.9 mu M against Colo-205. (C) 2009 Elsevier Ltd. All rights reserved.
Keywords: Aldehyde; beta-Naphthol; condensation; Cytotoxicity; One-pot reaction; Solvent-free; Tantalum(V) chloride; Xanthenes

Synthesis of catalytically active porous platinum nanoparticles by transmetallation reaction and proposition of the mechanism - Pasricha, Renu; Bala, Tanushree; Biradar, Ankush V.; Shubhangi B. Umbarkar; Sastry, Murali (Small, 2009)
A facile method for the synthesis of porous platinum nanoparticles by transmetallation reactions between sacrificial nickel nanoparticles and chloroplatinic acid (H(2)PtCl(6)) in solution, as well as at the constrained environment of the air water interface, using a Langmuir-Blodgett instrumental setup is presented. To carry out the transmetallation at the air-water interface hydrophobized nickel nanoparticles are assembled as a monolayer on the sub phase containing platinum ions. The porous Pt nanoparticles obtained as a result of the reaction are found to act as extremely good catalysts for hydrogenation reaction. The products are well characterized by TEM, HRTEM, EDAX, and STEM. Attempts are made to postulate the plausible mechanism of this reaction to generate this kind of nanoparticle with controllable geometric shape and structure. This simple strategy has the potential to synthesize other nanomaterials of interest too.
Keywords: Catalysts; Interfaces; Nickel nanoparticles; porous platinum; Transmetallation

Synthesis of hydroxy-functional PMMA macromonomers by anionic polymerization - Dhara, Mahua Ganguly; Sivaram, Swaminathan; Bhonde, Ramesh R.; Bhagavatula L. V. Prasad (Journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2009)
Living anionic polymerization has been utilized to synthesize hydroxy end-functionalized PMMA macromonomers with styryl or allyl functionalities as the polymerizable end-groups. Protected hydroxy-functionalized alkyl lithium initiators have been used to initiate anionic polymerization of MMA. Subsequently the living chains with protected hydroxyl function have been terminated using 4-vinylbenzyl chloride (4-VBC) or allyl methacrylate (ALMA) to form -hydroxy–styryl and -hydroxy–allyl PMMA, respectively. These protected hydroxy-functionalized PMMA macromonomers have been characterized by GPC and 1H-NMR. Termination using 4-VBC led to 50% functionalization, whereas that using allyl methacrylate led to 100% functionalization of the hydroxy-PMMA.
Keywords: Anionic polymerization; functionalized initiator; Macromonomer

Synthesis of hydroxy-functionalized star-branched PMMA by anionic polymerization - Dhara, Mahua Ganguly; Sivaram, Swaminathan; Baskaran, Durairaj (Polymer Bulletin, 2009)
Living anionic polymerization has been exploited to synthesize hydroxy end-functionalized PMMA star-branched polymers. Protected hydroxy-functionalized alkyl lithium initiators have been used to initiate anionic polymerization of MMA. Subsequently the living chains with protected hydroxyl function have been used to cross-link ethylene glycol dimethacrylate (EGDMA) in order to form star-branched polymers with cross-linked EGDMA core via `arm-first' method. The linear arms and the star molecules have been characterized by (1)HNMR, GPC, and light scattering. Variation in the number of arms with arm molecular weight and cross-linker loading has been studied. Star-branched PMMA-OH with as many as similar to 10 arms could be successfully made. Increased molecular weight of PMMA-OH led to decrease in the number of arms incorporated due to increased steric hindrance on the core. Increase in EGDMA concentration slightly increased the arm incorporation.
Keywords: Anionic polymerization; Star polymers; Star-branched PMMA

Synthesis of N-methylaniline by aniline alkylation with methanol over Sn-MFI molecular sieve - Niphadkar, P. S.; Joshi, P. N.; Gurav, H. R.; Deshpande, Suvarna S.; Bokade, Vijay V. (Catalysis Letters, 2009)
Sn-MFI molecular sieves (Tin silicalite-1) with SiO(2)/SnO(2) molar ratio of 50-150 were synthesized and characterized. Elemental analysis, XRD and DRUV-vis confirmed that prepared samples were of MFI zeolite structure and Sn was incorporated in MFI framework. Vapor phase methylation of aniline over Sn-MFI was systematically studied and optimizations of process parameters were carried out. Sn-MFI (SiO(2)/SnO(2) = 50) was found to be optimum catalyst with 55% aniline conversion and 60% N-methylaniline selectivity. At lower space velocity (higher contact time) of 1 h(-1), aniline conversion was found to be increased to 71% with reduction in N-methylaniline selectivity to 39% and increased in N,N-dimethylaniline selectivity to 58%. The reaction follows first order kinetics with respect to aniline having activation energy of 7.3 kcal/mol.
Keywords: Aniline; Lewis acid; Methanol; N-methylaniline; Sn-MFI

Tin-silicalite-1: synthesis by dry gel conversion, characterization and catalytic performance in phenol hydroxylation reaction - Niphadkar, Prashant S.; Kotwal, Mehejabeen S.; Deshpande, Shilpa S.; Bokade, Vijay V.; Joshi, Praphulla N. (Materials Chemistry and Physics, 2009)
Tin-silicalite-1 (Sn-MFI) has been successfully synthesized by dry gel conversion (DGC) method. The influence of various synthesis parameters such as crystallization time, temperature, water content at the bottom of autoclave, molar ratios of (TPA)(2)O/SiO(2) and SiO(2)/SnO(2) in dry gel on the crystallization kinetics and physico-chemical properties of Sn-MFI materials has been investigated. Powder-X-ray diffraction (XRD),XPS,AAS, DRUV-vis and SEM techniques were employed as characterization tools. Time-dependent studies revealed that, the progressive crystallization of Sn-MFI depend not only on the synthesis time but also on the other various synthesis parameters. Increase in the crystallization temperature, water content at bottom of autoclave (TPA)(2)O/SiO(2) and SiO(2)/SnO(2) molar ratios in dry gel resulted in the lowering of overall crystallization period. A good correspondence between the chemical composition of the surface and the bulk indicated the uniform distribution of Sn(4+) ions. The presence of these ions in tetrahedral coordination has been indicated by DRUV-vis spectral studies. Although, not better but comparable activity has been shown by Sn-MFI prepared by dry gel conversion method with Sn-MFI prepared by conventional hydrothermal crystallization method in the hydroxylation of phenol reaction. Increase in concentration of isolated Sn(4+) ions led to increase in phenol conversion and H(2)O(2) efficiency. (c) 2008 Elsevier B.V. All rights reserved.
Keywords: crystallisation; Dry gel conversion; microporous materials; Sn-MFI

Transesterification of edible and nonedible vegetable oils with alcohols over heteropolyacids supported on acid-treated clay - Bokade, Vijay V.; Yadav, Ganapati D. (Industrial & Engineering Chemistry Research, 2009)
In the current work, the novelty of heteropolyacid on clay (K-10) for the transesterification of vegetable oil with lower and higher alcohols is presented. Methyl esters (biodiesel) and glycerol were produced by the transesterification of vegetable oil with methanol in the presence of dodecatungestophosphoric acid (DTPA) supported on K-10 clay. The transesterification consists of three consecutive reversible reactions Diglycerides (DG) and monoglycerides (MG) are intermediate products. The optimal catalyst concentration was 5% w/w of oil. Detailed studies were done for optimization of the process parameters. The rate of transesterification in a batch reactor increased with temperature up to 170 degrees C. Higher temperatures did not reduce the time to reach maximum conversion. The study was also extended to reactions of different edible and nonedible oils with lower and higher alcohols. The conversion of TG, DG, and MG seemed to be a second-order mechanism for the forward and reverse reactions, where the reaction system could be described as a pseudo-heterogeneous catalyzed reaction. The reaction rate constants for the TG. DG, and MG transesterification reactions were 0.12-0.84 h(-1) and were higher for the MG reaction than for the TG transesterification. The activation energies were 4.2, 26, and 7.4 kcal/mol for the TG, DG, and MG transesterification reactions, respectively. The proposed kinetic model fits the experimental results well.

Transesterification of sunflower oil catalyzed by flyash-based solid catalysts - Kotwal, M. S.; Niphadkar, P. S.; Deshpande, Suvarna S.; Bokade, Vijay V.; Joshi, P. N. (Fuel, 2009)
Flyash-based base catalyst was used in the transesterification of sunflower oil with methanol to methyl esters in a heterogeneous manner. Catalyst preparation variables such as, the KNO(3) loading amount and calcination temperature were optimized. The catalysts were characterized by powder XRD. The catalyst prepared by loading of 5 wt.% KNO(3) on flyash followed by its calcination at 773 K has exhibited maximum oil conversion (87.5 wt.%). The influence of various reaction parameters such as % catalyst loading, methanol to oil molar ratio, reaction time, temperature, reusability of the catalyst on the catalytic activity was investigated. K(2)O derived from KNO(3) might be an essential component in the catalyst for its efficiency. (C) 2009 Elsevier Ltd. All rights reserved.
Keywords: Flyash; heterogeneous catalyst; Methyl ester; Sunflower oil; transesterification

Transfer of technology (ToT) document of polyimide binder resins - Ponrathnam, Surendra; Chelanattukizhakkemadath, Raman Rajan; Dwivedi, Mayank; Chavan. N. N.; Qureshi, Moham; Bhongale, Sunil Sitaram; Rao, Locanindi Hari Sarvothama; Dhansekharan, Janakiraman; Mohan, S. Krishna; Deokar, Sarika Babasaheb; Momin, Mohasin Shamshuddin (2009)

Two modes of O-H center dot center dot center dot O hydrogen bonding utilized in dimorphs of racemic 6-O-acryloyl-2-O-benzoyl-myo-inositol 1,3,5-orthoformate - Krishnaswamy, Shobhana; Gonnade, Rajesh G.; Bhadbhade, Mohan M.; Shashidhar, Mysore S. (Acta Crystallographica Section C-Crystal Structure Communications, 2009)
The title compound, C(17)H(16)O(8), yields conformational dimorphs [forms (I) and (II)] at room temperature, separately or concomitantly, depending on the solvent of crystallization. The yield of crystals of form (I) is always much more than that of crystals of form (II). The molecule has one donor -OH group that can make intermolecular O-H center dot center dot center dot O hydrogen bonds with one of the two acceptor C O groups, as well as with the hydroxyl O atom; interestingly, each of the options is utilized separately in the dimorphs. The crystal structure of form (I) contains one molecule in the asymmetric unit and is organized as a planar sheet of centrosymmetric dimers via O H center dot center dot center dot O hydrogen bonds involving the OH group and the carbonyl O atom of the acryloyl group. In the crystal structure of form (II), which contains two independent molecules in the asymmetric unit, two different O-H center dot center dot center dot O hydrogen bonds, viz. hydroxyl-hydroxyl and hydroxyl-carbonyl (benzoyl), connect the molecules in a layered arrangement. Another notable feature is the transformation of form (II) to form (I) via melt crystallization upon heating to 411 K. The higher yield of form (I) during crystallization and the thermal transition of form (II) to form (I) suggest that the association in form (I) is more highly favoured than that in form (II), which is valuable in understanding the priorities of molecular aggregation during nucleation of various polymorphs.

Ultrasound assisted synthesis of polyacrylic acid-nanoclay nanocomposite and its application in sonosorption studies of malachite green dye - Sonawane, S. H.; Chaudhari, P. L.; Ghodke, S. A.; Parande, M. G.; Bhandari, Vinay M.; Mishra, Satyendra; Kulkarni, R. D. (Ultrasonics Sonochemistry, 2009)
Synthesis of nanoclay nanocomposite has been undertaken by using polyacryalic acid (PAA) in aqueous medium and ultrasound environment and its application in dye removal has been investigated. The synthesized product was characterized by using FTIR and XRD techniques. The sonosorption capacity of the product namely PAA-nanoclay composite was determined by choosing malachite green (MG) dye as a model pollutant. The effects of various parameters such as nanocomposite loading, pH, various process conditions etc. have been studied. On comparing the results obtained with that of nanoclay as an adsorbent, it was found for an initial concentration of 500 mg/l, the PAA-nanoclay nanocomposite exhibited higher percentage of pollutant removal (68%) and for nanoclay it was 54%. The adsorption data has been correlated using Langmuir and Freundlich models. The fit of the Freundlich isotherm model was found to be good in the entire range of concentration for the experimental sorption data obtained on the nanoclay nanocomposite. A plausible reaction mechanism for use of PAA-nanoclay nanocomposite as ail adsorbent is also proposed. (c) 2008 Elsevier B.V. All rights reserved.
Keywords: Malachite Green; Nanocomposite; Polyacrylic acid; Sonosorption; Ultrasound

Vinyl-2-pyrrolidone derivatized guar gum based aqueous two-phase system - Kautharapu, Kumar; Pujari, Narahari S.; Golegaonkar, Sandeep B.; Ponrathnam, Surendra; Nene, Sanjay N.; Bhatnagar, D. (Separation and Purification Technology, 2009)
Aqueous two-phase systems (ATPs) are formed when certain combinations of two polymers or polymer and salt are added to water. Phase separation occurs at certain specific concentrations that have similar densities and low interfacial tensions. The present study involves synthesis and application of a novel derivatized guar in aqueous two-phase system. The derivation of guar gum was performed by grafting of 1-vinyl-2-pyrrolidone by a redox reaction in aqueous medium ceric ammonium nitrate (CAN) and potassium Peroxydisulfate(K2S2O8). The ratio of grafting efficiency (%GE) and ratio of grafting (%G) was 56% and 70.1% respectively. The grafted copolymers were characterized for percent yield and FTIR absorbance. A new aqueous two-phase extraction protocol was established using a mixture of derivatized guar and dextran. A phase diagram was constructed based on the phase separation exhibited by the system at 25 degrees C. The partition coefficient was determined for standard bovine serum albumin (BSA), lactate oxidase (LO) and phytase. The partitioning coefficients were 0.479, 1.981, and 2.586 respectively in the Dextran (2 mill ion)/V-GG/H2O system. The influence of an ionic salt sodium chloride (NaCl) was investigated on the partitioning of BSA. (C) 2008 Elsevier B.V. All rights reserved.
Keywords: Aqueous two phase; graft copolymers; Guar gum; Partition coefficient (K); Phase diagram; Vinyl pyrrolidone; viscosity

Wind tunnel investigation of the distortion of polluted water drops in the horizontal electric fields - Bhalwankar, Rohini V.; Kamra, A. K. (Journal of Geophysical Research-Atmospheres, 2009)
Distortion of the water drops freely suspended in a vertical wind tunnel is investigated when these drops are polluted with sulphate/nitrate salt and are also subjected to the horizontal electric fields. Results show that although the drops' average shape is not significantly affected, the magnitudes of drop oscillations decrease when these are formed from the water polluted with sulphate/nitrate salt. However, when these polluted drops are placed in a horizontal electric field, their oblateness increases with respect to that of the distilled water drops, and this increase in oblateness is more in higher electric fields. Results can possibly be explained because of the increase in surface tension, viscosity and density, and a more dominant effect due to the increase in electrical conductivity of the polluted water. Significance of the results is discussed in view of the possible modification of lightning activity in clouds formed over big cities.

Abrupt shear thickening of aqueous solutions of hydrophobically modified poly(N,N `-dimethylacrylamide-co-acrylic acid) - Lele, Ashish K.; Shedge, Aarti; Badiger, Manohar V.; Wadgaonkar, Prakash; Chassenieux, Christophe (Macromolecules, 2010)
We report some new and interesting observations on the abrupt and large shear-induced thickening of aqueous solutions of hydrophobically modified poly(N,N'-dimethylacrylamide-co-acrylic acid). High molecular weight copolymer was prepared by free radical copolymerization of N,N'-dimethylacrylamide [DMA] and acrylic acid [AA] and was subsequently modified to different extents using a hydrophobic compound, namely, 3-pentadecylcyclohexylamine [3-PDCA], which is derived from a renewable resource material, cashew nutshell liquid [CNSL]. The structural elucidation of the base copolymer and the hydrophobically modified copolymers was performed by (1)H and (13)C NMR spectroscopy. The zero shear viscosities [eta(0)] of the hydrophobically modified polymers were lower than that of the precursor poly(N,N'-dimethylacrylamide-co-acrylic acid) until some critical polymer concentration, which increased with increase in hydrophobic modification. Above the critical concentrations, the eta(0) of the hydrophobically modified copolymers surpassed that of the precursor at the same concentration. At moderate shear rates some of these hydrophobically modified copolymers exhibited an abrupt shear-induced thickening in which the viscosity of the samples increased severalfold. We show here from creep experiments that thickening occurs only when the shear rate reaches a critical value, (gamma) over dot(crit), and that the thickened samples can be trapped in different metastable states by controlling the applied stress. Interestingly, the shear thickened samples showed further thickening upon decreasing the applied stress. Eventually, the metastable samples revert to their equilibrium states at characteristic time that depends on (small) probe stress.

Adsorption of fluoride from aqueous solution by alumina of alkoxide nature: batch and continuous operation - Kamble, Sanjay P.; Deshpande, Gunavant; Barve, Prashant P.; Rayalu, Sadhana; Labhsetwar, Nitin K.; Malyshew, Alexander; Kulkarni, Bhaskar D. (Desalination, 2010)
In this investigation, we report the adsorption potential of alkoxide origin alumina for defluoridation of drinking water using batch and continuous mode of operations. The effects of different operating parameters such as adsorbent dose, initial fluoride concentration, pH of the solution and interfering ions (usually present in groundwater) were studied with a view to understand the adsorption behavior of the material under various conditions. A thermodynamic study shows that the adsorption of fluoride by alkoxide origin alumina is an exothermic and spontaneous process. The kinetic results showed that the fluoride sorption follows pseudo-second-order kinetics. The applicability of adsorbent in the field is also tested through column breakthrough studies. It has been observed that with an increase in the flow rate and initial fluoride concentration, the breakthrough curve becomes sharper and the breakthrough time and adsorbed fluoride ion concentration decrease. The breakthrough curve also becomes steeper as the bed height increases. The alkoxide origin alumina based adsorbent media can be used directly for field applications since it is also commercially available in granular form. (C) 2010 Elsevier B.V. All rights reserved.
Keywords: Adsorption; Alkoxide alumina; Breakthrough studies; Fluoride; Kinetic modeling

Amino functionalized oligoimides telechelics - Dwivedi, Mayank; Rao, Locanindi Hari Sarvothama; Reddy, Krishna Mohan Srinivasulu; Dhanasekharan, Janakiraman; Rao, Bevara Madhusudana; Kumar, Sriperambudur Rajesh; Ponrathnam, Surendra; Rajan, Chelanattukizhakkemadath Raman; Deokar, Sarika Babasaheb; Mulani, Khudbudin Baban; Ghorpade, Ravindra V.; Bhongale, Sunil Sitaram; et al. (2010)
This invention relates to a process for the preparation of amino functionalized oligoimide telechelics. More particularly it relates to a process for the preparation of soluble oligoimide prepolymers which can be used as matrix resins that can be rapidly cured to form stable polyimides with amino end functionalities. The amino functionalized oligoimide telechelics are suitable for conversion into three dimensional polymeric systems through condensation chemistry such as reaction with oligo epoxies (epoxy-imide resins), polyacids (polyamide imides) and polyhalogenated compounds (poly amine - imides) to form crosslinked structures having enhanced thermal stability and mechanical strength. The polymers prepared by the process of this invention can be used as materials in advanced composites having high temperature stability.

Bacterial synthesis of phtocatalytically active and biocompatible TiO2 and ZnO nanoparticles - Singh, Sanjay; Britto, Virginia D.; Bharde, Atul A.; Sastry, Murali; Dhawan, Alok; Bhagavatula L. V. Prasad (International Journal of Green Nanotechnology: Physics and Chemistry, 2010)
TiO2 and ZnO nanoparticles are well known for their photocatalytic and ultraviolet (UV)-absorbent properties and have successfully entered into the market as consumer products. Large volume production of these nanoparticles by industries require environmentally friendly processes of synthesis. In this article, we show that when challenged with an appropriate precursor, the bacterium Actinobacter spp. can lead to the extracellular synthesis of ZnO and TiO2 nanoparticles. The biological way of synthesizing these materials probably leads to the in situ doping of elements like C, F, and N into their crystal lattices, which is evidenced by a red shift in the absorption edge. Because the doping is expected to affect the photocatalytic activity of these materials under different light conditions, such investigations have also been undertaken here. Further, the biocompatibility of these nanomaterials (cytotoxicity and genotoxicity) has also been investigated in detail.
Keywords: Biosynthesis; genotoxicity; Nanoparticles; Nanotoxicity; Photocatalysis

Calculation of dipole transition matrix elements and expectation values by vibrational coupled cluster method - Banik, Subrata; Pal, Sourav; Prasad, M. Durga (Journal of Chemical Theory and Computation, 2010)
An effective operator approach based on the coupled cluster method is described and applied to calculate vibrational expectation values and absolute transition matrix elements. Coupled cluster linear response theory (CCLRT) is used to calculate excited states. The convergence pattern of these properties with the rank of the excitation operator is studied. The method is applied to a water molecule. Arponen-type double similarity transformation in extended coupled cluster (ECCM) framework is also used to generate an effective operator, and the convergence pattern of these properties is compared to the normal coupled cluster (NCCM) approach. It is found that the coupled cluster method provides an accurate description of these quantities for low lying vibrational excited states. The ECCM provides a significant improvement for the calculation of the transition matrix elements.

Carbon dissolution and segregation in Pd(110) - Bowker, Michael; Counsell, Jonathan; El-Abiary, Kareem; Gilbert, Lee; Morgan, Chris; Nagarajan, Sankaranarayanan; Gopinath, Chinnakonda S. (Journal of Physical Chemistry C, 2010)
The bulk-surface diffusion of carbon in Pd(110) has been investigated using Molecular beams to examine the clean-off of carbon with gas-phase oxygen. The dominant product of the reaction above 600 K is CO CO, is only produced at much lower temperatures where the lifetime of adsorbed CO is significant. The segregation from the bulk Only Occurs at a measurable rate at >750 K, while loss of carbon into the bulk call occur at much lower temperatures. The reaction of carbon at high temperatures shows two regimes: (i) a non steady-state evolution of CO due to the clean-off of surface carbon already present on the surface, followed by (ii) a near steady-state reaction due to the continuous diffusion of carbon to the surface.

Chemoselective hydrogenation of cinnamaldehyde over Pd/CeO2-ZrO2 catalysts - Bhogeswararao, Seemala; Srinivas, D. (Catalysis Letters, 2010)
Selective hydrogenation of cinnamaldehyde over Pd (2 wt%) supported on CeO2, ZrO2 and CeO2-ZrO2 catalysts is reported for the first time. In general, the olefinic (C=C) group of cinnamaldehyde is preferentially hydrogenated compared to the carbonyl (C=O) group. This selectivity preference could, however, be altered or reversed by adding alkali additives to the catalyst. The influence of additive on the structure and redox properties of the active sites and correlation of that with selective hydrogenation activity is investigated.
Keywords: alpha; beta-Unsaturated aldehyde; Ceria-zirconia; Cinnamaldehyde; Hydrogenation; palladium catalyst

Chronic inflammatory responses to microgel-based implant coatings - Bridges, Amanda W.; Whitmire, Rachel E.; Singh, Neetu; Templeman, Kellie L.; Babensee, Julia E.; Lyon, L. Andrew; Garcia, Andres J. (Journal of Biomedical Materials Research, 2010)

Clicking molecular hooks on silica nanoparticles to immobilize catalytically important metal complexes: the case of gold catalyst immobilization - Ganai, Anal Kumar; Bhardwaj, Rima; Hotha, Srinivas; Sen Gupta, Sayam; Bhagavatula L. V. Prasad (New Journal of Chemistry, 2010)
Gold mediated reactions have emerged as one of the best choices for affecting a variety of chemical transformations with a wide range of functional group tolerance. Application of such transformations to industrial processes necessitates immobilization of the Au ions into a matrix for easy separation of the catalyst after reaction. We report the synthesis and characterization of silica nanoparticles in which Au(III) has been immobilized through a 1,2,3-triazole linkage using an alkynalated picolinic acid exploiting ``click chemistry''. The Au( III) immobilized silica nanoparticle has been thoroughly characterized using FT-IR, C-13 CP MAS NMR and XPS. The utility of these particles as an easily separable catalyst for the Hashmi phenol synthesis is also reported.

Conformational polymorphism in racemic 2,4-Di-o-Benzoyl-6-o-Tosyl myo-Inositol 1,3,5-Orthoacetate - Manoj, Kochunnoonny; Gonnade, Rajesh G.; Bhadbhade, Mohan M.; Shashidhar, M. S. (Journal of Structural Chemistry, 2010)
The title compound, C(29)H(26)O(10)S, yields two conformational polymorphs concomitantly from dichloromethane-methanol mixture; the major polymorph grows as plates (Form I, monoclinic, P2(1)/n) and the minor polymorph grows as needles (Form II, triclinic, P-1). The two forms differ mainly in orientation of the tosyl group. In Form I, sulfonyl oxygen of the tosyl group makes intermolecular C -HaEuro broken vertical bar O interactions, whereas the same group in Form II is involved in an intramolecular short dipolar S=OaEuro broken vertical bar C=O (sulfonyl-carbonyl) contact. The molecular organization and the influence of various weak non-covalent interactions that stabilize these conformers in the crystal lattices are discussed.
Keywords: Conformation; crystal structure; dipolar interactions; Inositol; non-covalent interactions; polymorphism; sulfonyl-carbonyl contact

Coupling growth-factor engineering with nanotechnology for therapeutic angiogenesis - Roy, Rituparna Sinha; Soni, Shivani; Harfouche, Rania; Vasudevan, Pooja R.; Holmes, Oliver; de Jonge, Hugo; Rowe, Arthur; Paraskar, Abhimanyu; Hentschel, Dirk M.; Chirgadze, Dimitri; Blundell, Tom L.; Gherardi, Ermanno; et al. (Proceedings of the National Academy of Sciences of the United States of America, 2010)
Therapeutic angiogenesis is an emerging paradigm for the management of ischemic pathologies. Proangiogenic Therapy is limited, however, by the current inability to deliver angiogenic factors in a sustained manner at the site of pathology. In this study, we investigated a unique nonglycosylated active fragment of hepatocyte growth factor/scatter factor, 1K1, which acts as a potent angiogenic agent in vitro and in a zebrafish embryo and a murine matrigel implant model. Furthermore, we demonstrate that nanoformulating 1K1 for sustained release temporally alters downstream signaling through the mitogen activated protein kinase pathway, and amplifies the angiogenic outcome. Merging protein engineering and nanotechnology offers exciting possibilities for the treatment of ischemic disease, and furthermore allows the selective targeting of downstream signaling pathways, which translates into discrete phenotypes.
Keywords: cardiovascular disease; HGF/SF; ischemic disease; nanoparticle; protein engineering

Crystal-to-crystal thermal phase transition amongst dimorphs of hexa-O-p-toluoyl-myo-inositol conserving two-dimensional isostructurality - Gonnade, Rajesh G.; Bhadbhade, Mohan M.; Shashidhar, Mysore S. (Crystengcomm, 2010)
Triclinic (P-1) crystals of hexa-O-p-toluoyl-myo-inositol obtained from common organic solvents exhibited single crystal-to-single crystal irreversible phase transition centered at similar to 250 degrees C. The transformation of these crystals to monoclinic P2(1)/n form was revealed using DSC and X-ray diffraction studies. The latter crystals could also be produced by melt crystallization. Crystal structure analysis revealed that the molecules in both forms are linked via bifurcated C-H center dot center dot center dot O interactions to make almost identical centrosymmetric dimers. The neighbouring dimers are bridged via C-H center dot center dot center dot O and aromatic pi center dot center dot center dot pi stacking interactions to create two-dimensional isostructural assemblies. The difference in the two crystal forms arises from linking of the centrosymmetric dimers along the third dimension; the dimers are centrosymmetrically bridged in the triclinic form, while they have n-glide relationship in the monoclinic form. Comparison of the dimorph structures further revealed that they are actually an excellent case of morphotropism since dimorphs are related by non crystallographic rotation and translation of their basic motif (centrosymmetric dimers) that transforms the triclinic (P-1) phase to a monoclinic (P2(1)/n) phase.

Cytotoxic activity of 9,10-dihydro-2,5-dimethoxyphenanthrene-1,7-diol from Eulophia nuda against human cancer cells - Shriram, Varsha; Kumar, Vinay; Kishor, P. B. Kavi; Suryawanshi, Sharad B.; Upadhyay, Ankur K.; Bhat, Manoj K. (Journal of Ethnopharmacology, 2010)
Ethnopharmacological relevance: Eulophia nuda L. (Orchidaceae) is a medicinally important terrestrial orchid used for the treatment of tumours and various health problems by the local healers throughout the Western Ghats region in Maharashtra (India). Aim of the study: To isolate the active molecule from Eulophia nuda and to study its cytotoxic potential against human cancer cells. Materials and methods: The crude methanolic extract of Eulophia nuda tubers was fractionated by stepwise gradient of the solvents chloroform-methanol to isolate the pure compound. Isolated pure compound was assessed for its cytotoxic potential against human breast cancer cell lines, MCF-7 and MDA-MB-231 using MTT assay. Structure elucidation of the isolated active compound was carried out by extensive spectroscopic analysis including (1)H NMR, (13)C NMR, NOESY, COSY, LC-MS and IR. Results: The isolated active molecule was identified as phenanthrene derivative 9,10-dihydro-2,5-dimethoxyphenanthrene-1,7-diol. This compound showed good antiproliferative activity against human breast cancer cell lines MCF-7 (91%) and MDA-MB-231 (85%) at 1000 mu g/ml concentration. Conclusion: 9,10-Dihydro-2,5-dimethoxyphenanthrene-1,7-diol from Eulophia nuda tubers showed good growth suppressive effect against human cancer cell lines MCF-7 and MDA-MB-231 making it a potential biomolecule against human cancer. (C) 2009 Elsevier Ireland Ltd. All rights reserved.
Keywords: Cytotoxic activity; Eulophia nuda; Phenanthrene derivatives

Direct hydrogenation of amides to alcohols and amines under mild conditions - Balaraman, Ekambaram; Gnanaprakasam, Boopathy; Shimon, Linda J. W.; Milstein, David (Journal of the American Chemical Society, 2010)
The selective, direct hydrogenation of amides to the corresponding alcohols and amines with cleavage of the C−N bond was discovered. The expected products of C−O cleavage are not formed (except as traces in the case of anilides). The reaction proceeds under mild pressure and neutral, homogeneous conditions using a dearomatized, bipyridyl-based PNN Ru(II) pincer complex as a catalyst. The postulated mechanism involves metal−ligand cooperation by aromatization−dearomatization of the heteroaromatic pincer core and does not involve hydrolytic cleavage of the amide. The simplicity, generality, and efficiency of this environmentally benign process make it attractive for the direct transformations of amides to alcohols and amines in good to excellent yields.

Discovery of rifampicin as a new anti-glycating compound by matrix-assisted laser desorption/ionization mass spectrometry-based insulin glycation assay - Golegaonkar, Sandeep B.; Bhonsle, Hemangi S.; Boppana, Ramanamurthy; Kulkarni, Mahesh J. (European Journal of Mass Spectrometry, 2010)
An in vitro insulin glycation assay was developed for screening glycation inhibitors. The assay involves the use of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for monitoring the formation of glycated insulin. The assay is simple, rapid and amenable for high throughput screening. Using this assay we have discovered a strong anti-glycation activity for the anti-tuberculosis drug rifampicin. These results were compared with bovine serum albumin glucose fluorescence assay. In addition, the IC(50) of rifampicin was lower than that of aminoguanidine, a known anti-glycating agent, suggesting that rifampicin is a more potent glycation inhibitor.
Keywords: AGE; aminoguanidine; antibiotic; diabetic complication; drug repositioning; IC(50)

Dynamic study of N ` N-dimethylparanitroaniline encapsulated in silicalite-1 matrix using neutron spin-echo spectroscopy - Bhange, Deu S.; Dejoie, C.; Porcher, F.; Malikova, N.; Martinetto, P.; Dooryhee, E.; Anne, M. (European Physical Journal-Special Topics, 2010)
The present work focuses on the dynamic studies of N'N-dimethyl-paranitroaniline (dmpNA) encapsulated in silicalite zeolite. Quasielastic neutron scattering (QENS) experiments are carried out using neutron spin-echo technique. Polarisation of the scattered neutron beam is measured at carefully chosen values of Q = 0.35, 0.9, 1.1 and 1.45 angstrom(-1) at fixed T = 298K and at fixed Q = 0.9 angstrom(-1) at 150, 200, 250 and 298 K. This gives insight into the motion and the related activation energy of the guest dmpNA molecule. The quasielastic signal observed in the present system within the time range considered is due to fast local rotational motions of protons of the end methyl groups. The results are in good agreement with the dynamics of methyl group rotations reported in the literature by back-scattering QENS technique.

Effect of leakage current and dielectric constant on single and double layer oxides in MOS structure - Laha, Pinaki; Panda, A. B.; Dahiwale, S.; Date, Kalyani S.; Patil, K. R.; Barhai, P. K.; Das, A. K.; Banerjee, Indrani; Mahapatra, S. K. (Thin Solid Films, 2010)
MOS structure of Al/Al2O3/n-Si, Al/TiO2/n-Si and Al/Al2O3/TiO2/n-Si was obtained by deposition of Al2O3 and TiO2 on silicon substrate by RF Magnetron Sputtering system. The total thickness of the oxide layer similar to 40 +/- 5 nm in the MOS structure was kept constant. Samples were characterized by X-Ray diffraction (XRD). X-Ray photoelectron spectroscopy (XPS), Impedance analyzer and Current-voltage (J-V) characteristics. The variations in the dielectric constant and tan 8 of the MOS capacitor in the frequency range of 1000Hz-1MHz were measured by impedance analyzer. The variation in dielectric constant of the Al/Al2O3/TiO2/n-Si multilayer compared to single layer of Al/Al2O3/n-Si and Al/TiO2/n-Si is due to high probability of defects, lattice mismatch and interface interactions. The steep rise of Tan 6 values in the Al/Al2O3/TiO2/n-Si structure is due to the resonance effect of both Al2O3 and TiO2 layers. The leakage current mechanisms of MOS structures were extracted from Schottky coefficient and Poole-Frenkel coefficient. Theoretical values of Schottky coefficients (beta(SC)) and Poole-Frenkel coefficients (beta(PF)) for each sample were estimated using the real part of the dielectric constant. The experimental values were calculated from J-V characteristics and compared with theoretical values. The appropriate model has been proposed. It was found that Schottky and Poole-Frenkel mechanisms are applicable at low and high field respectively for all MOS structures. The combination of Al/Al2O3/TiO2/n-Si is found to be a promising structure with high dielectric constant and low leakage current suitable for MOS devices. (C) 2010 Elsevier B.V. All rights reserved.
Keywords: Al2O3; dielectric constant; Leakage current; MOS device; Poole-Frenkel emission; Schottky emission; TiO2

Effect of nanoparticle conjugation on gene silencing by RNA interference - Singh, Neetu; Agrawal, Amit C.; Leung, Anthony K. L.; Sharp, Phillip A.; Bhatia, Sangeeta N. (Journal of American Chemical Society, 2010)

Elucidation of the role of hexamine and other precursors in the formation of magnetite nanorods and their stoichiometry - Singh, Hema; Bhagwat, Shrikant; Jouen, Samuel; Lefez, Benoit; Athawale, Anjali A.; Hannoyer, Beatrice; Ogale, Satishchandra (Physical Chemistry Chemical Physics, 2010)
Hexamine is known to assist anisotropic growth of metal oxides and the same is also found to be true for magnetite nanosynthesis. In this work we elucidate the role of hexamine and other precursors in the formation of magnetite nanorods by the hydrothermal route and their stoichiometry. Various others hydrolyzing agents such as sodium hydroxide (NaOH), sodium hydroxide + hexamine, ammonia (NH(3)), ammonia + formaldehyde are also studied. The synthesized nanoparticles are characterized with the help of various techniques such as X-ray diffraction (XRD), FT-IR spectroscopy, UV-VIS-NIR spectroscopy, transmission electron microscopy (TEM), Mossbauer spectroscopy and SQUID magnetization measurements. It is found that only when ferric chloride, ferrous ammonium sulfate (FAS) and hexamine are used, well defined nanorods are formed. When sodium hydroxide and hexamine are used as a hydrolyzing system nearly spherical nanoparticles with small size (similar to 13 nm) are formed, as compared to the case of sodium hydroxide alone which leads to bigger cube like nanoparticles. Interestingly the decomposition products of hexamine do not lead to nanorod formation. Thus, slow decomposition of hexamine at elevated temperature and the consequent slow rise in pH is the key to the anisotropic growth of the iron oxide system.

Enantiospecific synthesis of sex pheromone of the obscure mealybug from pantolactone via tandem conjugate addition/cyclization - Hajare, Atul K.; Datrange, Laxmikant S.; Vyas, Samir; Bhuniya, Debnath; Reddy, D. Srinivasa (Tetrahedron Letters, 2010)
An efficient synthesis of an enantiomer of insect's natural pheromone is reported starting from chiral pool D-(-)-pantolactone. Highly stereoselective tandem conjugate addition/cyclization sequence and hydrogenation of exocyclic double bond are the key steps in the present synthesis. (C) 2010 Elsevier Ltd. All rights reserved.

Enhanced negative thermal expansion in MFI molecular sieves by varying framework composition - Bhange, Deu S.; Ramaswamy, Veda (Microporous and Mesoporous Materials, 2010)
In the present investigations we have carried out the high temperature X-ray diffraction (HTXRD) studies on the metallosilicate molecular sieves iron silicalite-1 (FeS-1) samples of different Si/M ratios (Si/Fe = 50, 75, 100 and infinity) for their negative thermal expansion (NTE) behavior. All the samples exhibit NTE behavior in the temperature range 373-773 K. Systematic increase in negative thermal expansion coefficient is observed as a function of increasing Fe content in the MFI framework. Strength of the negative thermal expansion increases in the order Si/Fe = infinity < 100 < 75 < 50. It is concluded that by changing the composition of the framework of MFI, enhanced negative thermal expansion can be obtained. (C) 2009 Elsevier Inc. All rights reserved.
Keywords: HTXRD; Negative thermal expansion; Silicalite-1

Evidence for the co-existence of distorted tetrahedral and trigonal bipyramidal aluminium sites in SrAl12O19 from Al-27 NMR studies - Harindranath, K.; Viswanath, K. Anusree; Chandran, C. Vinod; Braeuniger, Thomas; Madhu, Perunthiruthy K.; Ajithkumar, Thalasseril G.; Joy, Pattayil Alias (Solid State Communications, 2010)
Strontium aluminate, SrAl12O19, is a ceramic material having the hexagonal magnetoplumbite-type structure, with multiple Al coordination environments. An earlier low-field Al-27 solid-state NMR study reported five different Al sites in this system: one AlO4, one AlO5, and three AlO6 sites; whereas a later high-field study showed that the AlO5 site is a distorted AlO4 site with a very large quadrupolar coupling constant (similar to 20 MHz). Our magic angle spinning (MAS) and 3-quantum magic angle spinning (3QMAS) NMR studies at 7.05 T unambiguously show evidence for an AlO5 site. However, evidence for the presence of a distorted AlO4 site is obtained from studies at high fields (16.4 and 17.6 T), in addition to the AlO5 site. Thus the present solid-state NMR studies give evidence for the simultaneous presence of both the five-coordinated and distorted four-coordinated sites in this system. (C) 2009 Elsevier Ltd. All rights reserved.
Keywords: Local structure; MQMAS; Nuclear magnetic resonance; Strontium aluminate

Experimental and theoretical study on the remarkable influence of protecting groups on the selectivity of addition of amines to vinyl sulfone-modified hex-2-enopyranosides - Bhattacharya, Rahul; Kesharwani, Manoj K.; Manna, Chinmoy; Ganguly, Bishwajit; Suresh, Cheravakattu G.; Pathak, Tanmaya (Journal of Organic Chemistry, 2010)
Although phenylmethylene-protected vinyl sulfone-modified carbohydrate 2 alpha reacts with both primary and secondary amines in Michael fashion to afford aminated products, only primary amines react with the dibenzyl-protected 3 alpha, 6-O-trityl-protected 4 alpha, and unprotected 5 alpha, highlighting for the first time the remarkable influence of protecting, groups on the reaction patterns of vinyl sulfone-modified carbohydrates. The quantum chemical calculations suggest that the Michael addition of amines and proton transfer to vinyl sulfone-modified carbohydrates 2 alpha and 5 alpha are possible via relay process in a concerted mechanism. These calculations reveal that the addition of primary amines to vinyl sulfone-modified carbohydrate is preferential due to the low activation energy barriers, whereas the addition of secondary amines has relatively higher activation energy barriers. The theoretical conclusions are in line with the experimental observations.

Fabrication of In-doped SnO2 nanowire arrays and its field emission investigations - Bhise, Ashok B.; Late, Dattatray J.; Sathe, B.; More, Mahendra A.; Mulla, Imtiaz S.; Pillai, Vijayamohanan K.; Joag, Dilip S. (Journal of Experimental Nanoscience, 2010)
The field emission of In-doped SnO2 wire array has been performed in parallel plate diode configuration. A maximum current density of 60 mu A/cm2 is drawn from the emitter at an applied field of 4 V/mu m. The nonlinearity in the Fowler-Nordheim plot, characteristics of semiconductor emitter has been observed and explained on the basis of electron emission from both the conduction and the valence bands. The current stability recorded at a preset value of 1 mu A is observed to be good. The high emission current density, good current stability and mechanically robust nature of the wires offer unprecedented advantages as promising cold cathodes for many potential applications based on field emission.
Keywords: cold cathodes; device; Doping; field emission; Nanowires; SnO2

Ferrocene-Bis(thymine/uracil) conjugates: base pairing directed, spacer dependent self-assembly and supramolecular packing - Patwa, Amit N.; Gonnade, Rajesh G.; Kumar, Vaijayanti A.; Bhadbhade, Mohan M.; Ganesh, Krishna N. (Journal of Organic Chemistry, 2010)
X-ray crystallographic studies of methylene linked Ferrocene-bis(thymine/uracil) conjugates Fc(T:T)m and Fc(U:U)(M) reveal base dependent 2-D supramolecular assemblies generated via wobble self-pairing for bis-thymine and reverse wobble self-pairing for bis-uracil conjugates, differing in architecture from the corresponding butylene spacer linked conjugates

Flocculation of dimorphic yeast benjaminiella poitrasii is altered by modulation of NAD-glutamate dehydrogenase - Joshi, C. V.; Ghormade, Vandana; Kunde, P.; Kulkarni, P.; Mamgain, H.; Bhat, Suresh K.; Paknikar, K. M.; Deshpande, Mukund V. (Bioresource Technology, 2010)
A strategy to control flocculation is investigated using dimorphic yeast, Benjaminiella poitrasii as a model. Parent form of this yeast (Y) exhibited faster flocculation (11.1 min) than the monomorphic yeast form mutant Y-5 (12.6 min). Atomic force microscopy revealed higher surface roughness of Y (439.34 rms) than Y-5 (52 rms). Also, the former had a zeta potential of -65.97 +/- 3.45 as against -50.21 +/- 2.49 for the latter. Flocculation of both Y and Y-5 could be altered by supplementing either substrates or inhibitor of NAD-glutamate dehydrogenase (NAD-GDH) in the growth media. The rate of flocculation was promoted by alpha-ketoglutarate or isophthalic acid and decelerated by glutamate with a statistically significant inverse correlation to corresponding NAD-GDH levels. These interesting findings open up new possibilities of using NAD-GDH modulating agents to control flocculation in fermentations for easier downstream processing. (C) 2009 Elsevier Ltd. All rights reserved.
Keywords: Benjaminiella poitrasii; dimorphism; flocculation; NAD-glutamate dehydrogenase

Fluconazole analogues containing 2H-1,4-benzothiazin-3(4H)-one or 2H-1,4-benzoxazin-3(4H)-one moieties, a novel class of anti-Candida agents - Borate, Hanumant B.; Maujan, Suleman R.; Sawargave, Sangmeshwer P.; Chandavarkar, Mohan A.; Vaiude, Sharangi R.; Joshi, Vinay A.; Wakharkar, Radhika D.; Iyer, Ramki; Kelkar, Ramesh G.; Chavan, Subhash P.; Kunte, Sunita S. (Bioorganic & Medicinal Chemistry Letters, 2010)
As a part of our program to develop new antifungal agents, a series of fluconazole analogues was designed and synthesized wherein one of the triazole moieties in fluconazole was replaced with 2H-1,4-benzothiazin-3(4H)-one or 2H-1,4-benzoxazin-3(4H)-one moiety. The new chemical entities thus synthesized were screened against various fungi and it was observed that the compounds 4a and 4i are potent inhibitors of Candida strains. The structure-activity relationship for these compounds is discussed. (C) 2009 Elsevier Ltd. All rights reserved.
Keywords: antifungal; Benzothiazinone; Benzoxazinone; Fluconazole

Free radical graft copolymerization of N-vinyl-2-pyrrolidone onto k-carrageenan in aqueous media and applications - Mishra, Madan Mohan; Sand, Arpit; Mishra, Dinesh Kumar; Yadav, Mithilesh; Behari, Kunj (Carbohydrate Polymers, 2010)
In the present article, the graft copolymer of k-carrageenan with N-vinyl-2-pyrrolidone (NVP) has been synthesized using PMS/maleic acid as a redox initiator in aqueous medium and reaction conditions have been optimized to obtain maximum % grafting ratio (%G). The optimum conditions of maximum grafting have been found by varying the different parameters. On increasing the concentration of maleic acid and peroxymonosulphate from 1.6 x 10(-3) to 4.8 x 10(-3) mol dm(-3) and 0.6 x 10(-2) to 2.2 x 10(-2) mol dm(-3) respectively, the initially grafting parameters increased and after a certain range of concentration grafting parameters showed decreasing trend. The small increment of concentration in hydrogen ion causes increment in percentage grafting. It was observed that the grafting parameters increase as the concentration of N-vinyl-2-pyrrolidone increases up to 16 x 10(-2) mol dm(-3) after that it decreased. The optimum condition for maximum grafting has obtained at concentration 1.0 g dm(-3) of k-carrageenan at 40 degrees C and 120 min, respectively. (C) 2010 Elsevier Ltd. All rights reserved.
Keywords: flocculation; Graft copolymer; k-Carrageenan; Metal ion uptake; N-vinyl-2-pyrrolidone; swelling

Harnessing structure-activity relationship to engineer a cisplatin nanoparticle for enhanced antitumor efficacy - Paraskar, Abhimanyu S.; Soni, Shivani; Chin, Kenneth T.; Chaudhuri, Padmaparna; Muto, Katherine W.; Berkowitz, Julia; Handlogten, Michael W.; Alves, Nathan J.; Bilgicer, Basar; Dinulescu, Daniela M.; Mashelkar, Raghunath Anant; Sengupta, Shiladitya (Proceedings of the National Academy of Sciences of the United States of America, 2010)
Cisplatin is a first line chemotherapy for most types of cancer. However, its use is dose-limited due to severe nephrotoxicity. Here we report the rational engineering of a novel nanoplatinate inspired by the mechanisms underlying cisplatin bioactivation. We engineered a novel polymer, glucosamine-functionalized polyisobutylene-maleic acid, where platinum (Pt) can be complexed to the monomeric units using a monocarboxylato and an O –> Pt coordinate bond. We show that at a unique platinum to polymer ratio, this complex self-assembles into a nanoparticle, which releases cisplatin in a pH-dependent manner. The nanoparticles are rapidly internalized into the endolysosomal compartment of cancer cells, and exhibit an IC50 (4.25 + 0.16 mu M) comparable to that of free cisplatin (3.87 +/- 0.37 mu M), and superior to carboplatin (14.75 +/- 0.38 mu M). The nanoparticles exhibited significantly improved antitumor efficacy in terms of tumor growth delay in breast and lung cancers and tumor regression in a K-ras(LSL/+)/Pten(fl/fl) ovarian cancer model. Furthermore, the nanoparticle treatment resulted in reduced systemic and nephrotoxicity, validated by decreased biodistribution of platinum to the kidney as quantified using inductively coupled plasma spectroscopy. Given the universal need for a better platinate, we anticipate this coupling of nanotechnology and structure-activity relationship to rationally reengineer cisplatin could have a major impact globally in the clinical treatment of cancer.
Keywords: cancer; chemotherapy; nanomedicine

Helical self-assembly of molecules in pseudopolymorphs of racemic 2,6-di-O-(4-halobenzoyl)-myo-inositol 1,3,5-orthoformates: clues for the construction of molecular assemblies for intermolecular acyl transfer reaction - Krishnaswamy, Shobhana; Gonnade, Rajesh G.; Shashidhar, Mysore S.; Bhadbhade, Mohan M. (Crystengcomm, 2010)
The crystal structure of racemic 2,6-di-O-benzoyl-myo-inositol 1,3,5-orthoformate (1) which underwent a facile intermolecular benzoyl transfer reaction in the solid state, revealed a helical assembly of molecules along the two-fold screw axis via O-H center dot center dot center dot O hydrogen bond bringing the electrophile (C=O) and the nucleophile (-OH) in close proximity along the helical axis. However, structurally related racemic 2,6-di-O-(p-halobenzoyl)-myo-inositol 1,3,5-orthoformates (bromo (2) and chloro (3)) produced triclinic dimorphs (both P (1) over bar) when crystallized from methanol and ethyl acetate. Molecules in either form did not assemble spirally (like 1), and instead exhibited a one-dimensional isostructurality, bridging O-H center dot center dot center dot O linked identical molecular strings via C-H center dot center dot center dot O interactions across the inversion center. However, the molecules of 2 and 3 assembled in a helical manner similar to 1 with inclusion of solvent molecules in the crystal lattice when crystallized from other common organic solvents. Remarkably, in all the solvates the host molecules formed strikingly similar helices around the crystallographic 2(1)-screw axis through O-H center dot center dot center dot O bond involving the -OH group and carbonyl oxygen of the equatorial C2-O-benzoyl group. Comparison of the crystal structure of dimorphs and the solvatomorphs revealed that the solvent molecules, which interact with the orthoformate-bridge, trigger the helix formation of the host. The difference in the crystal structures of solvatomorphs arises in the interlinking of the neighbouring helices, which creates voids of different sizes to accommodate the solvent molecules. All the solvates crystallized in the monoclinic system distributed over three different space groups P2(1)/n, P2(1)/c and C2/c. In the P2(1)/n system, the adjacent helices are linked via C-X center dot center dot center dot O contacts, in P2(1)/c via C-H center dot center dot center dot X (X Cl, Br) contacts and in C2/c via short X center dot center dot center dot X contacts (X = Cl). The helical organization achieved through solvent mediation and inclusion is of significance in creating molecular packing for intermolecular acyl transfer reactions in crystals.

High aspect ratio nanoscale multifunctional materials derived from hollow carbon nanofiber by polymer insertion and metal decoration - Balan, Beena K.; Kale, Vinayak S.; Aher, Pradnya P.; Shelke, Manjusha V.; Pillai, Vijayamohanan K.; Kurungot, Sreekumar (Chemical Communications, 2010)
A novel high aspect ratio material which can simultaneously display multiple functions such as proton and electron conductivity and electrocatalytic activity has been developed by incorporating both platinum nanoparticles and phosphoric acid doped polybenzimidazole along the inner and outer surfaces of a hollow carbon nanofiber.

Hydrophobically modified poly(vinyl alcohol) using alkoxy-substituted methyl gallate: synthesis and rheology - Shedge, Aarti S.; Wadgaonkar, Prakash P.; Lele, Ashish K.; Badiger, Manohar V. (Journal of Polymer Science Part B-Polymer Physics, 2010)
Hydrophobically modified poly(vinyl alcohol) (HMPVA) polymers were synthesized by potassium t-butoxide-catalyzed reaction of PVA with methyl 3,4,5-tris(n-octyloxy) benzoate (MGC(8))/3,4,5-tris(n-dodecyloxy) benzoate (MGC(12)) and 1,3-propane sultone. The concentration of 1,3-propane sultone was kept constant at 10 mol %. and that of MGC(8) (2, 3, and 4 mol %)/MGC(12) (2 and 3 mol %) was varied to obtain HMPVAs with different hydrophobic contents. The incorporation of MGC(8)/MGC(12) and 1,3-propane sultone onto HMPVA was confirmed by NMR spectroscopy. Rheological properties of aqueous solutions also confirmed the presence of hydrophobic and charged functional groups on HMPVAs. In the semidilute regime, the specific viscosity of HMPVAs followed concentration scaling that is typical of polyelectrolytes. At higher concentrations, the HMPVA solutions with 3 and 4 mol % of MGC(8) exhibited large increase in specific viscosity. Oscillatory experiments on these solutions exhibited gel-like behavior at polymer concentrations of 40-50 g/L. Confocal microscopy images of HMPVA with 4 mol % of MGC(8) clearly indicated the existence of microgels. The tendency of formation of microgels further increased with increasing chain length of the hydrophobe, that is, with MGC(12). These samples exhibited rheological behavior that is typical of soft solids and was therefore probed by the strain-rate frequency superposition technique reported recently in the literature. HMPVAs with improved rheological properties show potential applications as thickeners in cosmetic creams, lotions and as drug carriers in pharmaceutical formulations. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1054-1063, 2010
Keywords: gallic acid; hydrophobically modified poly(vinyl alcohol); Rheology; water-soluble polymers

Influence of filler size and morphology in controlling the thermal emissivity of aluminium/polymer composites for space applications - Babrekar, Harshada A.; Kulkarni, Naveen V.; Jog, Jyoti Prakash; Mathe, Vikas L.; Bhoraskar, S. V. (Materials Science and Engineering B-Advanced Functional Solid-State Materials, 2010)
The paper has addressed the problem of controlling the thermal emissivities from metal/polymer composites prepared by solution method. Aluminium is used as a filler and polystyrene as a polymer-matrix. Aluminium particles, with micrometer and nanometer dimensions having different morphologies, were employed. The values of emissivities were reduced when the coarse grains and flakes of aluminium were used as fillers, whereas, no significant change was observed when nano-aluminium was used in the composite. Dielectric dispersion for the composites was measured and the results are analysed in view of Fresnel relation. The differences in the values of dielectric constants, between the experimentally measured and those which can be predicted theoretically, are thought to arise from the interfacial polarization. (C) 2009 Elsevier B.V. All rights reserved.
Keywords: Camouflaging; Composite; dielectric constant; Infra-red; Thermal emissivity

Intermolecular N-heterocyclic carbene-catalyzed hydroacylation of arynes - Biju, Akkattu T.; Glorius, Frank (Angewandte Chemie-International Edition, 2010)
A formal introduction: The conceptually new N-heterocyclic carbene catalyzed formal insertion of arynes into the Cformyl[BOND]H bond of aldehydes demonstrates the compatibility of nucleophilic NHCs with electrophilic arynes. This NHC-catalyzed hydroacylation of arynes allows the conversion of aliphatic, α,β-unsaturated, and aromatic aldehydes into aryl ketones; 27 examples and a preliminary mechanistic investigation are provided.

Kinetics studies and mechanism evolution of the epoxidation of styrene over nanoporous Au doped TS-1 - Saxena, Samidha; Dwivedi, Reena; Bhadauria, Sheenu; Chumbhale, Vilas R.; Prasad, Rajendra (Polish Journal of Chemical Technology, 2010)
{A kinetic investigation of the slurry phase epoxidation of styrene with hydrogen peroxide has been carried out, for the first time, over nanoporous Au doped TS-1 catalyst, in a batch reactor, in the temperature range of 313-333 K. It was found that product selectivity and the rate of reaction are greatly influenced by concentrations of styrene and hydrogen peroxide. Kinetics studies reveal that the mechanism of the reaction is of the ``Redox'' type. The rate equation
Keywords: Au/TS-1; epoxidation; kinetics; styrene; Styrene oxide

Large-bite bisphosphite, 1,3-C6H4OPOC10H6(μ-S)C10H6O2: synthesis, copper(I), and gold(I) complexes - Balakrishna, Maravanji S.; Kumar, Pawan; Punji, Benudhar; Mague, Joel T. (Journal of Organometallic Chemistry, 2010)
Large-bite bisphosphite ligand 1,3-C6H4{OPOC10H6(μ-S)C10H6O}2 (3), is obtained by reacting chlorophosphonite {OC10H6(μ-S)C10H6O}PCl (2) with resorcinol in the presence of triethylamine. Treatment of 3 with CuCl in 1:1 molar ratio produces a 1D-coordination polymer [CuCl{(–OC10H6(μ-S)C10H6O–)P(–OC6H4O–)P(–OC10H6(μ-S)C10H6O–)}-κP,κP]∞ (4) in good yield. Similar reaction of 3 with two equivalents of AuCl(SMe2) affords a dinuclear complex, [Au2Cl2{(–OC10H6(μ-S)C10H6O–)P(–OC6H4O–)P(–OC10H6(μ-S)C10H6O–)}-κP,κP] (5). Single crystal X-ray structures of the ligand 3 and the complexes 4 and 5 are reported. The gold complex 5 shows dimeric structure supported by strong Au···Au aurophilic interactions.

Mild, efficient, and regioselective monobromination of arylamines and phenols using [BBIm]Br-3 as a new reagent - Borikar, Sanjay P.; Daniel, Thomas; Paul, Vincent (Synthetic Communications, 2010)
We report here an efficient method for the synthesis and characterization of the room-temperature ionic liquid 1,3-di-n-butylimidazolium tribromide ([BBIm]Br-3) (2) and its application as an efficient reagent and solvent for regioselective bromination of arylamines and phenols under mild conditions. The bromination was carried out in the absence of organic solvents, and in most cases, the only extraction solvent needed was water. The spent 1,3-di-n-butylimidazolium bromide (1) was easily recycled.
Keywords: Ionic liquid; monobromination; Regioselective; Solvent-free; [BBIm]Br3

Mn-doped nanocrystals in light-emitting diodes: energy-transfer to obtain electroluminescence from quantum dots - Rath, Arup Kumar; Bhaumik, Saikat; Pal, Amlan J. (Applied Physics Letters, 2010)
We fabricatelight-emitting diodes(LEDs) based on Mn-doped ZnSnanocrystals along with hole-transporting bis(3-methylphenyl)--diphenyl-benzidine (TPD). With Mn-doping, ZnSnanostructures exhibit a strong photoluminescence. The LEDs exhibit electroluminescence(EL) from Mn-doped ZnSquantum dots and TPD. In order to open up channels for energy-transfer from TPD to quantum dots and to achieve EL from only the nanoparticles, we grow core-shell nanoparticles with Mn-doped ZnS in the core and CdS as the shell layer. Excitons formed in TPD can now transfer their energy directly to the shell-layer to yield EL from only the nanoparticles.

Monitoring structural defects and crystallinity of carbon nanotubes in thin films - Mahajan, S. S.; Bambole, M. D.; Gokhale, S. P.; Gaikwad, A. B. (Pramana-Journal of Physics, 2010)
We report the influence of catalyst formulation and reaction temperature on the formation of carbon nanotube (CNT) thin films by the chemical vapour deposition (CVD) method. Thin films of CNTs were grown on Fe-Mo/Al(2)O(3)-coated silicon wafer by thermal decomposition of methane at different temperatures ranging from 800 to 1000A degrees C. The electron microscopic investigations, SEM as well as HRTEM, of the as-grown CNT thin films revealed the growth of uniform multi-walled CNTs in abundance. The intensity ratio of D-band to G-band and FWHM of G-band through Raman measurements clearly indicated the dependency of structural defects and crystallinity of CNTs in thin films on the catalyst formulation and CVD growth temperature. The results suggest that thin films of multi-walled CNTs with negligible amount of defects in the nanotube structure and very high crystallinity can be obtained by thermal CVD process at 925A degrees C.
Keywords: Carbon nanotubes; chemical vapour deposition; Raman spectroscopy; scanning electron microscopy; Thin films

Nanoscale modulation of electronic states across unit cell steps on the surface of an epitaxial colossal magnetoresistance manganite film - Rana, Abhimanyu; Bogle, Kashinath A.; Game, Onkar S.; Patil, Shankar; Valanoor, Nagarajan; Ogale, Satishchandra B. (Applied Physics Letters, 2010)
The nature of electronic states near the edge of unit cell steps on the surface of epitaxial La(0.7)Sr(0.3)MnO(3) (LSMO) thin films grown by real-time reflection high energy electron diffraction monitored pulsed laser deposition is examined by scanning tunneling microscopy and scanning tunneling spectroscopy techniques. It is observed that the electronic states are strongly modulated near the step edge with considerably high gap at the edge and low gap on the terrace. This modulation weakens at low temperature. The temperature evolution of the density of states and the nature of gap in deep metallic state of LSMO are also discussed. (C) 2010 American Institute of Physics. [doi:10.1063/1.3455886]
Keywords: colossal magnetoresistance; electronic density of states; lanthanum compounds; magnetic epitaxial layers; Nanostructured materials; pulsed laser deposition; reflection high energy electron diffraction; scanning tunnelling microscopy; scanning tunnelling spectroscopy; strontium compounds

New organic-inorganic hybrid microporous organosilica having high metal ion adsorption capacity - Paul, Manidipa; Pal, Nabanita; Rajamohanan, P. R.; Rana, Bharat S.; Sinha, Anil K.; Bhaumik, Asim (Physical Chemistry Chemical Physics, 2010)
A new microporous organic-inorganic hybrid organosilica LHMM-2 containing a bis(propyliminomethyl)benzene moiety inside the framework has been synthesized hydrothermally without using any template or structure-directing agent. Powder XRD and TEM image analyses suggest a new disordered microporous structure with pores of dimension ca. 0.54 nm, and C-13 and Si-29 MAS NMR and spectroscopic results indicate the presence of bridging organic bis(propyliminomethyl) benzene moiety in this framework. TPD-NH3 results suggested that nearly 5 times as much bis(propyliminomethyl) benzene moiety is located inside the micropore walls (matrix) than in the surface of the pores. LHMM-2 shows very high adsorption capacity for metal cations like Fe3+, Cu2+ and Zn2+.

N-heterocyclic carbene-catalyzed cascade reaction involving the hydroacylation of unactivated alkynes - Biju, Akkattu T.; Wurz, Nathalie E.; Glorius, Frank (Journal of the American Chemical Society, 2010)
The N-heterocyclic carbene (NHC)-catalyzed hydroacylation of unactivated alkynes to provide α,β-unsaturated ketones is reported. In addition, a rare case of an efficient and selective dually NHC-catalyzed cascade reaction involving the hydroacylation of alkynes and a subsequent intermolecular Stetter reaction allows the formation of chromanones containing a 1,4-diketone moiety.

N-nitrosation of secondary amines using p-TSA-NaNO2 as a novel nitrosating agent under mild conditions - Borikar, Sanjay P.; Paul, Vincent (Synthetic Communications, 2010)
A combination of p-toluenesulfonic acid (p-TSA) and sodium nitrite was used as a novel effective nitrosating agent for the N-nitrosation of secondary amines to their corresponding nitroso derivatives under mild and heterogeneous conditions in moderate to excellent yields.
Keywords: N-nitrosation; nitroso amines; p-toluenesulfonic acid; secondary amines

Organocatalytic asymmetric synthesis of (-)-delta-coniceine based on sequential proline-catalyzed asymmetric alpha-amination-HWE olefination - Panchgalle, Sharad P.; Bidwai, Harshad B.; Chavan, Subhash P.; Kalkote, Uttam R. (Tetrahedron-Asymmetry, 2010)
An efficient asymmetric synthesis of (-)-delta-coniceine via sequential proline-catalyzed asymmetric alpha-amination and Horner-Wadsworth-Emmons olefination of an aldehyde with excellent enantiomeric excess (>99%) and high yields (overall yield 44%) is described. (C) 2010 Elsevier Ltd. All rights reserved.

Pd-catalyzed one-pot chemoselective hydrogenation protocol for the preparation of carboxamides directly from azides - Bavikar, Sudhir N.; Salunke, Deepak B.; Hazra, Braja G.; Pore, Vandana S.; Thierry, Josiane; Dodd, Robert H. (Tetrahedron Letters, 2010)
Carboxamides were obtained efficiently in high yields from azides on reaction with the corresponding pre-formed activated carboxylic acids in a single-step reductive transformation using hydrogen atmosphere (balloon) under Pd/BaSO(4) or Pd/CaCO(3) catalysis. The method is highly chemoselective and compatible with extremely labile functional groups such as benzyl carbamates, benzyl ethers, benzyl esters, and olefins. (C) 2010 Elsevier Ltd. All rights reserved.
Keywords: Azide; Carboxamide; Catalytic hydrogenation; Chemoselective; Palladium; Succinimide ester

Photodegradation of methanol under UV-visible irradiation by titania dispersed on polyester cloth - Bhattacharyya, Kaustava; Tripathi, Arvind K.; Gupta, Narendra M.; Tyagi, Avesh K. (Photochemistry and Photobiology, 2010)
Titania supported on polyester fabric (TiO(2)-PY) with varying titania loadings (2-7 wt%) were prepared via the dip-coating method at room temperature using an aqueous slurry of anatase titania. Structural and morphological characterizations by X-ray diffraction and scanning electron microscopy revealed that the titanium dioxide crystallites deposited on the surface of the polyester fabric were in the micrometer range while their phase remained to be anatase. Photocatalytic activity of TiO(2)-PY fabric catalysts was evaluated for vapor-phase oxidation of methanol in air as a test reaction in the presence of UV as well as solar radiation under ambient conditions. These catalysts were found to be quite active in both UV and solar irradiation with activity being higher in the former case. CO(2) yield from photo-oxidation of methanol depended on titania content and also on its dispersion over polyester fabric support.

Phylogeographical studies in disjunct populations of symplocos laurina wall. using cytoplasmic PCR-RFLP approach - Banu, Sofia; Lagu, Meena D.; Gupta, Vidya S. (Tree Genetics & Genomes, 2010)
Genetic variation, haplotype relationships, and potential regions of diversity in Symplocos laurina Wall. (Symplocaceae), a montane tree species from India, have been tested using molecular and biogeographical data to infer phylogeographic patterns. The polymerase chain reaction-restriction fragment length polymorphism technique was used to determine the chloroplast (cp) and mitochondrial (mt) DNA haplotypes of 218 individuals from 12 populations, collected from Northeast India (NEI), which is a part of Indo-Burma biodiversity hotspot, and South India, which includes the Western Ghats (WG), another biodiversity hotspot from India and Eastern Ghats (EG). Nine cpDNA (chlorotypes) and 24 mtDNA haplotypes (mitotypes) were identified; the WG region was identified as the most diverse for chlorotypes and the NEI region for mitotypes. Although a strong population differentiation was observed, phylogeographic structure was found to be absent for both the genomes. The haplotype network revealed the presence of two main lineages: NEI-WG lineage and EG lineage, largely without overlapping distributions. The study tests two hypotheses, namely vicariance and dispersal, to understand the distribution of plants in India. The population structure of S. laurina strongly suggests the persistence of the species in putative refugial areas preglaciation and further establishment of other populations of S. laurina from these refugial populations.
Keywords: Cytoplasmic genome; Genetic diversity; Phylogeography

Polyarylate based thin film composite (TFC) membranes: effects of coating parameters, gutter layer, and intrinsic material properties - Chendake, Yogesh J.; Bhole, Yogesh S.; Lohokare, Harshada R.; Kharul, Ulhas K. (Separation Science and Technology, 2010)
Investigations in thin film composite (TFC) membrane formation with polyacrylonitrile ultrafiltration membrane as a support and three polyarylates with sequentially increased polarity are reported. Effects of TFC membrane preparation parameters viz., concentration of the coating solution, dip time, presence of solvent in pores of UF membrane support, and presence of the gutter layer were examined towards the formation of the selective skin layer, which was assessed by gas permeation analysis. TFC membranes prepared using dimethyl bisphenol-A based polyarylate exhibited similar to 3 orders of magnitude higher permeability and comparable selectivity as that of its dense membrane.
Keywords: Gas permeation; gutter layer; polarity; polyarylates; TFC membrane

QTL mapping of multiple foliar disease and root-lesion nematode resistances in wheat - Rebecca S. Zwart; Thompson, J. P.; Milgate, A. W.; Bansal, Urmil K.; Williamson, P. M.; Raman, H.; Bariana, Harbans S. (Molecular Breeding, 2010)
A genetic linkage map, based on a cross between the synthetic hexaploid CPI133872 and the bread wheat cultivar Janz, was established using 111 F(1)-derived doubled haploid lines. The population was phenotyped in multiple years and/or locations for seven disease resistance traits, namely, Septoria tritici blotch (Mycosphaeralla graminicola), yellow leaf spot also known as tan spot (Pyrenophora tritici-repentis), stripe rust (Puccinia striiformis f. sp. tritici), leaf rust (Puccinia triticina), stem rust (Puccinia graminis f. sp. tritici) and two species of root-lesion nematode (Pratylenchyus thornei and P. neglectus). The DH population was also scored for coleoptile colour and the presence of the seedling leaf rust resistance gene Lr24. Implementation of a multiple-QTL model identified a tightly linked cluster of foliar disease resistance QTL in chromosome 3DL. Major QTL each for resistance to Septoria tritici blotch and yellow leaf spot were contributed by the synthetic hexaploid parent CPI133872 and linked in repulsion with the coincident Lr24/Sr24 locus carried by parent Janz. This is the first report of linked QTL for Septoria tritici blotch and yellow leaf spot contributed by the same parent. Additional QTL for yellow leaf spot were detected in 5AS and 5BL. Consistent QTL for stripe rust resistance were identified in chromosomes 1BL, 4BL and 7DS, with the QTL in 7DS corresponding to the Yr18/Lr34 region. Three major QTL for P. thornei resistance (2BS, 6DS, 6DL) and two for P. neglectus resistance (2BS, 6DS) were detected. The recombinants combining resistance to Septoria tritici blotch, yellow leaf spot, rust diseases and root-lesion nematodes from parents CPI133872 and Janz constitute valuable germplasm for the transfer of multiple disease resistance into new wheat cultivars.
Keywords: Pratylenchyus spp; Pyrenophora tritici-repentis; Rust diseases; Septoria tritici blotch; Synthetic hexaploid wheat; Triticum aestivum

Reductive dechlorination of gamma-hexachlorocyclohexane using Fe-Pd bimetallic nanoparticles - Nagpal, Varima; Bokare, Alok D.; Chikate, Rajeev C.; Rode, Chandrashekhar V.; Paknikar, Kishore M. (Journal of Hazardous Materials, 2010)
Nanoscale Fe-Pd bimetallic particles were synthesized and used for degradation of lindane (gamma-hexachlorocyclohexane) in aqueous solution. Batch studies showed that 5 mg/Lof lindane was completely dechlorinated within 5 min at a catalyst loading of 0.5 g/L and the degradation process followed first-order kinetics. GC-MS analysis in corroboration with GC-ECD results showed the presence of cyclohexane as the final degradation product. The proposed mechanism for the reductive dechlorination of lindane involves Fe corrosion-induced hydrogen atom transfer from the Pd Surface. The enhanced degradation efficiency of Fe-Pd nanoparticles is attributed to: (1) high specific surface area of the nanoscale metal particles (60 m(2)/g), manyfold greater that of commercial grade micro- or milli-scale iron particles (similar to 1.6 m(2)/g); and, (2) increased catalytic reactivity due to the presence of I'd on the Surface. Recycling and column studies showed that these nanoparticles exhibit efficient and sustained catalytic activity. (C) 2009 Elsevier B.V. All rights reserved.
Keywords: Bimetallic; Cyclohexane; Degradation; kinetics; Lindane; Nanoparticles

Renewable H-2 from glycerol steam reforming: effect of La2O3 and CeO2 addition to Pt/Al2O3 catalysts. - Montini, Tiziano; Singh, Rakesh; Das, Piyali; Lorenzut, Barbara; Bertero, Nicolas; Riello, Pietro; Benedetti, Alvise; Giambastiani, Giuliano; Bianchini, Claudio; Zinoviev, Sergey; Miertus, Stanislav; Fornasiero, Paolo (Chemsuschem, 2010)
Glycerol is the main byproduct of biodiesel production and its increased production volume derives from the increasing demand for biofuels. The conversion of glycerol to hydrogen-rich mixtures presents an attractive route towards sustainable biodiesel production. Here we explored the use of Pt/Al2O3-based catalysts for the catalytic steam reforming of glycerol, evidencing the influence of La2O3 and CeO2 doping on the catalyst activity and selectivity. The addition of the latter metal oxides to a Pt/Al2O3 catalyst is found to significantly improve the glycerol steam reforming, with high H-2 and CO2 selectivities. A good catalytic stability is achieved for the Pt/La2O3/Al2O3 system working at 350 degrees C, while the Pt/CeO2/Al2O3 catalyst sharply deactivates after 20 h under similar conditions. Studies carried out on fresh and exhausted catalysts reveal that both systems maintain high surface areas and high Pt dispersions. Therefore, the observed catalyst deactivation can be attributed to coke deposition on the active sites throughout the catalytic process and only marginally to Pt nanoparticle sintering. This work suggests that an appropriate support composition is mandatory for preparing high-performance Pt-based catalysts for the sustainable conversion of glycerol into syngas.
Keywords: biofuels; Glycerol; heterogeneous catalysis; platinum; supported catalysts

Room temperature synthesis of rutile TiO2 hierarchical nanoneedle flower morphology for dye sensitized solar cell - Hyam, Rajeshkumar S.; Bhosale, Reshma K.; Lee, Wonjoo; Han, Sung-Hwan; Hannoyer, Beatrice; Ogale, Satishchandra B. (Journal of Nanoscience and Nanotechnology, 2010)
Rutile TiO2 nanoneedle flowers (representing concurrent nano-micro hierarchical morphology) with high shape anisotropy ratio are synthesized at room temperature by using a simple and efficient one step electrochemical process of anodic dissolution. This process employs highly acidic bath of perchloric acid (pH < 2) and a large current density on the surface of Titanium foil to form nanostructures. The diameter and length of rutile TiO2 nanoneedle is similar to 8 nm and 100 nm respectively (aspect ratio > 10). Dye sensitized solar cell (DSSC) configured using such rutile TiO2 flowers is shown to exhibit IPCE of 30% and power conversion efficiency of similar to 3.6%.
Keywords: Anodization; DSSC; Nanoneedles; Rutile TiO2

Selective CO2 and H-2 adsorption in a chiral magnesium-based metal organic framework (Mg-MOF) with open metal sites - Mallick, Arijit; Saha, Subhadeep; Pachfule, Pradip; Roy, Sudip; Banerjee, Rahul (Journal of Materials Chemistry, 2010)
A rare porous magnesium-based metal-organic framework, Mg-MOF-1 [Mg(3,5-PDC)(H2O)], was synthesized solvothermally in DMF. Structural determination by X-ray single-crystal diffraction technique reveals that this chiral MOF (space group P6(1)22) is constructed by helical assembly of Mg2+ ions with achiral 3,5-pyridine dicarboxylates and coordinating water molecules, to form a three-dimensional framework with parallel hexagonal channels. The structural detail of its 0D analogue Mg-MOF-2 [Mg(2,4-PDC)(H2O)(3)] has been discussed to show how subtle variation in the ligand architecture changes the resulting structure from 0D to 3D. Mg-MOF-1 remains robust and porous upon evacuation of the coordinating water molecules. This is the first report of a chiral hexagonal Mg-MOF synthesized from an achiral organic building unit. Open Mg metal sites show selective hydrogen (H-2) adsorption (ca. 0.8 wt% at 77 K) and carbon dioxide (CO2) uptake (ca. 0.7 mmol g(-1) at 298 K) over nitrogen at 1 atm. Ab initio quantum chemical calculation of adsorption energies and possible adsorption sites of hydrogen molecules are also reported.

Selective hydrogenolysis of glycerol to 1,2-propanediol: comparison of batch and continuous process operations - Rode, Chandrashekhar V; Ghalwadkar, Ajay A.; Mane, R. B.; Hengne, Amol M.; Jadkar, Sachin T.; Biradar, Narayan S. (Organic Process Research & Development, 2010)
The screening of copper chromite catalysts with various promoters such as Al, Zn, and Ba for glycerol hydrogenolysis to 1,2-propanediol (1,2-PDO) in a batch reaction showed that Cu-Cr (Ba) catalyst gave the highest conversion of 34% and selectivity of 84% to 1,2-PDO. In a continuous operation (23 g catalyst bed) the same catalyst showed higher conversion of glycerol and selectivity for 1,2-PDO of 65% and > 90%, respectively, with an on-stream activity of similar to 800 h. Better performance in a continuous operation could be due to the in situ activation of the catalyst, suppression of glycerol cracking to ethylene glycol, as well as excessive hydrogenation of 1,2-PDO to 2-propanol due to lower contact time of 1.3 h as compared to that in a batch operation (5 h). Effects of various process parameters on conversion and selectivity also have been compared for batch and continuous operations.

Self-organizing maps: a tool to ascertain taxonomic relatedness based on features derived from 16S rDNA sequence - Raje, D. V.; Purohit, H. J.; Badhe, Yogesh P.; Tambe, S. S.; Kulkarni, B. D. (Journal of Biosciences, 2010)
Exploitation of microbial wealth, of which almost 95% or more is still unexplored, is a growing need. The taxonomic placements of a new isolate based on phenotypic characteristics are now being supported by information preserved in the 16S rRNA gene. However, the analysis of 16S rDNA sequences retrieved from metagenome, by the available bioinformatics tools, is subject to limitations. In this study, the occurrences of nucleotide features in 16S rDNA sequences have been used to ascertain the taxonomic placement of organisms. The tetra- and penta-nucleotide features were extracted from the training data set of the 16S rDNA sequence, and was subjected to an artificial neural network (ANN) based tool known as self-organizing map (SOM), which helped in visualization of unsupervised classification. For selection of significant features, principal component analysis (PCA) or curvilinear component analysis (CCA) was applied. The SOM along with these techniques could discriminate the sample sequences with more than 90% accuracy, highlighting the relevance of features. To ascertain the confidence level in the developed classification approach, the test data set was specifically evaluated for Thiobacillus, with Acidiphilium, Paracocus and Starkeya, which are taxonomically reassigned. The evaluation proved the excellent generalization capability of the developed tool. The topology of genera in SOM supported the conventional chemo-biochemical classification reported in the Bergey manual.
Keywords: Curvilinear component analysis; Principal component analysis; self-organizing maps

Small molecule inhibition of phosphatidylinositol-3,4,5-triphosphate (PIP3) binding to pleckstrin homology domains - Miao, Benchun; Skidan, Igor; Yang, Jinsheng; Lugovskoy, Alexey; Reibarkh, Mikhail; Long, Kai; Brazell, Tres; Durugkar, Kulbhushan A.; Maki, Jenny; Ramana, C. V.; Schaffhausen, Brian; Wagner, Gerhard; et al. (Proceedings of the National Academy of Sciences of the United States of America, 2010)
The PI3-kinase (PI3K) pathway regulates many cellular processes, especially cell metabolism, cell survival, and apoptosis. Phosphatidylinositol-3,4,5-trisphosphate (PIP3), the product of PI3K activity and a key signaling molecule, acts by recruiting pleckstrin-homology (PH) domain-containing proteins to cell membranes. Here, we describe a new structural class of nonphosphoinositide small molecule antagonists (PITenins, PITs) of PIP3-PH domain interactions (IC50 ranges from 13.4 to 31 mu M in PIP3/Akt PH domain binding assay). PITs inhibit interactions of a number of PIP3-binding PH domains, including those of Akt and PDK1, without affecting several PIP2-selective PH domains. As a result, PITs suppress the PI3K-PDK1-Akt pathway and trigger metabolic stress and apoptosis. A PIT-1 analog displayed significant antitumor activity in vivo, including inhibition of tumor growth and induction of apoptosis. Overall, our studies demonstrate the feasibility of developing specific small molecule antagonists of PIP3 signaling.
Keywords: Anticancer; PIP3 antagonist

On some aspects of fock-space multi-reference coupled-cluster singles and doubles energies and optical properties - Manohar, Prashant Uday; Shamasundar, K. R.; Bag, Arijit; Vaval, Nayana; Pal, Sourav (Recent progress in coupled cluster methods: theory and applications, 2010)

Static hyper-polarizability of open shell molecules computed at the FSMRCCSD level using constrained variational approach - Bag, Arijit; Bhattacharya, S.; Pal, S. (International Conference on Recent Advances in Spectroscopy - Theoretical, Astrophysical and Experimental Perspectives, 2010)
In recent years, there has been a significant development in the analytic derivatives of energy with respect to electric fields based on the state-of-the-art multi-reference coupled-cluster method using Lagrangian based constrained variational approach. So far, the Lagrangian based Fock space multi-reference coupled cluster (FSMRCC) method has been successfully used to calculate electrical dipole moment and polarizability of open shell molecules, particularly, doublet radicals at the ground state and the electronic excited states of closed shell molecules. In this article, Lagrangian based FSMRCC method has been implemented for the first time for calculation of hyper polarizabilites of a few doublet radicals such as OH, OF, NO and NO(2). Orbital-relaxed finite field FSMRCC values are reported for comparison.

Stereocontrolled route to the synthesis of (+/-)-3-amino-2,2-dimethyl-1,3-diphenylpropan-1-ol - Patil, M. N.; Bhowmick, Kartick C.; Joshi, Navalkishore N. (Tetrahedron Letters, 2010)
Both the diastereomers of (+/-)-3-amino-2,2-dimethyl-1,3-diphenylpropan-1-ol were synthesized starting from a common intermediate, namely,B-hydroxy, oxime 6. Diastereoselective reduction with NaBH(4)/TiCl(4) and H(2)-Pd/C provided syn- and anti-isomers, respectively. Good overall yield and selectivity were realized using a simple protocol. (C) 2010 Elsevier Ltd. All rights reserved.
Keywords: 1; 3-Aminoalcohol; Aldol-Tishchenko reaction; beta-Hydroxy oxime; Diastereoslective reduction

Structural diversity in a series of metal-organic frameworks (MOFs) composed of divalent transition metals, 4,4 `-bipyridine and a flexible carboxylic acid - Pachfule, Pradip; Panda, Tamas; Dey, Chandan; Banerjee, Rahul (Crystengcomm, 2010)
A series of flexible metal-organic frameworks (MOFs) have been successfully synthesized under hydrothermal condition using 1,3-adamantanediacetic acid (C(14)H(20)O(4), H(2)ADA) as a flexible dicarboxylate building block, 4,4'-bipyridine and transition metal ions [Cd(II), Zn(II), and Mn(II)] as metal centers in DMF and aqueous media. These MOFs formulated as [Cd(ADA)(4,4'-bipy)(0.5)]center dot(DMF) (Cd-ADA-1), [Mn(ADA)(4,4'-bipy)(0.5)]center dot(DMF) (Mn-ADA-1), Zn(ADA)(4,4'-bipy)(0.5) (Zn-ADA-1), and [Mn(HADA)(2)(4,4'-bipy)(H(2)O)(2)] (Mn-ADA-2) (ADA = 1,3-adamantanediacetate, 4,4'-bipy = 4,4'-bipyridine and DMF = N,N'-dimethyl formamide) display interesting 1D, 2D and 3D structural features depending on the solvent of synthesis. All these MOFs were structurally determined by single-crystal X-ray diffraction. The coordination modes of this ligand are discussed and in addition, thermal stability and hydrogen (H(2)) and carbon-dioxide (CO(2)) adsorption properties of Cd-ADA-1, Mn-ADA-1 and Zn-ADA-1 are also presented. Hydrogen sorption at 77 K and up to 1 atm is found to be 0.42, 0.72 and 1.36 wt% without saturation for Zn-ADA-1, Mn-ADA-1 and Cd-ADA-1 samples.

Structural diversity in partially fluorinated metal organic frameworks (F-MOFs) composed of divalent transition metals, 1,10-phenanthroline, and fluorinated carboxylic acid - Pachfule, Pradip; Dey, Chandan; Panda, Tamas; Vanka, Kumar; Banerjee, Rahul (Crystal Growth & Design, 2010)
Seven new partially fluorinated metal-organic frameworks (F-MOFs) have been synthesized under different solvothermal conditions (H(2)O or N,N-dimethylformamide (DMF)) from transition metal cations [Zn(II), Co(II), and Mn(II)], 1,10-phenanthroline (phen), and 4,4'-(hexafluoroisopropylidene) bis(benzoic acid) (C(17)H(10)F(6)O(4), H(2)hfbba) to determine the influence of reaction conditions on the formation of metal-organic frameworks. This family of materials displays a striking degree of structural similarity depending on the solvent of synthesis. Of the seven materials, two contain three-dimensional connectivity: Co(3)(hfbba)(6)(phen)(2) (F-MOF-6) and Mn(3)(hfbba)(6)(Phen)(2) (F-MOF-10). Three materials are one-dimensional structures: Zn(hfbba)(0.5)(phen)(HCO(2)) (F-MOF-8), Mn(Hhfbba)(2)(Phen) (F-MOF-11), and [Mn(hfbba)(2)(dm-phen)]center dot(H(2)O) (F-MOF-11A). Lastly, Co(hfbba)(phell)(2)center dot 2(H(2)hfbba)(H(2)O)(HCO(2)) (F-MOF-7) and Zn(hfbba)(phen)(2)center dot 2(H(2)hfbba) (H(2)O)-(HCO(2)) (F-MOF-9) are discrete zero-dimensional molecular complexes. F-MOF-6 and -10, which feature it three-dimensional (3D) framework with pcu topolgy are formed in DMF like F-MOF-8 and at 85 degrees C. The remaining F-MOFs are formed by a solvothermal reaction at 120 degrees C in water. F-MOF-7 and -9 are isostructural discrete zero-dimensional molecular complexes (a similar to 19.5; b similar to 13.7; c similar to 26.2/29.6 angstrom; beta similar to 99.9/120.04; V similar to 6840 angstrom(3)). All these F-MOFs were structurally determined by single-crystal X-ray diffraction. Solid-state properties such its UV-vis and the thermal stability of F-MOF-6 to -11A have also been studied. Insight into the factors influencing the preferred crystallization of a specific complex over others has been obtained from full quantum chemical (QM) calculations using density functional theory (DFT).

Structural, magnetic, and gas adsorption study of a two-dimensional tetrazole-pyrimidine based metal-organic framework - Pachfule, Pradip; Das, Raja; Poddar, Pankaj; Banerjee, Rahul (Crystal Growth & Design, 2010)
A new two-dimensional (2D) metal-organic framework, Cu-TP-1, has been synthesized under solvothermal conditions (DMF) from the transition metal cation Cu(II) and 2-tetrazole pyrimidine (C5H5N6, H-TP). The structure has been determined by single crystal X-ray crystallography which shows a (6,3) honeycomb 2D net with perpendicular one-dimensional channels. Permanent porosity of Cu-TP-1 has been determined by the nitrogen adsorption isotherm. Cu-TP-1 show interesting H-2 and CO2 uptake. CO2 uptake of Cu-TP-1 (at 298 K, 1 atm pressure) is seen to be comparable to the recently reported ZIF-95 which outperforms ZIF-100 and BPL carbon. The magnetic properties show an antiferromagnetically coupled Cu ... Cu interaction down to 8 K with a Weiss temperature around 108 K.

Structure, electronic structure, optical, and dehydrogenation catalytic study of (Zn1-zInz)(O1-xNx) solid solution - Mapa, Maitri; Sivaranjani, Kumarsrinivasan; Bhange, Deu S.; Saha, Biswajit; Chakraborty, Purushottam; Viswanath, Annamraju Kasi; Gopinath, Chinnakonda S. (Chemistry of Materials, 2010)
Indium and nitrogen codoping in ZnO leads to a solid solution of InN in ZnO with I composition of(Zn1-zInz)(O1-xNx). A simple solution combustion method has been adopted to prepare the above materials in less than 10 min with metal nitrates as the metal loll source and urea as fuel. With reference to ZnO, significant increase in lattice parameters was observed with increasing In-content. However, the In2O3 phase was Observed along with InN for]it content >= 10%. Optical absorption extended into the Visible region, at least LIP to 550 nm, demonstrates an effective reduction of optical band gap due to the formation of solid Solution. A new feature observed just above O2p valence band in X-ray photoelectron spectroscopy (XPS) suggests the creation of N 2p states from InN; the N Is core level XPS result too confirms nitride contribution. Raman spectroscopy and secondary ion mass spectrometry results show direct In-N, Zn-N. and In-N-Zn fragments in (Zn1-zInz)(O1-x,N-x). Catalytic activity explored for Oxidation of 2-butanol to ethyl methyl ketone demonstrates a high selectivity at 350 and 400 degrees C. All of the above characteristics suggest the multifunctional nature of (Zn1-zInz)(O1-xNx) and its potential for other applications.

Study of the effect of plasma-striking atmosphere on Fe-oxidation in thermal dc arc-plasma processing - Banerjee, Indrani; Khollam, Y. B.; Mahapatra, S. K.; Das, A. K.; Bhoraskar, S. V. (Journal of Vacuum Science & Technology A, 2010)
The effect of plasma-striking atmosphere: air and air+Ar-gas on the crystallization of Fe-oxide phases was studied using dc thermal arc-plasma processing route. The powders were characterized by x-ray diffraction, vibrating sample magnetometry, transmission electron microscopy, and Mossbauer spectroscopy techniques. At room temperature and O(2) rich atmosphere, arc-evaporated Fe(2+) ions oxidize into either gamma-Fe(2)O(3) or Fe(3)O(4) depending upon the combining ratio of Fe with molecular O(2). Fe/O ratio could be adjusted using proper flow rate of Ar gas to crystallize the pure gamma-Fe(2)O(3). (C) 2010 American Vacuum Society. [DOI: 10.1116/1.3504597]

Syntheses, characterisation and vapour pressure of metallo-organic titanium precursor for MOCVD applications - Arockiasamy, S.; Manoj, Kochunnoonny; Bhadbhade, Mohan M.; Mallika, C.; Nagaraja, K. S. (Inorganica Chimica Acta, 2010)
Metallo-organic complexes of titanium such as [Ti(bzac)(2)(O(i)Pr)(2)] (1) and [Ti(bzac)(2)en(O(i)Pr)(2)] (2) were synthesised using 1-phenyl-1,3-butanedione (bzac) and the Schiff's base ligand N, N0-ethylene-bis(1-phenyl-1,3-butanediimine) [(bzac)(2)en]. A novel ligand 1-phenyl-3-N-(2-hydroxy-2-methylethylimino)-1-butanone (bzac1a2pol, 3) synthesised by condensing benzoylacetone (bzac) with 1-amino-2-propanol (1a2pol) was used in the synthesis of the complex bis(1-phenyl-3-N-(2-hydroxy-2-methylethylimino)-1-butanoato)titanium (IV), [Ti(bzac1a2pol)(2), 4]. These complexes were synthesised by replacing the isopropoxy group (O(i)Pr) of titanium tetra-isopropoxide, Ti(O(i)Pr)(4) by the appropriate ligands. Complexes 1, 2 and 4 were characterised for their volatility/thermal stability using TG/DTA and complex 4 was found to be volatile giving a residue of similar to 5.0% (TG) at 377 degrees C and similar to 3.0% (reduced pressure, 1 mbar) at 285 degrees C. Ligand 3 and its Ti complex 4 were characterised by (1)H NMR, (13)C NMR, elemental analysis, mass spectrometry and single crystal XRD. A value of 164.2 +/- 5.2 kJ mol(-1) for the standard enthalpy of sublimation (Delta H(sub)(0)) was evaluated for 4 from its vapour pressure. (C) 2010 Elsevier B. V. All rights reserved.
Keywords: MOCVD; Single crystal; Syntheses; Ti complexes; Vapour pressures; Volatile complexes

Synthesis and biodegradation studies of new copolymers based on sucrose derivatives and styrene - Barros, M. Teresa; Petrova, Krasimira T.; Singh, Raj P. (European Polymer Journal, 2010)
Novel unsaturated esters of sucrose were synthesised directly and in good yields from sucrose using a simple, mild, and selective Mitsunobu procedure. These regioisomerically pure vinyl sugars have been copolymerised with styrene by a free radical process, yielding unbranched linear polymer materials with pendant sucrose moieties. Their physical properties indicate that these polymers have potential technological relevance as amphiphilic and biodegradable materials. Biodegradation tests on the copolymer samples by a fungal (Aspergillus niger) culture method showed a fungal growth >= 60%, indicating good biodegradability and that the copolymers were partiallybio-assimilated during microbial attack. (C) 2010 Elsevier Ltd. All rights reserved.
Keywords: Biodegradable copolymers; Biodegradation culture test; free radical copolymerization; Vinyl sucrose ester monomers

Synthesis and characterization of new aromatic polyesters containing pendent naphthyl units - Honkhambe, Pandurang N.; Biyani, Mahesh V.; Bhairamadgi, Nagendra S.; Wadgaonkar, Prakash P.; Salunkhe, Manikrao M. (Journal of Applied Polymer Science, 2010)
Two bisphenols, viz., 4,4'-[1-(2-naphthaleny-1)ethylidene]bisphenol and 4,4'-[1-(2-naphthalenyl) ethylidene]bis-3-methylphenol were prepared by condensation of commercially available 2-acetonaphthanone with phenol and o-cresol, respectively. A series of new aromatic polyesters containing pendent naphthyl units was synthesized by phase-transfer-catalyzed interfacial polycondensation of these bisphenols with isophthaloyl chloride, terephthaloyl chloride, and a mixture of isophthaloyl chlorideiterephthaloyl chloride (50 : 50 mol %). Inherent viscosities of polyesters were in the range 0.83-1.76 dL g(-1), while number average molecular weights (M(n)) were in the range 61,000-235,000 g mol(-1). Polyesters were readily soluble in organic solvents such as dichloromethane, chloroform, tetrahydrofuran, m-cresol, pyridine, N,N-dimethylformamide, N,N-dimethylacetarnide, and 1-methyl-2-pyrrolidinone at room temperature. Tough, transparent, and flexible films were cast from a solution of polyesters in chloroform. X-Ray diffraction measurements displayed a broad halo at 20 congruent to 19 degrees indicating the amorphous nature of polyesters. Glass transition temperatures of polyesters were in the range 209-259 degrees C. The temperature at 10% weight loss (T(10)), determined by TGA in nitrogen atmosphere, of polyesters was in the range 435-500 degrees C indicating their good thermal stability. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117: 2545-2552, 2010
Keywords: Aromatic polyesters; bisphenol; interfacial polycondensation; pendent naphthyl units

Synthesis and characterization of new aromatic polyesters containing cardo decahydronaphthalene groups - Honkhambe, Pandurang N.; Bhairamadgi, Nagendra S.; Biyani, Mahesh V.; Wadgaonkar, Prakash P.; Salunkhe, Manikrao M. (European Polymer Journal, 2010)
Three cardo bisphenols containing decahydronaphthalene group viz., 4,4'-(octahydro-2(1H)-naphthylidene)bisphenol, 4,4'-(octahydro-2(1H)-naphthylidene)bis-3-methylphenol and 4,4'-(octahydro-2(1H)-naphthylidene)bis-3,5-dimethylphenol were synthesized starting from commercially available 2-naphthol and were utilized for synthesis of new aromatic polyesters by phase transfer-catalyzed interfacial polycondensation with isophthaloyl chloride, terephthaloyl chloride and a mixture of isophthaloyl chloride and terephthaloyl chloride (50:50 mol %). Inherent viscosities and number average molecular weights (M(n)) of polyesters were in the range 0.35-0.84 dL/g and 13300-48,500 (Gel Permeation Chromatography, polystyrene standard), respectively. Polyesters were readily soluble in organic solvents such as dichloromethane, chloroform, tetrahydrofuran, meta-cresol, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, and 1-methy1-2-pyrrolidinone at room temperature and could be cast into tough, transparent and flexible films from their chloroform solutions. Wide-angle X-ray diffraction measurements revealed the amorphous nature of polyesters. The glass transition temperature of polyesters was in the range 207-287 degrees C. The temperature at 10% weight loss (T(10)), determined from thermogravimetric analysis of polyesters, was in the range 425-460 degrees C indicating their good thermal stability. (C) 2010 Elsevier Ltd. All rights reserved.
Keywords: bisphenol; Cardo; Decahydronaphthalene; polyester; Structure-property relationship

Synthesis and characterization of polyesters from 2,3-bis (4 `-hydroxy phenyl) quinoxaline and 2,3-bis (2 `-hydroxynaphthalene-6 `-yl) quinoxaline - Patil, V. B.; Medhi, M.; Bhairamadgi, Nagendra S.; Wadgaonkar, P. P.; Maldar, Noormahamad N. (Materials Science and Engineering B-Advanced Functional Solid-State Materials, 2010)
Two bisphenols containing pendant, quinoxaline moiety; 2,3-bis (4'-hydroxy phenyl) quinoxaline (BHPQ) and 2,3-bis (2'-hydroxynaphthalene-6-yl) quinoxaline (BHNQ) were synthesized and characterized by FT-IR, (1)H, (13)C NMR and mass spectrometry. Aromatic polyesters and copolyesters were prepared by interfacial polymerization from BHPQ or BHNQ and isophthaloyl chloride or terephthaloyl chloride or a mixture of different mole proportions of (IPC + TPC). These polyesters and copolyesters were characterized by spectroscopic technique, viscosity measurement, solubility, thermal stability. DSC and XRD. Polymers had moderate to high molecular weights as evidenced by the inherent viscosities in the range 0.35-0.78 dL/g for BHPQ series and 0.27-0.52 dL/g for BHNQ series. BHPQ polyesters and copolyesters dissolved in m-cresol, NMP and conc. H(2)SO(4) whereas, BHNQ polyesters and copolyesters were readily soluble in NMP, DMAc, (TCE + phenol) and partly soluble in solvent like CHCl(3), pyridine, etc. Wide angle X-ray diffraction (WAXD) results showed that introduction of quinoxaline moiety into polymer chain and aromatic phenyl/rigid naphthyl structures lead to crystalinity. Differentional scanning calorimetry of BHNQ polyesters showed the glass transition temperatures in the range of 131-151 degrees C. BHPQ polyesters did not show any weight loss below 330 degrees C and retained 27-55% weight at 900 degrees C when investigated by TGA under nitrogen atmosphere demonstrating good thermal stability BHNQderived polyesters showed initial decomposition temperatures in range 211-234 degrees C. The structure-property relationships for the mentioned polyesters are analyzed, as these polyesters are of interest as materials for electronics, microelectronics and membrane separation. (C) 2009 Elsevier B.V. All rights reserved.
Keywords: 2; 3-Bis (2 `-hydroxynaphthalene-6 `-yl) quinoxaline; 3-Bis (4 `-hydroxy phenyl) quinoxaline; Aromatic polyesters; Glass transition temperature; solubility; Thermal properties

Synthesis and structural comparisons of five new fluorinated metal organic frameworks (F-MOFs) - Pachfule, Pradip; Dey, Chandan; Panda, Tamas; Banerjee, Rahul (Crystengcomm, 2010)
A series of fluorinated metal-organic frameworks (F-MOFs) have been successfully synthesized under hydrothermal condition using 4,40-(hexafluoroisopropylidene) bis(benzoic acid) (C(17)H(10)F(6)O(4), H(2)hfbba) as a flexible dicarboxylate building block, Cu(+2) and various heterocyclic co-ligands. These F-MOFs formulated as [Cu(hfbba)(phen)(2)]center dot 2(H(2)hfbba)(H(2)O)(HCO(2)) (F-MOF-1), [Cu(hfbba)(2)(2,2'-bipy) 2(H(2)O)] (F-MOF-2), [Cu(hfbba)(4,4'-dime-2,2'-bipy)(HCO(2))]center dot(hfbba)(H(2)O) (F-MOF-3), [Cu(2)(hfbba)(2)(3-mepy)(2)]center dot(DMF) 2(3-mepy) (F-MOF-4), and [Cu(hfbba)(2)(phen)(2)]center dot 0.5(DMF) (F-MOF5) (hfbba = 4,4'-(Hexafluoroisopropylidene) bis(benzoate), phen 1,1'-phenanthroline; 2,2'-bipy 2,2'-bipyridine; 4,4'dime-2,2'-bipy 4,4'-dimethyl 2,2'-bipyridine; 3-mepy 3-methyl-pyridine and DMF dimethyl formamide) display interesting H-bonded, 1D and 2D structural features. All these F-MOFs were structurally determined by single-crystal X-ray diffraction. F-MOF-1 and 5 form a distorted octahedral Cu(+2) secondary building unit (SBU). F-MOF-5 forms a one-dimensional architecture constructed from Cu(2+) ions bridged by phen anions and two types of 4 hfbba ligands while in F-MOF-1, two among the three acid co-ligands are not coordinated with Cu(2+) ions. F-MOF-2 displays dinuclear SBUs within the three-dimensional frameworks whereas F-MOF-3 displays mononuclear SBUs and forms a one-dimensional chain. F-MOF-4 display a interesting 2D framework with conventional Cu(2)(CO(2))(4) paddle wheel SBU. In the crystal structures four hfbba ligands, each coordinated to a dicopper paddlewheel unit via one of their carboxylate groups. Solid-state properties such as UV-vis and thermal stability of F-MOF-1-5 have also been studied.

Synthesis of azepane and nojirimycin iminosugars: the sharpless asymmetric epoxidation of D-glucose-derived allyl alcohol and highly regioselective epoxide ring opening using sodium azide - Jadhav, Vrushali H.; Bande, Omprakash P.; Puranik, Vedavati G.; Dhavale, Dilip D. (Tetrahedron-Asymmetry, 2010)
The Sharp less asymmetric epoxidation of D-glucose-derived ally! alcohol 4 afforded alpha- and beta-epoxides 5a and 5b in high stereoselectivity. The epoxide ring opening in 5a/5b was studied with different nucleophilic azido reagents, under various reaction conditions, and was found to be highly regioselective to give the preferential formation of 6-azido diol 6a/6b over 5-azido-diol 7a/7b. The 6-azido diol 6a/6b and 5-azido dial 7a/7b thus obtained were converted to the corresponding seven- and six-membered iminosugar, namely, azepane 1a/1b and 1-deoxy-nojirimycin 2a/2b. (C) 2010 Elsevier Ltd. All rights reserved.

Synthesis of eight-membered iminocyclitols from D-glucose - Jadhav, Vrushali H.; Bande, Omprakash P.; Puranik, Vedavati G.; Dhavale, Dilip D. (Tetrahedron, 2010)
The Baylis-Hillman reaction of 3-o-benzyl-alpha-d-xylo-pentodialdo-1,4-furanose 2 afforded a diastereomeric mixture of L-ido- and D-gluco-configurated alpha-methylene-beta-hydroxy esters 3a and 3b, respectively, in 1:1 ratio. Conjugate addition of benzyl amine on 3a gave adduct 4a as a major product while, addition of benzyl amine to 3b gave only one diastereomer 4b. Reduction of ester functionality in 4a/4b, opening of 1,2-acetonide functionality followed by reductive amino-cyclization under hydrogenation condition afforded azocanes 1c/1d in good yield. (C) 2010 Elsevier Ltd. All rights reserved.
Keywords: Baylis-Hillman reaction; Conjugate addition; diastereoselectivity; Iminosugars

Synthesis of ethyl acetate by esterification of acetic acid with ethanol over a heteropolyacid on montmorillonite K10 - Gurav, Hanumant; Bokade, Vijay V. (Journal of Natural Gas Chemistry, 2010)
In present work, liquid phase esterification of acetic acid with ethanol over dodecatungestophosphoric acid (DTPA) supported on K10 mommorillonite was systematically studied and optimization of process parameters was carried out The 20% m/m urpAtK tO was found to be the optimum catalyst with 90% acetic acid conversion and 100% ethyl acetate selectivity The study was also explored to see the feasibility of 20% m/m DTPA/K10 as a catalyst for the alkylation of acetic acid with other alcohols like methanol, iso-propanol and sr-butanol. The 20% m/m DTPA/K10 has shown increased activity with the increase in carbon number, at the same alcohol reflux The results are novel
Keywords: Acetic acid; Ethanol; ethyl acetate; Heteropolyacid; montmorillonite K10

Synthesis of hydrophilic and amphiphilic acryl sucrose monomers and their copolymerisation with styrene, methylmethacrylate and alpha- and beta-pinenes - Barros, Maria Teresa; Petrova, Krasimira T.; Singh, Raj P. (International Journal of Molecular Sciences, 2010)
Herein, we report the synthesis of monomethacryloyl sucrose esters, and their successful free radical homo- and co-polymerisation with styrene, methylmethacrylate, alpha- and beta-pinene. The chemical, physical, structural and surface chemical properties of these polymers, containing a hydrophobic olefin backbone and hydrophilic sugar moieties as side chains, have been investigated. Biodegradation tests of the copolymer samples by a microbial fungal culture (Aspergillus niger) method showed good biodegradability. The chemical structure and surface chemistry of the synthesized homo- and co-polymers demonstrate their potential technological relevance as amphiphilic and biodegradable polymers.
Keywords: Biodegradable copolymers; Biodegradation culture test; free radical copolymerization; Vinyl sucrose ester monomers

Synthesis of optically pure 2,3,4-trisubstituted tetrahydrofurans via a two-step sequential Michael-Evans aldol cyclization strategy: total synthesis of (+)-magnolone - Pandey, Ganesh; Luckorse, Srikanth; Budakoti, Asha; Puranik, Vedavati G. (Tetrahedron Letters, 2010)
Synthesis of optically pure 2,3,4-trisubstituted tetrahydrofurans is described employing a two-step Michael-Evans aldol cyclization strategy. The approach is successfully applied for the total synthesis of furano lignan natural product (+)-magnolone. (C) 2010 Elsevier Ltd. All rights reserved.
Keywords: HWE reaction; Lignans; Magnolone; Michael-Evans aldol reaction; Tetrahydrofuran

Synthesis of the antibacterial benzoquinone primin and its water-soluble analogue, primin acid - Bhattacharya, Asish K.; Kaur, Tanpreet; Ganesh, Krishna N. (Synthesis-Stuttgart, 2010)
The biologically active natural product, primin and its water-soluble acid analogue, primin acid are prepared in 34% and 25% overall yields, respectively, from a common intermediate using a Grignard reaction and a Johnson-Claisen rearrangement as the key steps.
Keywords: 1; 4-benzoquinones; Antibacterial; Johnson-Claisen rearrangement; primin; primin acid

Synthetic view of an analogue of the spiro-beta-lactone-gamma-lactam ring in oxazolomycins and lajollamycin - Mondal, Dhananjoy; Bera, Smritilekha (Synthesis-Stuttgart, 2010)
Herein, we describe a new synthetic strategy towards an analogue of the spiro-beta-lactone-gamma-lactam ring found in a class of potent antibiotics, the oxazolomycins and lajollamycin. The synthetic idea relies on the construction of two rings (beta-lactone and pyrrolidinone). The formation of the spiro-beta-lactone was accomplished by a crossed Cannizzaro reaction, while the 3,4-disubstituted pyrrolidinone ring was constructed by a titanium(IV) chloride mediated chelation-controlled double stereodifferentiating Crimmins aldol reaction of Garner's aldehyde.
Keywords: Crimmins aldol reaction; crossed Cannizzaro reaction; Garner's aldehyde; lactones; Mitsunobu reaction; pyrrolidine

Template assisted highly ordered novel self assembly of micro-reservoirs and its replication - Hire, Santosh L.; Shelke, Manjusha V.; Kale, Vinayak S.; Galopin, Elisabeth; Kulkarni, Mohan G.; Boukherroub, Rabah; Ogale, Satishchandra B. (Lab on a Chip, 2010)
A novel method is developed for template assisted fabrication of a regular assembly of microcavity arrays. Simple micropatterns on PDMS mold are used to create complex geometries via solvent vapor back pressure in a biodegradable polymer. Cavities are in turn replicated in complimentary PDMS mushroom like microstructures.

Uncatalyzed synthesis of thiomorpholide using polyethylene glycol as green reaction media - Gawande, Shrikant S.; Bandgar, Babasaheb P.; Kadam, Prasad D.; Sable, Shailesh S. (Green Chemistry Letters and Reviews, 2010)
Polyethylene glycol-600 was used as an efficient and recyclable solvent for the one-pot three component condensation reactions of aryl alkyl ketones, sulfur, and morpholine to produce the corresponding thiomorpholide. This protocol has advantages of high yields, short reaction times, mild reaction conditions, minimal environmental pollution, and simple work up procedure. [GRAPHICS] .
Keywords: polyethylene glycol-600; Sulfur; thiomorpholide; Willgerodt-Kindler reaction

Understanding the genetic structure of symplocos laurina wall. populations using nuclear gene markers - Banu, Sofia; Bhagwat, Rasika M.; Kadoo, Narendra Y.; Lagu, Meena D.; Gupta, V. S. (Genetica, 2010)
To characterize the genetic diversity of present populations of Symplocos laurina, which grow in the montane forests in India, we analyzed the DNA sequences of a nuclear gene. Using the 881 bp sequence of cytosolic Glyceraldehyde-3-phosphate dehydrogenase gene, we detected 24 haplotypes among 195 individuals sampled from 14 populations. Two dominant haplotypes were distributed over the entire range of this species in India and several private haplotypes were found. Low genetic diversity within population, high differentiation, number of population specific haplotypes and deviation from neutral evolution characterized the present populations of S. laurina. An analysis of molecular variance indicated the presence of geographic structure within the haplotype distribution. The occurrence of S. laurina preglaciation in India is the most parsimonious explanation for the current geographic structure observed. The populations are presumably ancient and might have spread across its extant distribution range in India through a recent range expansion event.
Keywords: GapC; Genetic diversity; Glaciation; Refugium

Volume transition of PNIPAM in a nonionic surfactant hexagonal mesophase - Jijo, V. J.; Sharma, Kamendra P.; Mathew, Renny; Kamble, Samruddhi; Rajamohanan, P. R.; Ajithkumar, Thalasseril G.; Badiger, Manohar V.; Kumaraswamy, Guruswamy (Macromolecules, 2010)
We investigate the volume transition of a thermoresponsive polymer, poly(N-isopropylacrylamide), PNIPAM, in the presence of an aqueous solution of nonionic surfactant, C(12)E(9). We combine turbidimetry with optical microscopy, NMR, and SAXS to follow the volume transition of the PNIPAM and the H(1)-isotropic transition of the surfactant/water system. Nonionic surfactants such as C(12)E(9) are known to interact weakly with PNIPAM. Accordingly, we show that there is only a small change in the volume transition temperature for the PNIPAM in isotropic micellar solutions of C(12)E(9), even for relatively high concentrations of C(12)E(9). Interestingly, once the surfactant forms an H(1) phase, there is a dramatic decrease in the coil globule transition onset temperature. We believe that this behavior results from a competition between C(12)E(9) in the H(1) phase, and PNIPAM to associate with water. When PNIPAM in the H(1) phase is cooled to low enough temperatures so as to be in the coil state, it locally disturbs the hexagonal phase ordering. Thus, we show that for PNIPAM in a weakly interacting surfactant matrix, it is the phase behavior of the matrix rather than the matrix chemistry that governs the coil globule transition. Finally, we show that in a PNIPAM copolymer with a higher LCST we observe an interesting sequence of transitions in the surfactant phase: on cooling from a high temperature free-blowing turbid globular state (similar to 75 degrees C), we enter a free-flowing translucent coil phase (similar to 47 degrees C), then a turbid gel (similar to 25 degrees C) where the copolymer is collapsed in the HI phase, and finally a low-temperature clear gel (similar to 5 degrees C) where the copolymer is in the expanded coil state.

Active pharmaceutical ingredient (api) from an estuarine fungus, microdochium nivale (Fr.) - Bhosale, Siddharth H.; Patil, K. B.; Parameswaran, P. S.; Naik, C. G.; Jagtap, T. G. (Journal of Environmental Biology, 2011)
Various marine habitats sustain variety of bio-sources of ecological and biotech potentials. Pharmaceutical potential compound Cyclosporine A was reported from marine fungus Microdochium nivale associated with Porteresia coarctata, a marine salt marsh grass from mangrove environment distributed along the Central West Coast (CWC) of India. This study involves association of M. nivale with P. coarctata plant, fermentation conditions, purification of Cyclosporine A, chemical characterization etc. Its antifungal inhibition and MIC (Minimum inhibitory concentration) against Aspergillus strains (A. niger, A. japonicus, A. fresenii), yeasts and dermatophytes (Candida sp., Cryptococcus neoformans, Trichophyton mentagrophytes, T tonsurans, T violaceum, Microsporium gypsum and Fusarium sp.) were evaluated. However, the MIC against A. japonicus, C. neoformans, Candida sp. and T. tonsurans were confirmed to be as low as 12.5-25 mg disc(-1). The antifungal properties of Cyclosporine A against Aspergillus species, yeast and dermatophytes revealed that Cyclosporine A would be a potential compound for life threatening diseases caused by above fungi in both human and animals. Furthermore, we have reported herewith another source of Cyclosporin A derived from filamentous fungus, M. nivale. occurring in marine environment.
Keywords: antifungal; Cyclosporine A; Estuarine environment; Microdochium nivale

Alginic acid-g-poly(N-vinylformamide) graft copolymer: synthesis, characerization, swelling, and flocculation property - Sand, Arpit; Yadav, Mithilesh; Mishra, Dinesh Kumar; Behari, Kunj (Journal of Applied Polymer Science, 2011)
The graft copolymer of N-vinylformamide with alginic acid was synthesized by free radical polymerization using potassium peroxymonosulphate and thiourea as redox pair in inert atmosphere. The optimum conditions for maximum grafting have been determined by varying the concentrations of N-vinylformamide, potassium peroxymonosulphate, thiourea, sulfuric acid, alginic acid as well as time duration and temperature. The grafting parameters increase up to the certain concentrations of N-vinylformamide, potassium peroxymonosulhate, thiourea, and hydrogen ion while thereafter grafting parameters decrease. The effect of alginic acid concentration on grafting parameters has been observed to decrease continuously. It has also been found that grafting parameters increase up to certain time and temperature, respectively, and thereafter decrease. The swelling properties of graft copolymer in terms of swelling ratio and percent swelling are investigated. Flocculation property of pure and grafted sample for both coking and noncoking coals is also investigated for the treatment of coal mine waste water. The graft copolymer has been characterized by Fourier transform infrared spectroscopy as well as thermogravimetic analysis. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 121: 1400-1407, 2011
Keywords: alginic acid; flocculation; Graft copolymer; N-vinylformamide; swelling

Alkynyl and phosphonyl substituted nucleobases: a case of thermally induced conformational polymorphism - Swamy, K. C. Kumara; Allu, Srinivasarao; Srinivas, Venu; Balaraman, Ekambaram; Kumar, K. V. P. Pavan (Crystal Growth & Design, 2011)
Substituted nucleobases with alkynyl and phosphonyl groups were investigated in the context of supramolecular interactions and possible use toward synthesis of nucleoside phosphonic acids (NPAs). The adeninyl compound (adeninyl-N-9)-CH2CH2CH2CH2C≡CH exhibits conformational polymorphism as revealed by X-ray structures determined at 200 and 298 K. Interestingly, in the compound (adeninyl-N-9)-(CH2)15CH3, the long aliphatic carbon chain does not show disorder. A rather unusual bending of alkyl chain, likely due to C–H···O interactions, is observed in the case of the thymine compound (thyminyl)-CH2CH2CH2C≡CH that possesses a terminal alkyne group. The powerful hydrogen bond acceptor property of the phosphoryl oxygen (P═O) does not perturb (unless assisted by other hydrogen bonding partners) the homo base-pairing in the structures of most of the phosphonyl substituted nucleobases studied.

Amino functionalized zeolitic tetrazolate framework (ZTF) with high capacity for storage of carbon dioxide - Panda, Tamas; Pachfule, Pradip; Chen, Yifei; Jiang, Jianwen; Banerjee, Rahul (Chemical Communications, 2011)
A three dimensional -NH(2) functionalized Zeolitic Tetrazolate Framework (ZTF-1) has been reported. The framework adopts a dia topology (M-L-M angle is close to 156 degrees). ZTF-1 shows high CO(2) (273 K) and H(2) (77 K) uptake due to the presence of the free -NH(2) group and uncoordinated tetrazolate nitrogen.

Aromatic bromination of aldehydes and ketones using 1,3-di-n-butylimidazolium tribromide [BBIm]Br3 ionic liquids under solvent-free conditions - Borikar, Sanjay P.; Daniel, Thomas (Journal of the Iranian Chemical Society, 2011)
An environmentally benign and efficient process for the preparation of monobromo derivatives of aryl aldehydes and ketones was developed by simple and practical reactions of aryl aldehydes or ketones with 1,3-di-n-butylimidazolium tribromide ([BBIm]Br-3), as a brominating reagent under solvent-free conditions in very high yields. The process has several advantages: high conversions, short reaction time, mild reaction conditions, simple workup with good to quantitative yields and re-usable ionic liquid.
Keywords: Bromination; green chemistry; Ionic liquid; Solvent-free; [BBIm]Br-3

Azide derivatized anticancer agents of vitamin K-3: X-ray structural, DSC, resonance spectral and API studies - Badave, Kirti D.; Patil, Yogesh; Gonnade, Rajesh G.; Srinivas, Darbha; Dasgupta, Rajan; Khan, Ayesha A.; Rane, Sandhya (Journal of Molecular Structure, 2011)
Compound 1 [1-imino (acetyl hydrazino)-Vitamin K-3], displays valence tautomerically related electronic isomers as Form land Form II. Form I exhibits 2D packing fragment with 1D ribbon chains of N-H center dot center dot center dot O hydrogen bonds and shows EPR silent features. While Form II is EPR active and exhibits biradical nature with double quantum transitions at g = 2.0040. H-1 NMR of compound 2, [1-imino (hydrazino carboxylate)-Vitamin K-3] and Form II exhibit pi delocalization via resonance assisted H-bonding [RAHB] effect compared to Form I. Molecular interactions in Form I and II are visualized by DSC. The electronic structures of compounds 1 and 2 have been correlated to their API values by measuring anticancer activities, mitochondrial potentials and DNA shearing patterns. Form II and compound 2 indicate mitochondria mediated apoptosis (similar to 75% cell death) while Form I causes 35% cell death. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Anticancer agents; API (Active Pharmaceutical Ingredients); Electronic isomers; RAHB (resonance assisted H-bonding); Vitamin K-3

Biocompatible gellan gum-reduced gold nanoparticles: cellular uptake and subacute oral toxicity studies - Dhar, Sheetal; Mali, Vishal; Bodhankar, Subhash L.; Shiras, Anjali; Bhagavatula L. V. Prasad; Pokharkar, Varsha (Journal of Applied Toxicology, 2011)
Currently gold nanoparticles are being explored for drug delivery and other biomedical applications; therefore it is necessary to study the fate of such nanoparticles inside the body. The objective of the present study was to investigate the cellular uptake and toxicity of the gold nanoparticles synthesized using a microbial polysaccharide, gellan gum, as a capping and reducing agent. The cellular uptake of gold nanoparticles was studied on mouse embryonic fibroblast cells, NIH3T3 and human glioma cell line, LN-229. The cellular uptake study indicated that the gellan gum-reduced gold nanoparticles were located in cancer cells (LN-229) while no uptake was observed in normal mouse embryonic fibroblast cells (NIH3T3). The toxicity of the gold nanoparticles was evaluated by carrying out subacute 28 day oral toxicity studies in rats. Subacute administration of gum-reduced gold nanoparticles to the rats did not show any hematological or biochemical abnormalities. The weight and normal architecture of various organs did not change compared with control. The current findings, while establishing the specific uptake of nanoparticles into cancerous cells, also demonstrates that the gellan gum-reduced gold nanoparticles are devoid of toxicity in animals following oral administration. Copyright (c) 2010 John Wiley & Sons, Ltd.
Keywords: cell lines; cellular uptake; Gellan gum; gold nanoparticles; subacute toxicity

Bioresponsive mesoporous silica nanoparticles for triggered drug release - Singh, Neetu; Karambelkar, Amrita; Gu, Luo; Lin, Kevin; Miller, Jordan S.; Chen, Christopher S.; Sailor, Michael J.; Bhatia, Sangeeta N. (Journal of the Americal Chemical Society, 2011)

Catalytic dehydroaromatization of n-alkanes by pincer-ligated iridium complexes - Ahuja, Ritu; Punji, Benudhar; Findlater, Michael; Supplee, Carolyn; Schinski, William; Brookhart, Maurice; Goldman, Alan S. (Nature Chemistry, 2011)
Aromatic hydrocarbons are among the most important building blocks in the chemical industry. Benzene, toluene and xylenes are obtained from the high temperature thermolysis of alkanes. Higher alkylaromatics are generally derived from arene–olefin coupling, which gives branched products—that is, secondary alkyl arenes—with olefins higher than ethylene. The dehydrogenation of acyclic alkanes to give alkylaromatics can be achieved using heterogeneous catalysts at high temperatures, but with low yields and low selectivity. We present here the first catalytic conversion of n-alkanes to alkylaromatics using homogeneous or molecular catalysts—specifically ‘pincer’-ligated iridium complexes—and olefinic hydrogen acceptors. For example, the reaction of n-octane affords up to 86% yield of aromatic product, primarily o-xylene and secondarily ethylbenzene. In the case of n-decane and n-dodecane, the resulting alkylarenes are exclusively unbranched (that is, n-alkyl-substituted), with selectivity for the corresponding o-(n-alkyl)toluene.

Chemoenzymatic total synthesis of potent HIV RNase H inhibitor (-)-1,3,4,5-tetragalloylapiitol - Batwal, Ramesh U.; Patel, Ramesh M.; N. P. Argade (Tetrahedron-Asymmetry, 2011)
Starting from racemic dimethyl 2-acetoxy-3-methylenesuccinate, the chemoenzymatic facile total synthesis of (-)-1,3,4,5-tetragalloylapiitol has been demonstrated via an efficient lipase catalyzed resolution followed by a DIBAL reduction-double gallyolation, osmium tetroxide dihydroxylation-double gallyolation, and reductive global O-benzyl deprotection pathway. (C) 2010 Elsevier Ltd. All rights reserved.

Chlorate ion mediated rutile to anatase reverse phase transformation in the TiO2 nanosystem - Bhosale, Reshma; Hyam, Rajeshkumar S.; Dhanya, P.; Ogale, Satishchandra B. (Dalton Transactions, 2011)
Rutile TiO2 nanoneedles (8 nm x 100 nm) synthesized at room temperature by anodization in perchloric acid (pH < 1) are shown to undergo an interesting reverse phase transformation to anatase nanoparticles (8 nm) at 300 degrees C only if the chlorate ions are maintained in the ambient medium. When chlorate ions are removed by multiple washing, the rutile phase and the needle morphology are maintained. The mechanism of formation of the ion-stabilized solid and its thermal evolution is discussed.

Classification of Indian power coals using K-means clustering and self organizing map neural network - Pandit, Yogesh P.; Badhe, Yogesh P.; Sharma, B. K.; Tambe, Sanjeev S.; Kulkarni, Bhaskar D. (Fuel, 2011)
The present study reports results of the classification of Indian coals used in thermal power stations across India. For classifying these power coals a classical unsupervised clustering technique, namely ``K-Means Clustering'' and an artificial intelligence (AI) based nonlinear clustering formalism known as ``Self-Organizing Map (SOM)'' have been used for the first time. To conduct the said classification, five coal descriptor variables namely moisture, ash, volatile matter, carbon and gross calorific value (GCV) have been used. The classification results thereof indicate that Indian power coals from different geographical origins can be classified optimally into seven classes. It has also been found that the K-means and SOM based classification results exhibit similarity in close to 75% coal samples. Further, K-means and SOM based seven coal categories have been compared with as many grades of a commonly employed Useful Heat Value (UHV) based Indian non-coking coal grading system. Here, it was observed that a number of UHV-based grades exhibit similarity with the categories identified by the K-means and SOM methods. The classification of Indian power coals as provided here can be gainfully used in selecting application-specific coals as also in their grading and pricing. (C) 2010 Elsevier Ltd. All rights reserved.
Keywords: Coal classification; Indian power coals; K-means clustering; Self-Organizing Map

Comparative and chemical proteomic approaches reveal gatifloxacin deregulates enzymes involved in glucose metabolism - Suresh, Kesavan K.; Bhosale, Santosh D.; Thulasiram, Hirekodathakallu V.; Kulkarni, Mahesh J. (Journal of Toxicological Sciences, 2011)
Gatifloxacin has been associated with increased risks of hypoglycemic and hyperglycemic side effects. In order to understand the molecular mechanism of gatifloxacin induced deregulation of glucose metabolism, a Combination of comparative and chemical proteomic approaches were employed using yeast as a model system. Differential protein expression studies using two dimensional electrophoresis and mass spectrometry reveal that gatifloxacin deregulates the expression of key enzymes involved in glucose metabolism. Furthermore, affinity chromatography and LC-MSE analysis led to identification of enolase, as one of the key gatifloxacin binding proteins. Fluorescence spectrometric studies confirmed that the gatifloxacin indeed binds to enolase. Role of enolase in regulation of gatifloxacin induced dysglycemic effect is discussed.
Keywords: antibiotics; Differential protein expression; Fluoroquinolone; Glycolysis; Yeast

Comparative genomics of the pathogenic ciliate Ichthyophthirius multifiliis, its free-living relatives and a host species provide insights into adoption of a parasitic lifestyle and prospects for disease control - Coyne, Robert S.; Hannick, Linda; Shanmugam, Dhanasekaran; Hostetler, Jessica B.; Brami, Daniel; Joardar, Vinita S.; Johnson, Justin; Radune, Diana; Singh, Irtisha; Badger, Jonathan H.; Kumar, Ujjwal; Saier, Milton; et al. (Genome Biology, 2011)
Background: Ichthyophthirius multifiliis, commonly known as Ich, is a highly pathogenic ciliate responsible for 'white spot', a disease causing significant economic losses to the global aquaculture industry. Options for disease control are extremely limited, and Ich's obligate parasitic lifestyle makes experimental studies challenging. Unlike most well-studied protozoan parasites, Ich belongs to a phylum composed primarily of free-living members. Indeed, it is closely related to the model organism Tetrahymena thermophila. Genomic studies represent a promising strategy to reduce the impact of this disease and to understand the evolutionary transition to parasitism. Results: We report the sequencing, assembly and annotation of the Ich macronuclear genome. Compared with its free-living relative T. thermophila, the Ich genome is reduced approximately two-fold in length and gene density and three-fold in gene content. We analyzed in detail several gene classes with diverse functions in behavior, cellular function and host immunogenicity, including protein kinases, membrane transporters, proteases, surface antigens and cytoskeletal components and regulators. We also mapped by orthology Ich's metabolic pathways in comparison with other ciliates and a potential host organism, the zebrafish Danio rerio. Conclusions: Knowledge of the complete protein-coding and metabolic potential of Ich opens avenues for rational testing of therapeutic drugs that target functions essential to this parasite but not to its fish hosts. Also, a catalog of surface protein-encoding genes will facilitate development of more effective vaccines. The potential to use T. thermophila as a surrogate model offers promise toward controlling 'white spot' disease and understanding the adaptation to a parasitic lifestyle.

Competitive binding of Ba2+and Sr2+ to 18-crown-6 in a receptor with a 1-methoxyanthraquinone analogue as the other binding site - Banerjee, Tanmay; Suresh, Moorthy; Ghosh, Hirendra N.; Das, Amitava (Europian Journal of Inorganic Chemistry, 2011)
Owing to their immense biological significance, development of sensors for the selective detection of alkaline earth metal ions has attracted vast research interest. In this article we have reported the synthesis, characterisation and ion binding studies of a new RuII-polypyridyl-crown-anthraquinone complex (5). Studies confirm selective binding of BaII, SrII and CaII ions, with Kmath image > Kmath image >> Kmath image, over all other metal ions, to the crown ether moiety and not to the methoxy anthraquinone component, the latter being the second binding site available and known for its affinity towards alkaline earth metal ions from one of our previous reports.

Composition-structure-property (Zn2+ and Ca2+ ion release) evaluation of Si-Na-Ca-Zn-Ce glasses: potential components for nerve guidance conduits - Zhang, X. F.; Kehoe, S.; Adhi, S. K.; Ajithkumar, Thalasseril G.; Moane, S.; O'Shea, H.; Boyd, D. (Materials Science & Engineering C-Materials for Biological Applications, 2011)
Bioactive glasses have demonstrated tailored therapeutic ion release, primarily with respect to the augmentation of hard tissues. However, controlled degradation and release of therapeutic ions from biomaterials may also play an important role in soft tissue regeneration such as repair of peripheral nerve discontinuities. In this study, three silica based glasses (0.5SiO(2)-0.2CaO-0.13ZnO-XNa2O-(0.17-X) CeO2) where, (0.04 < X < 0.14) were synthesised and characterised. The local environment of the Si-29 isotope was probed for each glass using Si-29 MAS-NMR, whilst the thermal characteristics of each glass were examined using DTA. Following these analyses, ion release profiles for Ca2+ and Zn2+ were evaluated; an equivalent specific surface area of 1 m(2) of each glass powder was incubated (37 degrees C) in 10 ml of citric acid buffer and TRIS-HCl buffer solution (pH 3.0 and pH 7.4 respectively) for incubation periods of up to 30 days. The Zn2+ concentration of each filtrate was analysed using flame Atomic Absorption Spectroscopy (Varian AA240FS Fast Sequential AAS) and the Ca2+ concentration of each filtrate was determined using Inductively Coupled Plasma-Mass Spectrometer (Varian 820 ICP-MS). Results obtained from the Si-29 MAS-NMR spectra indicated Q(2) structures pervading the network. An analytical model was proposed to analyse the ion release profiles for each glass, and indicated heterogeneous dissolution of glass networks. The ion release data demonstrates that ion release in the range (19.26-3130 ppm) for Ca2+ and in the range (5.97-4904 ppm) for Zn2+ occurred. Release of such elements, at appropriate levels, from peripheral nerve guidance conduits may be advantageous with respect to the repair of peripheral nerve discontinuities. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Bioglass; Dissolution; Modelling

Control of competing hydrogenation of phenylhydroxylamine to aniline in a single-step hydrogenation of nitrobenzene to p-aminophenol - Nadgeri, Jayprakash M.; Biradar, Narayan S.; Patil, Priyanka B.; Jadkar, Sachin T.; Garade, Ajit C.; Rode, Chandrashekhar V. (Industrial & Engineering Chemistry Research, 2011)
Two steps involving catalytic hydrogenation of nitrobenzene to phenylhydroxylamine (PHA) in acid medium and its rearrangement to p-aminophenol (PAP) were studied separately in a batch reactor, using a well-characterized 3% Pt/C catalyst. The first step of hydrogenation of nitrobenzene to PHA could be carried out at 303 K and a H(2) pressure of 0.69 MPa with complete conversion of nitrobenzene, while the achieved selectivity to PHA was higher than 90% with some formation of aniline, even at lower temperature. The second step of PHA rearrangement to PAP could be achieved under a hydrogen atmosphere at elevated temperature of 353 K to give a maximum selectivity to PAP of 74%.

Convenient and efficient protocol for the synthesis of acylals catalyzed by bronsted acidic ionic liquids under ultrasonic irradiation - Borikar, Sanjay P.; Daniel, Thomas (Ultrasonics Sonochemistry, 2011)
The synthesis of acylals (1,1-diacetates) via the reactions of aldehydes with acetic anhydride was carried Out in 85-97% yields at room temperature under ultrasound irradiation catalyzed by the Bronsted acidic ionic liquid [bmpy]HSO(4). This method provides several advantages, such as solvent-free conditions, operational simplicity, higher yields, and reduced environmental consequences. The ionic liquid was recovered and reused. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: 1; 1-Butyl-3-methylpyridinium hydrogen sulfate; 1-Diacetates; Acylals; Ionic liquid; Solvent-free; Ultrasonic irradiation

Cyclodiphosph(III)azane chemistry – ylides from the reaction of [(RNH)P-N(t-Bu)]2 [R = t-Bu, i-Pr] with dimethyl maleate and chiral ansa-type derivatives from reaction of [ClP-N(t-Bu)]2 with a substituted BINOL - Swamy, K.C. Kumara; Gangadhararao, G.; Srinivas, Venu; Kumar, N. N. Bhuvan; Balaraman, Ekambaram; Chakravarty, Manab (Inorganica Chimica Acta, 2011)
Use of a simple inorganic ring system with the cyclodiphosph(III)azane skeleton [e.g. [(RNH)P-N(t-Bu)]2 [R = t-Bu (7), i-Pr (8)] to probe some of the intermediates proposed in phosphine mediated organic reactions is highlighted. Thus the reaction of 7–8 with the allenylphosphine oxide Ph2P(O)C(Ph)double bond; length as m-dashCdouble bond; length as m-dashCH2 (9) affords the phosphinimines [(RNH)P(μ-N-t-Bu)2P(double bond; length as m-dashN-R)-C(double bond; length as m-dashCH2)CH(Ph)-P(O)Ph2] [R = t-Bu (10), i-Pr (11)], while a similar reaction of 7–8 with dimethyl maleate (or dimethyl fumarate) affords the ylides [(RNH)P(μ-N-t-Bu)2P(NH-R)double bond; length as m-dashC(CO2Me)-CH2(CO2Me) [R = t-Bu (18), i-Pr (19)]. The implication of such reactions on phosphine mediated organic transformations including Morita–Baylis–Hillman reaction is mentioned. In a rather rare type of situation, an unusually long phosphoryl (Pdouble bond; length as m-dashO) bond [1.538 (5) Å] as revealed the X-ray structure of {(R)-6,6′-(t-Bu)2-1,1′-(C10H5)2-2,2′-O2-}{P(O)(N-t-Bu)2-P(Se)} (27) is rationalized by means of crystallographic disorder in packing after comparing the data with that in the literature and {1,1′-(C10H6)2-2,2′-O2}{P(Se)(N-t-Bu)2-P(Se)} (29). X-ray structures of the new compounds 10–11, 18–19, 27 and 29 are discussed. Compound 10 crystallizes in the chiral space group Pca2(1) with (S)-chirality at the carbon center [–C(double bond; length as m-dashCH2)CH(Ph)-P] suggesting a case of spontaneous resolution through crystallization.

Design and in situ synthesis of a Cu-based porous framework featuring isolated double chain magnetic character - Dey, Chandan; Das, Raja; Saha, Binoy Krishna; Poddar, Pankaj; Banerjee, Rahul (Chemical Communications, 2011)
A Cu-based double chain MOF was synthesized in hydrothermal conditions using an in situ ligand formation method. This double chain MOF shows temperature dependent ferromagnetic (long range ordering) and antiferromagnetic (intra double chain) coupling. The magnetic behaviour originating from the individual double chain remains almost same even after structural collapse due to the removal of guest water molecules.

Design, synthesis and biological evaluation of peptidyl-vinylaminophosphonates as novel cysteine protease inhibitors - Bhattacharya, Asish K.; Rana, Kalpeshkumar C. (Bioorganic & Medicinal Chemistry, 2011)
We report herein, design and synthesis of vinylaminophosphonates, a novel class of compounds as possible cysteine protease inhibitors. The synthesis of vinylaminophosphonates has been accomplished employing Tsuji-Trost reaction as a key step. The synthesized compounds were assayed against papain, a model cysteine protease and some of our synthesized compounds showed IC50 values in the range of 30-54 mu M thereby suggesting that these chemical entities thus could constitute an interesting template for the design of potential novel protease inhibitors. (C) 2011 Elsevier Ltd. All rights reserved.
Keywords: Cysteine; Inhibitor design; Protease inhibitors; synthesis; Tsuji-Trost reaction; Vinylaminophosphonates

Determination of organic acid impurities in lactic acid obtained by fermentation of sugarcane juice - Qureshi, Mohd Shadbar; Bhongale, Sunil Sitaram; Thorave, Archana K. (Journal of Chromatography A, 2011)
Lactic acid produced by fermentation process mostly contains a number of aliphatic carboxylic acids as impurities. In this work, carboxylic acid impurities in lactic acid samples from a number of sources were determined at ppm levels. A simple HPLC method was developed that utilized a new generation polar embedded reverse phase, 20 mM phosphate buffer at pH 2.20 (+/- 0.05) and UV detection at 210 nm. The method enabled quantitative analysis of the above acids in lactic acid matrix. The experimental conditions for column temperature, mobile phase pH and flow rate were optimized. A detailed validation of the method was performed for linearity, precision, accuracy, selectivity, limit of detection (LOD), limit of quantitation (LOQ), ruggedness and repeatability and reproducibility (R&R). (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Lactic acid; Method validation; Organic acid impurities; Polar embedded RP-HPLC; Sugarcane juice fermentation

Diamine derivative of a ruthenium(II)-polypyridyl complex for chemodosimetric detection of nitrite ion in aqueous solution - Ghosh, Amrita; Das, Priyadip; Saha, Sukdeb; Banerjee, Tanmay; Bhatt, Harshad B.; Das, Amitava (Inorganica Chimica Acta, 2011)
Nitrite is quite an abundant anion in the environment. It, however, becomes toxic to human life, as well as aquatic animals when present above the permissible concentration level. We have reported here a Ru(II)-polypyridyl-based complex (1) for chemodosimetric detection of nitrite ion in aqueous solution. Formation of the new triazole based complex, generated by reaction of 1 and N2O3, is ascertained by comparing its properties with a presynthesised triazole complex.

Differential induction, purification and characterization of cold active lipase from Yarrowia lipolytica NCIM 3639 - Yadav, K. N. Sathish; Adsul, Mukund G.; Bastawade, Kulbhushan B.; Jadhav, D. D.; Thulasiram, H. V.; Gokhale, D. V. (Bioresource Technology, 2011)
The production, purification and characterization of cold active lipases by Yarrowia lipolytica NCIM 3639 is described. The study presents a new finding of production of cell bound and extracellular lipase activities depending upon the substrate used for growth. The strain produced cell bound and extracellular lipase activity when grown on olive oil and Tween 80, respectively. The organism grew profusely at 20 degrees C and at initial pH of 5.5, producing maximum extracellular lipase. The purified lipase has a molecular mass of 400 kDa having 20 subunits forming a multimeric native protein. Further the enzyme displayed an optimum pH of 5.0 and optimum temperature of 25 degrees C. Peptide mass finger printing reveled that some peptides showed homologues sequence (42%) to Yarrowia lipolytica LIP8p. The studies on hydrolysis of racemic lavandulyl acetate revealed that extracellular and cell bound lipases show preference over the opposite antipodes of irregular monoterpene, lavandulyl acetate. (C) 2011 Elsevier Ltd. All rights reserved.
Keywords: Cell bound lipase; Cold active lipase; Extracellular lipase; Lavandulyl acetate; Oligomeric lipase

Direct synthesis of well-ordered mesoporous Al-SBA-15 and its correlation with the catalytic activity - Bhange, Pallavi; Bhange, Deu S.; Pradhan, Sivaram; Ramaswamy, Veda (Applied Catalysis A-General, 2011)
The synthesis of Al-SBA-15 under milder acidic conditions were made through an adjusting the molar H(2)O/HCl ratio which indicate the formation of Si-O-Al linkages that lead to isomorphous substitution of Si(4+) by some Al(3+) ions. By adjusting the H(2)O/HCl molar ratio, Al gets incorporated into the lattice of SBA-15, which is evidenced by XRD. N(2) adsorption, TEM, (29)Si and (27)Al MAS NMR spectroscopic data. Aluminium incorporated SBA-15 samples retained both structural and textural properties of SBA-15. The (27)Al MAS NMR confirms that a large proportion of the Al is inserted into tetrahedral positions within the framework. The Al(3+) ions could assume a tetrahedral coordination and be part of the hexagonal structure of silica in Al-SBA-15. In the present study, we have examined the effectiveness of Al-SBA-15, as an acid catalyst for the esterification of acetic acid and in benzylation of anisole. The high activity of Al-20 sample in esterification reaction has been attributed to isolated, generally tetrahedrally coordinated, framework Al species. While in benzylation of anisole, the best result was achieved with Al-5 catalyst. The selectivity for benzylanisole increases and that for dibenzylether decreases with increase in the Si/Al ratio of Al-SBA-15. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Al-SBA-15; Benzylation of anisole; Esterification of acetic acid

Diversifying the structural architecture of synthetic oligomers: the hetero foldamer approach - Roy, Arup; Prabhakaran, Panchami; Baruah, Pranjal Kumar; Sanjayan, Gangadhar J. (Chemical Communications, 2011)
Conformationally ordered synthetic oligomers, also called ``foldamers'', have attracted considerable attention in recent years owing to their ability to mimic the structural architecture of biopolymers and also because of their potential applications in biomedical and material science fields. Until recently, the major focus in this area has been the development of oligomers featuring a single type of monomer building blocks. However, due to the enormous possibility of augmenting the conformational space available for oligomer design, the hetero foldamer approach has been introduced very recently. This feature article aims to describe foldamers with unique structural architectures, exclusively featuring heterogeneous backbones (hetero foldamers).

Ecofriendly hydrogen production from abundant hydrogen sulfide using solar light-driven hierarchical nanostructured ZnIn2S4 photocatalyst - Chaudhari, Nilima S.; Bhirud, Ashwini P.; Sonawane, Ravindra S.; Nikam, Latesh K.; Warule, Sambhaji S.; Rane, Vilas H.; Kale, Bharat B. (Green Chemistry, 2011)
It is quite well-known that refineries are producing huge amount of H2S which has been used to produce sulphur and water using the well-known Claus process. This process is not an economically viable process, due to the high-cost chemical process and creates further acute environmental problems. Therefore, we have demonstrated the conversion of poisonous H2S into H-2 using an ecofriendly phocatalysis process which is a green unconventional energy source. We have investigated ecofriendly nanostructured ZnIn2S4 photocatalyst to produce hydrogen from H2S using solar light. We also demonstrate the controlled synthesis of hierarchical nanostructured ZnIn2S4 using a facile hydrothermal method. The morphologies obtained have been greatly influenced by the presence of triethylamine (TEA) with various concentrations during the reaction. Surprisingly, a highly crystalline hexagonal layer structured ZnIn2S4 was obtained instead of cubic spinel. The hierarchical nanostructure, i.e. marigold flower-like morphology, was obtained without any surfactant. The thin and transparent petals self-assembled to form the unique nanostructured marigold flower. The highly crystalline puffy marigold flowers and nanoplates/nanostrips were obtained using TEA-assisted hydrothermal synthesis. Optical study shows the band gap in the range of 2.34-2.48 eV. Considering the band gap in the visible region, ZnIn2S4 is used as photocatalyst for hydrogen production from hydrogen sulphide under solar light which is hitherto unattempted. The constant photocatalytic activity of hydrogen evolution, i.e. 5287 mu mol h(-1), was obtained using such hierarchical nanostructured ZnIn2S4 under visible light irradiation. It is noteworthy that the H-2 evolution rate obtained is much higher compared to earlier reported photocatalysts. Considering the significance of morphologies for photocatalytic application, the formation mechanism has also been furnished. The unique hierarchical nanostructured ZnIn2S4 ternary semiconductor having hexagonal layer will have potential applications in solar cells, LEDs, charge storage, electrochemical recording, thermoelectricity and other prospective electronic and optical devices.

Effect of aluminium doping on structural and gas sensing properties of zinc oxide thin films deposited by spray pyrolysis - Badadhe, Satish S.; Mulla, Imtiaz S. (Sensors and Actuators B-Chemical, 2011)
A facile spray pyrolysis route is used to deposit aluminium doped ZnO (AZO) thin films on to the glass substrates. It is observed that on aluminium doping the particle size of ZnO reduces significantly; moreover, uniformity of particle also gets enhanced. Their XRD study reveals that intensity ratio of crystal planes depend on the aluminium doping concentration. The gas response studies of; similar to 800 nm thick Al-doped ZnO films at different operating temperatures show that 5 at% Al-doped ZnO thin film exhibits highest response towards H(2)S gas at 200 degrees C. The results suggest that the gas response strongly depends on the particle size and aluminium doping in the ZnO. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Aluminium; H(2)S sensor; Spray pyrolysis; thin film; Zinc oxide

Efficient hydrogenation of organic carbonates, carbamates, and formates indicates alternative routes to methanol based on CO2 and CO - Balaraman, Ekambaram; Gunanathan, Chidambaram; Zhang, Jing; Shimon, Linda J. W.; Milstein, David (Nature Chemistry, 2011)
Catalytic hydrogenation of organic carbonates, carbamates and formates is of significant interest both conceptually and practically, because these compounds can be produced from CO2 and CO, and their mild hydrogenation can provide alternative, mild approaches to the indirect hydrogenation of CO2 and CO to methanol, an important fuel and synthetic building block. Here, we report for the first time catalytic hydrogenation of organic carbonates to alcohols, and carbamates to alcohols and amines. Unprecedented homogeneously catalysed hydrogenation of organic formates to methanol has also been accomplished. The reactions are efficiently catalysed by dearomatized PNN Ru(II) pincer complexes derived from pyridine- and bipyridine-based tridentate ligands. These atom-economical reactions proceed under neutral, homogeneous conditions, at mild temperatures and under mild hydrogen pressures, and can operate in the absence of solvent with no generation of waste, representing the ultimate ‘green’ reactions. A possible mechanism involves metal–ligand cooperation by aromatization–dearomatization of the heteroaromatic pincer core.

Efficient synthesis of benzodiazepinyl phosphonates as clostripain inhibitors via FeCl3 catalyzed four-component reaction - Bhattacharya, Asish K.; Rana, Kalpeshkumar C.; Raut, Dnyaneshwar S.; Mhaindarkar, Vaibhav P.; Khan, Mohammad Islam (Organic & Biomolecular Chemistry, 2011)
A novel one-pot route for the synthesis of benzodiazepinyl phosphonates (BDPs) has been achieved. FeCl3 efficiently catalyzed four-component condensation of diamines, acetone and phosphites in the presence of molecular sieves to furnish BDPs as novel chemical entities with good yield. The synthesized BDPs have shown significant protease inhibition activity against clostripain, a disease model for gas gangrene, suggesting that these novel chemical entities could be further explored as cysteine protease inhibitors.

Efficient synthesis of benzofuranones: N-heterocyclic carbene (NHC)/base-catalyzed hydroacylation-stetter-rearrangement cascade - Padmanaban, Mohan; Biju, Akkattu T.; Glorius, Frank (Organic Letters, 2011)
A N-heterocyclic carbene/base-catalyzed cascade reaction leading to the formation of functionalized benzofuranones is reported. The reaction proceeds via an intramolecular hydroacylation of unactivated alkynes followed by an intermolecular Stetter reaction and a base-catalyzed chromanone to benzofuranone rearrangement.

Electron-rich PNP- and PNN-type Ru(II) hydrido-borohydride complexes. synthesis, structure and catalytic activity towards dehydrogenation of alcohols and hydrogenation of esters - Zhang, Jing; Balaraman, Ekambaram; Leitus, Gregory; Milstein, David (Organometallics, 2011)
Electron-rich PNP- and PNN-type ruthenium(II) hydrido borohydride pincer complexes, [RuH(BH4)(tBu-PNP)] (tBu-PNP = (2,6-bis(di-tert-butylphosphinomethyl)pyridine) (5) and [RuH(BH4)(tBu-PNN)] (tBu-PNN = 2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) (6), were prepared from their corresponding N2-bridged dinuclear Ru(II) complexes [(tBu-PNP)RuCl2]2(μ-N2) (3) and [(tBu-PNN)RuCl2]2(μ-N2) (4), respectively. The X-ray structure of 5 reveals a BH4– anion η2 coordinated to ruthenium through two bridging hydrides. A variable-temperature 1H NMR study of 6 exhibits interesting fluxional behavior of the BH4– ligand. Similarly, the Ru(II) hydrido borohydride complex 9, in which the BH4– moiety is coordinated in a η1 bonding mode, was obtained by reaction of [RuCl2(PPh3)(iPr-PNP)] (iPr-PNP = 2,6-bis(diisopropylphosphinomethyl)pyridine) (8) with two equivalents of NaBH4 at room temperature. The hydrido borohydride pincer complexes 5, 6, and 9 catalyze the acceptorless dehydrogenative coupling of primary alcohols to esters and the dehydrogenation of secondary alcohols to the corresponding ketones, accompanied by evolution of hydrogen gas. The reactivity follows the order 6 > 9 > 5. With the hydrido borohydride complex 6 as catalyst, high yields (up to 98%) and high turnover numbers (TON ∼1000) were obtained in the dehydrogenation of primary alcohols under mild and neutral conditions. In addition, 6 effectively catalyzes the hydrogenation of nonactivated aromatic and aliphatic esters to the corresponding alcohols with TON ∼200 under a relatively mild pressure of dihydrogen and neutral and homogeneous conditions. Thus, an efficient homogeneous catalytic system for the dehydrogenation–hydrogenation reactions of alcohols is developed, which is relevant to the current interest in hydrogen storage.

Employing homoenolates generated by NHC catalysis in carbon-carbon bond-forming reactions: state of the art - Nair, Vijay; Menon, Rajeev S.; Biju, Akkattu T.; Sinu, C. R.; Paul, Rony Rajan; Jose, Anu; Sreekumar, Vellalath (Chemical Society Reviews, 2011)
Homoenolate is a reactive intermediate that possesses an anionic or nucleophilic carbon beta to a carbonyl group or its synthetic equivalent. The recent discovery that homoenolates can be generated from alpha,beta-unsaturated aldehydes via N-Heterocyclic Carbene (NHC) catalysis has led to the development of a number of new reactions. A majority of such reactions include the use of carbon-based electrophiles, such as aldehydes, imines, enones, dienones etc. resulting in the formation of a variety of annulated as well as acyclic products. The easy availability of chiral NHCs has allowed the development of very efficient enantioselective variants of these reactions also. The tolerance showed by NHCs towards magnesium and titanium based Lewis acids has been exploited in the invention of cooperative catalytic processes. This tutorial review focuses on these and other types of homoenolate reactions reported recently, and in the process, updates the previous account published in 2008 in this journal.

Enantioselective total syntheses of (-)-isonitramine, (-)-sibirine, and (+)-nitramine by ring-closing metathesis - Pandey, Ganesh; Kumara, Prasanna C.; Burugu, Shiva Kumar; Puranik, Vedavati G. (European Journal of Organic Chemistry, 2011)
Concise enantioselective total syntheses of naturally occurring 2-azaspiro[5,5]undecan-7-ol (Nitraria) alkaloids viz. ()-isonitramine, ()-sibirine, and (+)-nitramine are accomplished in 42, 38, and 25?% overall yield, respectively, in six steps starting from enantiomerically pure (S)-methyl 3-allyl-2-oxo-1,2,3,6-tetrahydropyridine-3-carboxylate (>99?%?ee). The key feature of the syntheses involves diastereoselective HosomiSakurai allylation followed by ring-closing metathesis.
Keywords: Alk-aloids; Allylation; Amino alcohols; Metathesis; Total synthesis

Enantiospecific route to (+)-(1R, 3S)-cis-chrysanthemic acid from (-)-D-pantolactone(1) - Hajare, Atul K.; Datrange, Laxmikant S.; Murthy, Y. L. N.; Bhuniya, Debnath; Reddy, D. Srinivasa (Synthesis-Stuttgart, 2011)
In this paper, a novel route for the synthesis of (+)-(1R,3S)-cis-chrysanthemic acid is described. The use of readily available (-)-D-pantolactone as a starting point, application of ring-closing metathesis to form the cyclopentene intermediate, and Haller-Bauer/Grob-type fragmentation to form the target compound are the highlights of the present synthesis.
Keywords: alkenes; Metathesis; ring closure; stereoselective synthesis; Wittig reaction

Enhanced DNA binding of 9-omega-amino alkyl ether analogs from the plant alkaloid berberine - Islam, Md Maidul; Basu, Anirban; Hossain, Maidul; Sureshkumar, Gopalsamy; Hotha, Srinivas; Kumar, Gopinatha Suresh (DNA and Cell Biology, 2011)
To understand the structure-activity relationship of isoquinoline alkaloids, absorption, fluorescence, circular dichroism, and thermodynamics were employed to study the interaction of five C-9-omega-amino alkyl ether analogs from the plant alkaloid berberine with double-stranded calf thymus DNA. The C-9 derivatization resulted in dramatic enhancements in the fluorescence emission of these compounds. The most remarkable changes in the spectral and binding properties were in the BC4 and BC5 derivatives. Interactions of these analogs, which have an additional recognition motif with DNA, were evaluated through different spectroscopic and calorimetric titration experiments. The analogs remarkably enhanced the DNA binding affinity and the same was directly dependent on the alkyl chain length. The analog with six alkyl chains enhanced the DNA binding affinity by about 33 times compared with berberine. The binding became more entropically driven with increasing chain length. These results may be of potential use in the design of berberine derivatives and understanding of the structure-activity relationship for improved therapeutic applications.

Enhanced DSSC performance with high surface area thin anatase TiO2 nanoleaves - Dhas, Vivek V.; Muduli, Subas; Agarkar, Shruti A.; Rana, Abhimanyu; Hannoyer, Beatrice; Banerjee, Rahul; Ogale, Satishchandra B. (Solar Energy, 2011)
Thin anatase TiO2 nanoleaves (NLs) with high surface area (similar to 93 m(2)/g) are synthesized by hydrothermal route and dye-sensitized solar cells (DSSC) made using such NLs are compared with those made with hydro-thermally synthesized TiO2 nanoparticles and the Degussa P25 powder. The NLs-based DSSCs show increment of 16% and 24% in the total conversion efficiency over the cells made with NPs and P25 respectively. Interestingly, the highest increment in the conversion efficiency (similar to 35%) is achieved for cells made using a 50:50 (wt/wt) mixture of NLs and NPs. In this case the dye loading is found to be >50% higher than the case of NP films. Moreover the DC resistance of diffusion of I-3(-) in electrolyte (as revealed by the electrochemical impedance spectroscopy) is substantially lower than the NP film case, other cell parameters being nominally comparable. (C) 2011 Elsevier Ltd. All rights reserved.
Keywords: Dye-sensitized solar cells; Electrochemical impedance spectroscopy; hydrothermal

Enhanced electrocatalytic performance of functionalized carbon nanotube electrodes for oxygen reduction in proton exchange membrane fuel cells - Kannan, Ramaiyan; Bipinlal, Unni; Kurungot, Sreekumar; Pillai, Vijayamohanan K. (Physical Chemistry Chemical Physics, 2011)
Although nitrogen doped CNTs (N-CNTs) are considered as a promising alternative to platinized carbon for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs), the origin of the enhanced ORR activity with N-CNTs is not clear at present. Among several plausible reasons, the exposure of edge plane and creation of impurity band/surface states near the Fermi level are considered as major causes behind the catalytic activity. However, CNTs without nitrogen doping are not known to catalyze the ORR. In this work, we study the ORR activity of functionalized carbon nanotubes with different functional groups, such as sulfonic acid and phosphonic acid, in order to understand the role of surface functionalities in catalyzing the reaction. Functionalized CNTs show significantly enhanced activity towards the ORR, while CNTs without such surface functional groups do not reveal any such special ORR activity. Linear sweep voltammetry experiments with different rotation rates show diffusion controlled limiting current values for functionalized CNTs, and the `n' values derived from Koutecky-Levich plots are 3.3 and 1.7 for S-MWCNTs and P-MWCNTs, respectively. This work demonstrates the ORR activity of functionalized MWCNTs, which opens up new strategies for electrocatalyst design in PEMFCs.

Enhanced electrocatalytic performance of interconnected Rh nano-chains towards formic acid oxidation - Sathe, Bhaskar R.; Balan, Beena K.; Pillai, Vijayamohanan K. (Energy & Environmental Science, 2011)
A chain-like assembly of rhodium nanoparticles (5-7 nm mean diameter) has been synthesized from rhodium chloride with the help of polydentate molecules like tartaric and ascorbic acids (1 : 3 in mM scale) as capping agents at room temperature. Subsequent characterization using transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy reveals a unique inter-connected network like features, while their electrochemical behavior using cyclic voltammetry and current-time transient suggests potential applications as electrocatalysts in fuel cells. A significant negative shift in the onset potential as well as higher anodic peak current density for formic acid oxidation on Rh-tartaric acid (Rh-TA) as compared to that of bulk Rh metal confirms their higher electrocatalytic activity. Interestingly, the enhancement factor (R) with respect to that of bulk metallic Rh towards formic acid oxidation ranges up to 2000% for Rh-TA and 1200% for Rh-AA (Rh-ascorbic acid) respectively. The composition of Rh nano-chains has been further analyzed with thermogravimetry and Fourier transform infra-red spectroscopy to demonstrate the importance of controlling the chain topology using polyfunctional organic molecules. These findings open up new possibilities for tailoring nanostructured electrodes with potential benefits since the development of a better electrocatalysts for many fuel cell reactions continues to be an important challenge.

Enhanced electron transport through template-derived pore channels in dye-sensitized solar cells - Phadke, Sarika; Du Pasquier, Aurelien; Birnie, Dunbar P. (Journal of Physical Chemistry C, 2011)
Dye-sensitized solar cells use porous nanoparticle TiO(2) coating as their photoanode. To obtain effective dye adsorption and better electrolyte permeation in the TiO(2) coating, the porosity structure must be fully, three-dimensionally interconnected. Templated processing offers the advantage of preparing TiO(2) photoanodes in controlled shape and interconnection to the porosity structures that result, including the creation of dual size scale porosity in some cases. In the present work, an emulsion templating method was employed to obtain the dual porosity in the titania coating. We have studied the effect of the enhanced permeation of the electrolyte provided by these interconnected pore channels using electrochemical impedance spectroscopy. The change in internal resistances of the dye-sensitized solar cell during operation is correlated with the microstructural features using scanning electron microscopy, mercury porosimetry and I-V characterization.

Esterification of levulinic acid to n-butyl levulinate over heteropolyacid supported on acid-treated clay - Dharne, S.; Bokade, Vijay V. (Journal of Natural Gas Chemistry, 2011)
Levulinic acid has been identified as a promising green, biomass-derived platform chemical. n-Butyl levulinate is used as an important intermediate having diverse applications. The present work focuses on the synthesis of n-butyl levulinate by esterification of levulinic acid with n-butanol using heteropolyacid (HPA) supported on acid-treated clay montmorillonite (K10). 20% (w/w) dodecatungestophosphoric acid (DTPA) supported on K10 was found to be the most efficient catalyst with 97% levulinic acid conversion and 100% selectivity towards n-butyl levulinate. Effects of various process parameters were studied to examine the efficacy of 20% (w/w) DTPA/K10 for optimization of the activity.
Keywords: dodectungestophosphoric acid; K10; levulinic acid; n-butanol; n-Butyl levulinate

Evidence of lateral heat transfer during laser assisted atom probe tomography analysis of large band gap materials - Bachhav, Mukesh N.; Danoix, R.; Vurpillot, F.; Hannoyer, Beatrice; Ogale, Satishchandra B.; Danoix, F. (Applied Physics Letters, 2011)
Investigation of wustite (FeO), iron (Fe), and silicon (Si) specimens by infrared laser assisted three dimensional atom probe tomography shows evidence of confined surface absorption of the laser energy as the mechanism of laser assisted field evaporation for high band gap materials. The absorption region is shown to be located on the laser illumination side, close to the specimen apex. A simple model based on thermal diffusivity and spatial extent of the absorption region is derived and applied to the experimental results. The values of thermal diffusivity thus obtained are in good agreement with the published data. (C) 2011 American Institute of Physics. [doi:10.1063/1.3622647]

Experimental and computational approach of understanding the gas adsorption in amino functionalized interpenetrated metal organic frameworks (MOFs) - Pachfule, Pradip; Chen, Yifei; Jiang, Jianwen; Banerjee, Rahul (Journal of Materials Chemistry, 2011)
Two isostructural, three dimensional, interpenetrated, amino (-NH2) functionalized Metal Organic Frameworks [Cd(ANIC)(2)] (Cd-ANIC-1) and [Co(ANIC)(2)] (Co-ANIC-1) with amine-lined pores have been reported. The framework adopts dia topology with interpenetration. Cd-ANIC-1 and Co-ANIC-1 show high CO2 (273 K) and H-2 (77 K) uptake due to the presence of free -NH2 groups and framework interpenetration. The effect of interpenetration and amino functionalization on gas uptake properties of MOFs has been analysed experimentally and computationally, in the isostructural MOFs Cd-ANIC-1 and Co-ANIC-1.

Extending nhc-catalysis: reaction of aldehydes with unconventional reaction partners - Biju, Akkattu T.; Kuhl, Nadine; Glorius, Frank (Accounts of Chemical Research, 2011)
Transition metal catalysis is a powerful means of effecting organic reactions, but it has some inherent drawbacks, such as the cost of the catalyst and the toxicity of the metals. Organocatalysis represents an attractive alternative and, in some cases, offers transformations unparalleled in metal catalysis. Unique transformations are a particular hallmark of N-heterocyclic carbene (NHC) organocatalysis, a versatile method for which a number of modes of action are known. The NHC-catalyzed umpolung (that is, the inversion of polarity) of electrophilic aldehydes, through formation of the nucleophilic Breslow intermediate, is probably the most important mode of action. In this Account, we discuss the reaction of Breslow intermediates with unconventional reaction partners.

Extrudate swell of linear and branched polyethylenes: ALE simulations and comparison with experiments - Ganvir, Vivek; Gautham, Basavarsu P.; Pol, Harshawardhan; Bhamla, M. Saad; Sclesi, Lino; Thaokar, Rochish; Lele, Ashish K.; Mackley, Malcolm (Journal of Non-Newtonian Fluid Mechanics, 2011)
Extrudate swell is a common phenomenon observed in the polymer extrusion industry. Accurate prediction of the dimensions of an extrudate is important for appropriate design of dies for profile extrusion applications. Prediction of extrudate swell has been challenging due to (i) difficulties associated with accurate representation of the constitutive behavior of polymer melts, and (ii) difficulties associated with the simulation of free surfaces, which requires special techniques in the traditionally used Eulerian framework. In a previous work we had argued that an Arbitrary Lagrangian Eulerian (ALE) based finite element formulation may have advantages in simulating free surface deformations such as in extrudate swell. In the present work we reinforce this argument by comparing our ALE simulations with experimental data on the extrudate swell of commercial grades of linear polyethylene (LLDPE) and branched polyethylene (LOPE). Rheological behavior of the polymers was characterized in shear and uniaxial extensional deformations, and the data was modeled using either the Phan-Thien Tanner (PTT) model or the eXtended Pom-Pom (XPP) model. Additionally, flow birefringence and pressure drop measurements were done using a 10:1 contraction-expansion (CE) slit geometry in a MultiPass Rheometer. Simulated pressure drop and contours of the principal stress difference were compared with experimental data and were found to match well. This provided an independent test for the accuracy of the ALE code and the constitutive equations for simulating a processing-like flow. The polymers were extruded from long (L/D=30) and short (L/D=10) capillaries dies at 190 degrees C. ALE simulations were performed for the same extrusion conditions and the simulated extrudate swell showed good agreement with the experimental data. Crown Copyright (C) 2010 Published by Elsevier B.V. All rights reserved.
Keywords: ALE-FEM; extrudate swell; Flow birefringence; MultiPass Rheometer; PSD; PTT; XPP

Fe(III) complex of biuret-amide based macrocyclic ligand as peroxidase enzyme mimic - Panda, Chakadola; Ghosh, Munmun; Panda, Tamas; Banerjee, Rahul; Sen Gupta, Sayam (Chemical Communications, 2011)
An Fe(III) complex of a biuret-amide based macrocyclic ligand that exhibits both excellent reactivity for the activation of H(2)O(2) and high stability, especially at low pH and high ionic strength, is reported.

Ferroelectric and electrical characterization of multiferroic BiFeO3 at the single nanoparticle level - Vasudevan, R. K.; Bogle, Kashinath A.; Kumar, A.; Jesse, S.; Magaraggia, R.; Stamps, R.; Ogale, Satishchandra B.; Potdar, H. S.; Nagarajan, V. (Applied Physics Letters, 2011)
Ferroelectric BiFeO3 (BFO) nanoparticles deposited on epitaxial substrates of SrRuO3 (SRO) and La1-xSrxMnO3 (LSMO) were studied using band excitation piezoresponse spectroscopy (BEPS), piezoresponse force microscopy (PFM), and ferromagnetic resonance (FMR). BEPS confirms that the nanoparticles are ferroelectric in nature. Switching behavior of nanoparticle clusters were studied and showed evidence for inhomogeneous switching. The dimensionality of domains within nanoparticles was found to be fractal in nature, with a dimensionality constant of similar to 1.4, on par with ferroelectric BFO thin-films under 100 nm in thickness. Ferromagnetic resonance studies indicate BFO nanoparticles only weakly affect the magnetic response of LSMO. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3671392]

Field emission studies of silver nanoparticles synthesized by electron cyclotron resonance plasma - Purohit, Vishwas; Mazumder, Baishakhi; Bhise, Ashok B.; Poddar, Pankaj; Joag, Dilip S.; Bhoraskar, S. V. (Applied Surface Science, 2011)
Field emission has been studied for silver nanoparticles (25-200 nm), deposited within a cylindrical silver target in an electron cyclotron resonance (ECR) plasma. Particle size distribution was controlled by optimum biasing voltages between the chamber and the target. Presence of non-oxidized silver was confirmed from the X-Ray diffraction analysis; however, thin protective layer of oxide was identified from the selective area electron diffraction pattern obtained with transmission electron microscopy. The silver nanoparticles were seen to exhibit hilly pointed like structures when viewed under the atomic force microscopy (AFM). The emissive properties of these particles were investigated by field emission microscopy. It is found that this technique of deposition is ideal for formation of nanoparticles films on different substrate geometries with size controllability as well as its application to emission devices. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Cold plasma; field emission; Nanoparticles; thin film

First total synthesis of 5-hydroxy-3-methyl-4-propylsulfanyl-5H-furan-2-one: a cancer chemopreventive agent - Borikar, Sanjay P.; Paul, Vincent; Puranik, Vedavati G.; Sathe, Vilas T.; Lagunas-Rivera, Selene; Ordonez, Mario (Synthesis-Stuttgart, 2011)
The first total synthesis of 5-hydroxy-3-methyl-4-propylsulfanyl-5H-furan-2-one, a newly discovered natural product with anticancer property is described by two different routes. A sequence involving an incorporation of a methyl group via a Gilman reagent and a chemoselective reduction of a cyclic anhydride functionality are the key steps. The methods proposed start from easily available starting materials and allow ready preparation of the final compound in good overall yield.
Keywords: Allium cepa; chemopreventive; Gilman reagent; selective; synthesis

Fluorescence resonance energy transfer from tryptophan to folic acid in micellar media and deionised water - Mote, U. S.; Patil, S. R.; Bhosale, Siddharth H.; Han, Sung-Hwan; Kolekar, G. B. (Journal of Photochemistry and Photobiology B-Biology, 2011)
The fluorescence resonance energy transfer (FRET) from tryptophan (Trp) to folic acid (FA) in aqueous sodiumdodecyl sulphate, cetyltrimethyl ammonium bromide, and Brij-35 as well as deionised water was investigated using steady state and time resolved fluorescence techniques. The data obtained from steady state fluorescence spectral studies and time resolved measurement indicated that the FRET from Trp to FA occurred most effectively in aqueous sodium dodecyl sulphate micellar solutions. The distance between Trp and FA were evaluated. Binding constant, number of binding sites and thermodynamic parameters were determined for Trp-FA interactions in deionised water. The values of the thermodynamic parameters suggest that the hydrophobic forces and hydrogen bonding are the key interacting forces between Trp-FA interaction. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Fluorescence quenching; Fluorescence resonance energy transfer (FRET); Folic acid; Foster theory; Stern-Volmer plot; Tryptophan

Fractal impeller for stirred tank reactors - Kulkarni, Amol A.; Jha, Neha; Singh, Abhishek; Bhatnagar, Sumit; Kulkarni, Bhaskar D. (Industrial & Engineering Chemistry Research, 2011)
Stirred tank reactors are used for variety of applications at different scales of operation. The conventional impellers tend to develop regions having nonuniform energy dissipation rates in the stirred reactor. In this work, we propose a novel fractal impeller, which helps in reducing such nonuniformities and help develop a uniform randomness throughout the reactor. The impeller geometry is discussed in detail. Experimental measurements of the power consumption, mixing time, suspension quality, and the ability for gas dispersion were carried out, and the performance is compared with the conventional impellers. The impeller is seen to have a low power number, and it can generate a uniform suspension of particles even at relatively lower impeller speeds and can efficiently disperse gas into liquid to yield relatively higher gas hold-up values. The Fourier analysis of the power consumption time series data indicates that no specific prominent frequency events exist in the reactor, and the spectrum showed several frequency events to exist in the reactor with almost identical prominence.

Growth of aligned ZnO nanorods array on ITO for dye sensitized solar cell - Yengantiwar, Ashish; Sharma, Ramakant; Game, Onkar S.; Banpurkar, Arun G. (Current Applied Physics, 2011)
Aligned ZnO films of nanorods arrays were grown on Indium doped Tin oxide (ITO) glass substrate for the Dye Sensitized Solar Cells (DSSCs) applications. Two-step approach was employed for the deposition, which offers advantages such as excellent surface adhesion, large area deposition, high reproducibility and yield. Structural characterization using X-ray diffraction (XRD) shows a preferred c-axis (002) oriented growth. Scanning Electron Microscopy (SEM) images reveals uniformly distributed hexagonal ZnO nanorods with average diameter varying from 80 to 250 nm. Average growth rate of the films was estimated using Surface Profilometer which was found to be similar to 1 mu m/h. Optical characterizations were carried out using Photo-spectrometer and Raman spectroscopy. The DSSCs using these ZnO films of nanorods array as photo-electrodes show conversion efficiency ranging from 0.24 to -0.71 %, the maximum efficiency was obtained for films deposited for time duration 8 h. (C) 2010 Elsevier B.V. All rights reserved.
Keywords: Aligned ZnO nanorod growth; Dye sensitized solar cell; Open aqueous solution deposition

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

Halogen bonding in 2,5-dichloro-1,4-benzoquinone: insights from experimental and theoretical charge density analysis - Hathwar, Venkatesha R.; Gonnade, Rajesh G.; Munshi, Parthapratim; Bhadbhade, Mohan M.; Row, Tayur N. Guru (Crystal Growth & Design, 2011)
Experimental charge density distribution in 2, 5-dichloro-1, 4-benzoquinone has been carried out using high resolution X-ray diffraction data at 90 K to quantitatively evaluate the nature of C-Cl center dot center dot center dot O=C halogen bond in molecular crystals. Additionally, the halogen bond is studied from geometrical point of view and the same has been visualized using Hirshfeld surface analysis. The obtained results from experimental charge density analysis are compared with periodic quantum calculations using B3LYP 6-31G(d,p) level of theory. The topological values at bond critical point, three-dimensional static deformation density features and electrostatic potential isosurfaces unequivocally establish the attractive nature of C-Cl center dot center dot center dot O=C halogen bond in crystalline lattice.

Helical water chain mediated proton conductivity in homochiral metal-organic frameworks with unprecedented zeolitic unh-topology - Sahoo, Subash Chandra; Kundu, Tanay; Banerjee, Rahul (Journal of the American Chemical Society, 2011)
Four new homochiral metal-organic framework (MOF) isomers, [Zn(l-L-Cl)(Cl)](H2O)(2) (1), [Zn(l-L-Br)(Br)]-(H2O)(2) (2), [Zn(d-L-Cl)(Cl)(H2O)(2) (3), and [Zn(d-L-Br)-(Br)] (H2O)(2) (4) [L = 3-methyl-2-(pyridin-4-ylmethylamino)-butanoic acid], have been synthesized by using a derivative of L-/D-valine and Zn(CH3COO)(2)center dot 2H(2)O. A three-periodic lattice with a parallel ID helical channel was formed along the crystallographic c-axis. Molecular rearrangement results in an unprecedented zeolitic unh-toparigy in 1-4. In each case, two lattice water molecules (one H-bonded. to halogen atoms) form a secondary helical continuous water chain inside the molecular helix. MOFs 1 and 2 shows different water adsorption properties and hence different water affinity. The arrangement of water molecules inside the channel Was monitored by variable temperature single crystal X-ray diffraction, which indicated that MOF 1 has a higher water holding capacity than MOF 2. In MOF 1, water escapes. at 80 degrees C, while in T the same happens at a much lower temperature (similar to 40 degrees C). All the MOFs reported here shows reversible crystallization by readily reabsorbing moisture. In MOFs 1 and 2, the frameworks are stable after solvent removal, which is confirmed by a single-crystal to single crystal transformation. MOFs 1 and 3 show high proton conductivity of 4.45 x 10(-5) and 4.42 x 10(-5) S cm(-1), respectively, while 2 and 4 shows zero proton conductivity. The above result is attributed to the fact that MOF 1 has a higher water holding capacity than MOF 2.

Heteropolyacid supported on montmorillonite catalyst for dehydration of dilute bio-ethanol - Bokade, Vijay V.; Yadav, Ganapati D. (Applied Clay Science, 2011)
Vapour phase dehydration of dilute bio-ethanol (EtOH) to ethylene (E) and diethyl ether (DEE) is industrially relevant. Ethylene is an important raw material for many petrochemical products and Diethyl ether (DEE) can be used as an alternative fuel. The efficacy of montmorillonite (K-10) and dodecatungestophosphoric acid (DTPA) supported on montmorillonite (DTPA/K-10), has been evaluated in the current work in the dehydration of dilute bio-ethanol (80%m/m). The dehydration of ethanol and cracking of diethyl ether were studied independently. 30% m/m DTPA/K-10 was found to be more active with 74% ethanol conversion and 92% ethylene selectivity at 250 degrees C in comparison with other acid catalysts used. The merit of the process lies in its use of dilute bio-ethanol, a new avenue for ethylene production from a non-petroleum feedstock. Kinetic interpretation has been made by studying the important process parameters by using 30%m/m DTPA/montmorillonite as the catalyst. The mechanism of the dehydration of ethanol reaction suggests that two types of sites are responsible. The dehydration of ethanol and cracking of diethyl ether are second order reactions with weak adsorption of species. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Bio-ethanol; dehydration; Diethyl ether; Ethylene; Heteropolyacid

High level phytase production by aspergillus niger NCIM 563 in solid state culture: response surface optimization, up-scaling, and its partial characterization - Bhavsar, Kavita P.; Kumar, V. Ravi; Khire, Jayant Malhar (Journal of Industrial Microbiology & Biotechnology, 2011)
Phytase production by Aspergillus niger NCIM 563 was optimized by using wheat bran in solid state fermentation (SSF). An integrated statistical optimization approach involving the combination of Placket-Burman design (PBD) and Box-Behnken design (BBD) was employed. PBD was used to evaluate the effect of 11 variables related to phytase production, and five statistically significant variables, namely, glucose, dextrin, NaNO(3), distilled water, and MgSO(4)center dot 7H(2)O, were selected for further optimization studies. The levels of five variables for maximum phytase production were determined by a BBD. Phytase production improved from 50 IU/g dry moldy bran (DMB) to 154 IU/g DMB indicating 3.08-fold increase after optimization. A simultaneous reduction in fermentation time from 7 to 4 days shows a high productivity of 38,500 IU/kg/day. Scaling up the process in trays gave reproducible phytase production overcoming industrial constraints of practicability and economics. The culture extract also had 133.2, 41.58, and 310.34 IU/g DMB of xylanase, cellulase, and amylase activities, respectively. The partially purified phytase was optimally active at 55A degrees C and pH 6.0. The enzyme retained ca. 75% activity over a wide pH range 2.0-9.5. It also released more inorganic phosphorus from soybean meal in a broad pH range from 2.5 to 6.5 under emulated gastric conditions. Molecular weight of phytase on Sephacryl S-200 was approximately 87 kDa. The K (m) and V (max) observed were 0.156 mM and 220 mu m/min/mg. The SSF phytase from A. niger NCIM 563 offers an economical production capability and its wide pH stability shows its suitability for use in poultry feed.
Keywords: Aspergillus niger; Phytase; Response surface optimization; Solid state fermentation; Statistical methods

Highly exposed and activity modulated sandwich type Pt thin layer catalyst with enhanced utilization - Balan, Beena K.; Kurungot, Sreekumar (Journal of Materials Chemistry, 2011)
A Pt thin layer catalyst supported on an in situ prepared `RuO(2)-carbon-RuO(2)' sandwich type hybrid support is presented. This is achieved by the extensive functionalization of a hollow carbon nanofiber support to introduce oxygen containing functional groups (FCNF) with the specific aim to accomplish the exclusive adsorption of Ru ions along its inner cavity and outer surfaces. Preferential adsorption of Ru ions from a mixture of Pt and Ru with sufficient time for adsorption and reorganization of ions on the carbon nanofiber surface leads to the in situ renovation of FCNFs to form a hybrid `RuO(2)-carbon-RuO(2)' sandwich type support followed by Pt nanoparticle decoration. While the selective exposure of Pt on the hybrid support surface is confirmed from the HRTEM analysis, the electronic changes effected in the CNF support are evident from the XPS and XRD analysis. Finally, the potential benefit of such a design is also demonstrated using electrochemical studies, where the three-fold increase in the electrochemically active surface area from cyclic voltammetric analysis, a four-fold improvement in the limiting current density coupled with a 80 mV gain in onset potential from rotating disc electrode studies for the oxygen reduction reaction, and a drastic reduction in the CO poisoning for methanol oxidation reaction underlines the superb performance of this material. Such an exceptionally high performance can be attributed to the strong electronic perturbations occurring in the Pt and the FCNF support due to the presence of a continuous RuO(2) layer in between. Such a high aspect ratio core-shell type design with an unusual enhancement in the Pt utilization establishes the roles of both the hybrid support and active catalyst to address the future challenges in the area of utilization improvement.

Hydrogen bond directed honeycomb-like porous network structure of tris (bipyridyl-glycoluril)cobalt(III) chloride - Kawade, Vitthal A.; Kumbhar, Avinash S.; Erxleben, Andrea; Pachfule, Pradip; Banerjee, Rahul (Crystengcomm, 2011)
The [Co(bpg)3]Cl-3 complex (1), where bpg = 4b, 5, 7, 7a-tetrahydro4b,7a-epiminomethan-oimino-6H-imidazo [4,5-f][1,10]-phenanthroline-6,13-dione has been synthesized and characterized by various spectroscopic techniques and single crystal X-ray diffraction. The combination of bipyridyl-glycoluril (bpg) ligands and cobalt ion self-organise to form a honeycomb-like porous network structure resulting in the formation of zeolite like channels which adsorb gases, is described.

Hyper-production of beta-glucosidase and beta-xylosidase by aspergillus niger NCIM 1207 In Xylan-Containing Media - Khisti, Ujwala; Bastawade, Kulbhushan B.; Gokhale, Digambar V. (Bioresources, 2011)
Aspergillus niger NCIM 1207 produced significantly high levels of beta-glucosidase and beta-xylosidase activities in submerged fermentation. Cellulose induced only beta-glucosidase, while xylan induced both beta-glucosidase and beta-xylosidase activities. Both the enzymes of this strain were found to undergo catabolite repression in the presence of high concentrations of glucose and glycerol. The sudden drop in pH of the fermentation medium below 3.5 caused the inactivation of enzymes when the fungus was grown in glycerol-containing media at lower temperatures. The growth of the organism at 36 degrees C led to an increase in pH of the fermentation above 6.0 that affected beta-xylosidase activity significantly. Highest levels of beta-glucosidase ((19 IU mL(-1) or 633 IU g(-1) of substrate) and beta-xylosidase (18.7 IU/mL(-1) or 620 IU g(-1) of substrate) activities were detected when A. niger was grown at 30 degrees C for first five days followed by further incubation at 36 degrees C. Such a process of growing the organism at lower temperatures (growth phase) followed by producing the enzymes at higher temperatures (production phase) in case of fungal systems has not been reported so far. The zymogram staining of the beta-glucosidase demonstrated that A. niger produced only single species of beta-glucosidase. We feel that A. niger NCIM 1207 is a potential candidate to produce both beta-glucosidase and beta-xylosidase in high amounts that can be used to supplement commercial cellulase preparations.
Keywords: Aspergillus niger NCIM 1207; beta-glucosidase production; beta-xylosidase production

Influence of Al3+ insertion in the stannosilicate MFI framework on the catalytic performance in vapor phase aniline N-methylation - Niphadkar, P. S.; Joshi, P. N.; Deshpande, Suvarna S.; Bokade, Vijay V. (Applied Catalysis A-General, 2011)
Silica-based Sn-MFI, Al-MFI and Al-Sn-MFI molecular sieves were synthesized by hydrothermal crystallization of gels having molar compositions SiO2:xSnO(2):yAl(2)O(3):0.23 (TPA)(2)O:35H(2)O, where x ranges from 1/0 to 1/200 and y from 1/0 to 1/400. Keeping molar Si/(Al + Sn) = 50, the amount of tin and aluminum in hydrogel was varied (Sn:Al molar ratios = 1:0, 1:0.33, 1:1, 1:3, 0:1) to investigate the synergy between Lewis and Bronsted acid sites in acid catalyzed aniline N-methylation reaction. Catalyst characterization was done by Powder X-ray diffraction, DRUV-vis spectroscopy, temperature programmed ammonia desorption (TPAD) and FTIR spectroscopy. An increase in the Al3+ insertion in Sn-MFI framework resulted in the increase in the stronger acid sites. Al-Sn-MFI showed higher aniline conversion than their monometallic counterparts. A sample having B/L ratio in between 0.67 and 0.91 was found to be optimum for maximizing the NMA yield, indicating the existence synergistic properties of Al-Sn-MFI. Upon process parameter optimization, the optimum sample M50 [Si/Al = 50.2, Si/Sn = 93.8, Si/(Al + Sn) = 43.2] showed the maximum aniline conversion (67%) and NMA selectivity (81%) at reaction temperature = 220 degrees C, weight hourly space velocity (WHSV) = 3 h(-1), molar ratio (aniline to methanol) = 1:8 and TOS = 4 h. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Al-Sn-MFI; Aniline; Bronsted and Lewis acid; Methanol; N-methylaniline

Interfacial electron transfer dynamics of two newly synthesized catecholate bound ruII polypyridyl-based sensitizers on TiO2 nanoparticle surface - a femtosecond pump probe spectroscopic study - Banerjee, Tanmay; Rawalekar, Sachin; Das, Amitava; Ghosh, Hirendra Nath (Europian Journal of Inorganic Chemistry, 2011)
Two new catecholate-bound RuII–polypyridine based sensitizers, (2,2′-bipyridine){ethyl 3-(4-hydroxyphenyl)-2-[(4′-methyl-2,2′-bipyridinyl-4-carbonyl)amino]propionate}{4-[2-(4′-methyl-2,2′-bipyridinyl-4-yl)vinyl]benzene-1,2-diol)}ruthenium(II) hexafluorophosphate (5) and [(2,2′-bipyridine)-(4-2,2′-bipyridinyl-4-yl-phenol)-(4-{2-(4′-methyl-2,2′-bipyridinyl-4-yl)vinyl}benzene-1,2-diol)]ruthenium(II) hexafluorophosphate (6) with secondary electron-donating groups (tyrosine and phenol, respectively) were synthesized and characterized. Steady-state optical absorption and emission studies confirm strong coupling between the sensitizers and TiO2 nanoparticles. Femtosecond visible transient absorption spectroscopy has been employed to study interfacial electron transfer (IET) dynamics in the dye–nanoparticle systems to explore the influence of the secondary electron-donating groups on IET dynamics. Electron injection into the conduction band of nanoparticulate TiO2 has been confirmed by detection of the conduction band electrons in TiO2 ([e–]TiO2CB) and radical cation of the adsorbed dye (D·+) in real time monitored by transient absorption spectroscopy. A single exponential and pulse-width limited (< 100 fs) electron injection has been observed. Back electron transfer (BET) dynamics have been studied by monitoring the decay kinetics of the injected electron in the conduction band of TiO2 and by the recovery of the ground state bleach. BET dynamics in dye–TiO2 systems for complexes 5 and 6 have been compared with those of [bis(2,2′-bpy)-(4-{2-(4′-methyl-2,2′-bipyridinyl-4-yl)vinyl}benzene-1,2-diol)]ruthenium(II) hexafluorophosphate (7), which does not have a secondary electron-donating group.

Intermolecular benzoyl group transfer reactivity in crystals of racemic 2,6-di-O-benzoyl-myo-inositol 1,3,5-orthobenzoate: controlling reactivity by solvate (pseudopolymorph) formation - Krishnaswamy, Shobhana; Shashidhar, Mysore S.; Bhadbhade, Mohan M. (Crystengcomm, 2011)
Racemic 2,6-di-O-benzoyl-myo-inositol 1,3,5-orthobenzoate (rac-3), which usually crystallizes in a monoclinic lattice (Form I, P2(1)/c) from common organic solvents, when crystallized from 2-propanol yielded concomitantly, thin whisker like crystals (Form II, triclinic, P (1) over bar) with inclusion of 2-propanol and water molecules, along with the Form I crystals. Thin fibre-like crystals were also obtained on crystallization from toluene, with inclusion of toluene and water in the crystal lattice (Form III). The Form II and Form III crystals could be converted into the Form I crystals thermally via melt crystallization. Form I crystals exhibit a facile transesterification reaction, but the solvated crystals are unreactive under the same conditions until their transformation to the reactive form. The reactivity patterns of the Form I and Form II crystals correlate well with the molecular organization in them. Since reactivity of the crystals of rac-3 depends on the solvent and the method of crystallization, and the thermal transition of one crystal form to the other, these phase changes can be used as a switch to control the benzoyl transfer reactivity of the constituent molecules in crystals.

Investigation of wustite (Fe1-xO) by femtosecond laser assisted atom probe tomography - Bachhav, Mukesh N.; Danoix, R.; Danoix, F.; Hannoyer, Beatrice; Ogale, Satishchandra B.; Vurpillot, F. (Ultramicroscopy, 2011)
In this paper, we report results obtained from laser assisted three-dimensional (3-D) atom probe tomography (APT) on wustite (Fe1-xO). Oxides are generally insulating and hence hard to analyse in conventional electrical assisted APT. To overcome this problem, femtosecond laser pulses are used instead of voltage pulses. Here we discuss some aspects of pulsed laser field evaporation and optimization of parameters to achieve better chemical accuracy. (C) 2010 Elsevier B.V. All rights reserved.
Keywords: Atom probe tomography; Laser assisted field evaporation; Wustite

Investigations of magnetic and dielectric properties of cupric oxide nanoparticles - Bhalerao-Panajkar, Rohini S.; Shirolkar, Mandar M.; Das, Raja; Maity, Tuhin; Poddar, Pankaj; Kulkarni, S. K. (Solid State Communications, 2011)
Cupric oxide nanoparticles of similar to 8-10 nm width and 40-45 nm length self assembled as large particles similar to 1-1 5 mu m have been investigated in the 10-325 K temperature range using magnetic and dielectric measurements In magnetic measurements a single broad peak at similar to 230 K in a zero field cooled sample has been observed Coercivity in magnetization measurements at 10 K suggests that the nanoparticles are core-shell type particles with an antiferromagnetic core and a ferromagnetic shell Dielectric measurements at various frequencies from 3 7 Hz to 949 kHz exhibit a sharp peak at 284 K followed by weak anomalies around 213 and 230 K (C) 2010 Elsevier Ltd All rights reserved
Keywords: CuO nanoparticles; Dielectric; Ferroelectric transition; Ferromagnetic

Isolation, identification and optimization of a new extracellular lipase producing strain of rhizopus sp. - Kantak, Jayshree B.; Bagade, Aditi V.; Mahajan, Siddharth A.; Pawar, Shrikant P.; Shouche, Yogesh S.; Prabhune, Asmita (Applied Biochemistry and Biotechnology, 2011)
A lipolytic mesophilic fungus which produces lipase extracellularly was isolated from soil. Based on ITS1-5.8S-ITS4 region sequences of ribosomal RNA, it was concluded that the isolate JK-1 belongs to genus Rhizopus and clades with Rhizopus oryzae. The present paper reports the screening, isolation, identification, and optimization of fermentation conditions for the production of lipase (EC 3.1.1.3). Culture conditions were optimized, and the highest lipase production was observed in basal medium with corn steep liquor as nitrogen source and glucose as carbon source. Maximum lipase production was observed at 72 h, which is about 870 U/ml. Optimization of fermentation conditions resulted in 16-fold enhancement in enzyme production.
Keywords: Corn steep liquor; Fermentation; ITS region; Lipase; Medium optimization; Rhizopus

Liquid phase oxidation of p-vanillyl alcohol over synthetic Co-saponite catalyst - Garade, Ajit C.; Biradar, Narayan S.; Joshi, S. M.; Kshirsagar, V. S.; Jha, Ratnesh Kumar; Rode, Chandrashekhar V. (Applied Clay Science, 2011)
Effect of cobalt loading on porosity of synthetic Co-saponite catalysts and on the air oxidation of p-vanillyl alcohol was studied by varying Co content in the range of 5% to 30% using in situ precipitation method. The pore size increased from 1.29 to 3.69 nm indicating a transition from micro to meso porosity, with increase in Co loading from 5% to 30%. The distribution ratio of Co(3)O(4)/CoO phases as estimated from TPR studies, also increased from 0.84 to 1.67 with increase in Co loading from 5% to 13% and remained almost constant (1.7) with further increase in Co loading up to 30%. The highest activity (conversion 55%) and selectivity of 99% to p-vanillin obtained for 13% Co-saponite in p-vanillyl alcohol oxidation was due to the highest distribution ratios of Co(3)O(4)/CoO phases. (C) 2010 Elsevier B.V. All rights reserved.
Keywords: Co-saponite; Cobalt oxide phase ratio; p-Vanillin; p-Vanillyl alcohol oxidation; Porosity transition; Temperature programmed reduction

Low thermal emissive surface properties of ZnO/polyimide composites prepared by pulsed laser deposition - Babrekar, Harshada A.; Jejurikar, S. M.; Jog, Jyoti Prakash; Adhi, K. P.; Bhoraskar, S. V. (Applied Surface Science, 2011)
We report the low thermal-emissive surface properties of composites of ZnO-polyimide. The composites were synthesized by depositing ZnO on polyimide surface by pulsed laser deposition technique. ZnO target was ablated at different incident energy densities and the substrate (polyimide) was held at elevated temperature. This facilitated the c-axis oriented growth of ZnO, which was inferred from the X-ray diffraction analysis. The composites consisted of multilayers having different electrical resistivities. The values of which are also estimated from Hagen-Rubens relation. The reduced infrared emissivities of the composite films, as compared to polyimide, were correlated to the increased carrier concentration and reduced surface resistivity estimated from the Hall measurements. (C) 2010 Elsevier B.V. All rights reserved.
Keywords: pulsed laser deposition; Thermal emissivity; Thin films; Zinc oxide

Magnetic properties of thermal plasma synthesized nanocrystalline nickel ferrite (NiFe2O4) - Nawale, Ashok B.; Kanhe, Nilesh S.; Patil, K. R.; Bhoraskar, S. V.; Mathe, Vikas L.; Das, A. K. (Journal of Alloys and Compounds, 2011)
A rapid synthesis method is reported for magnetic nanoparticles of nickel ferrite involving thermal plasma assisted vapor phase condensation process. The as-synthesized samples were characterized by X-ray Diffraction, Transmission Electron Microscopy, Vibrating Sample Magnetometer and X-ray Photoelectron Spectroscopy techniques. The average particle size was determined from the TEM micrographs and found to be around 30 nm. The effects of reactor parameters on the magnetic and structural properties have been evaluated, to find the optimized parameters so as to achieve the highest values of saturation magnetization and coercivity. Reasonably high saturation magnetization (48 emu/g) has been assigned to the high degree of crystallinity, achieved on account of high temperature during the growth, and the cation redistribution. The high value of coercivity (1150e) is explained on the basis of possible lattice defects arising from the cation redistribution. Detailed analysis of cation distribution using the XRD line intensity data leads to the conclusion that these samples are iron deficit and nickel rich. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: crystal structure; Magnetic measurements; Magnetization; Nanostructured materials; TEM

MgCl2 center dot 6PhCH(2)OH - a new molecular adduct as support material for ziegler-natta catalyst: synthesis, characterization and catalytic activity - Gnanakumar, Edwin S.; Thushara, K. S.; Bhange, Deu S.; Mathew, Renny; Ajithkumar, Thalasseril G.; Rajamohanan, P. R.; Bhaduri, Sumit; Gopinath, Chinnakonda S. (Dalton Transactions, 2011)
Benzyl alcohol has been used to prepare a single phase MgCl2 center dot 6BzOH molecular adduct as a support for an ethylene polymerization catalyst (Ziegler catalyst). The structural, spectroscopic and morphological aspects of the MgCl2 center dot 6BzOH molecular adduct and the Ziegler catalyst have been thoroughly studied by various physicochemical characterization techniques. The presence of MgO6 octahedrons due to the interaction of Mg2+ with six -OH groups of the benzyl alcohol is confirmed from a Raman feature at 703 cm(-1), and structural studies. The supported catalyst activity has been evaluated for the ethylene polymerization reaction. The lower polymerization activity of the titanated Ziegler-Natta catalyst compared with a standard catalyst is attributed to the strong interaction of titanium chloride with the support and associated electronic factors.

Mode-coupling glass transition in a fluid confined by a periodic potential - Nandi, Saroj Kumar; Bhattacharyya, Sarika Maitra; Ramaswamy, Sriram (Physical Review E, 2011)
We show that a fluid under strong spatially periodic confinement displays a glass transition within mode-coupling theory at a much lower density than the corresponding bulk system. We use fluctuating hydrodynamics, with confinement imposed through a periodic potential whose wavelength plays an important role in our treatment. To make the calculation tractable we implement a detailed calculation in one dimension. Although we do not expect simple 1d fluids to show a glass transition, our results are indicative of the behavior expected in higher dimensions. In a certain region of parameter space we observe a three-step relaxation reported recently in computer simulations [S. H. Krishnan, Ph.D. thesis, Indian Institute of Science (2005); Kim et al., Eur. Phys. J. Special Topics 189, 135 (2010)] and a glass-glass transition. We compare our results to those of Krakoviack [Phys. Rev. E 75, 031503 (2007)] and Lang et al. [Phys. Rev. Lett. 105, 125701 (2010)].

Molecular dynamics simulations of ch4 clathrate hydrate dissociation adjacent to hydrated silica surfaces - Bagherzadeh, A.; Englezos, Peter; Alavi, S.; Kumar, Rajnish; Ripmeester, John A. (7th International Conference on Gas Hydrates, 2011)
We use molecular dynamics simulations to study the decomposition of structure I CH4 clathrate hydrate exposed to water. Simulations are performed for a hydrate + water system and two related cases with the hydrate adjacent to hydrate silica layers. The simulations are in the NVE adiabatic ensemble paying careful attention to the non-isothermal nature of the hydrate dissociation process. The effects of mass and energy transfer on the hydrate dissociation rate are studied. The effect of the silica surface on the dissociation rate and mechanism are studied. It is observed that the hydrate layer decomposes more quickly in simulations where it is in contact with silica. The implications on decomposition of the hydrate in hydrate reservoirs adjacent to sand sediments are discussed.

Money handling and obesity: a test of the exaptation hypothesis - Karve, Shraddha; Shurpali, Ketaki; Dahanukar, Neelesh; Paranjape, Sharayu; Jog, Maithili; Belsare, Prajakta; Watve, Milind (Current Science, 2011)
The food reward centres in the brain play a central role in the regulation of food intake and thereby obesity. In the modern lifestyle, a number of artificial rewards such as money have been introduced and brain areas evolved for handling food rewards appear to be exapted to handle money and other rewards. This implies that the changing behaviour related to these rewards could influence obesity. Considering money as a reward, we conducted a survey of 211 full-time cashiers to test whether ownership over cash, amount of cash handled and duration of cash-handling work correlated with obesity parameters. Body mass index was significantly affected by sex, ownership, amount of money handled and duration of cash-handling service. Waist-to-hip ratio was significantly affected by sex, amount of money handled and marginally by ownership. The results are compatible with the exaptation hypothesis. It is possible that increasing importance of non-food rewards may play a significant role in the obesity epidemic.
Keywords: Body weight; economics of obesity; exaptation hypothesis; money handling

Nanoparticles that communicate in vivo to amplify tumour targeting - von Maltzahn, Geoffrey; Park, Ji-Ho; Lin, Kevin Y.; Singh, Neetu; Schwoeppe, Christian; Mesters, Rolf; Berdel, Wolfgang E.; Ruoslahti, Erkki; Sailor, Michael J.; Bhatia, Sangeeta N. (Nature Materials, 2011)

New CNN-type ruthenium pincer NHC complexes. synthesis and catalytic activity. mild, efficient hydrogenation of esters - Fogler, Eran; Balaraman, Ekambaram; Ben-David, Yehoshoa; Leitus, Gregory; Shimon, Linda J. W.; Milstein, David (Organometallics, 2011)
New pincer ruthenium complexes (2–6) based on the new bipyridine-NHC ligand 1 were prepared and studied, resulting in an efficient catalytic hydrogenation of esters to the corresponding alcohols under mild conditions. Reaction of the ligand 1 with RuH(Cl)CO(PPh3)3, followed by reaction with one equivalent of the base KHMDS, gave the mixed phosphine-NHC complex 2, incorporating a C–H-activated bipyridine ligand. Complex 2 has an octahedral structure containing two phosphorus atoms trans to each other, a hydride trans to the NHC ligand, and CO trans to the C–H-activated carbon of the bipyridine ligand. Using the precursor complex Ru(p-cymene)Cl2(CO), reaction with 1 followed by treatment of the intermediate product with one equivalent of KHMDS resulted in formation of the dichloride pincer complexes 3a and 3b, which are in equilibrium, as indicated by variable-temperature 1H NMR. Complex 3a is an octahedral, neutral, and symmetric complex with the CO ligand positioned trans to the central pyridine group of the pincer ligand and the two chlorides trans to each other, as indicated by single-crystal X-ray diffraction. Complex 3b is cationic, with an outer-sphere chloride. Reaction of the NHC ligand 1 with LiHMDS at low temperature followed by addition of RuH(Cl)CO(PPh3)3 resulted in the mixed phosphine-NHC complex 4, which has an octahedral structure containing phosphorus trans to the hydride, a CO trans to the NHC ligand, and an outer-sphere chloride. Chloride substitution by BArF– gave the X-ray-characterized complex 5. Deprotonation of complex 4 with KHMDS resulted in formation of the dearomatized complex 6. The in situ prepared 6 (from complex 4 and an equivalent of base) is among the best catalysts known for the hydrogenation of nonactivated esters to the corresponding alcohols under mild conditions.

N-Heterocyclic carbene catalyzed umpolung of michael acceptors for intermolecular reactions - Biju, Akkattu T.; Padmanaban, Mohan; Wurz, Nathalie E.; Glorius, Frank (Angewandte Chemie-International Edition, 2011)
eahciM! The N-heterocyclic carbene catalyzed umpolung of Michael acceptors proceeds through the formation of a deoxy-Breslow intermediate (see scheme; EWG=electron-withdrawing group). This nucleophilic species can react with other Michael acceptors in an intermolecular fashion, thereby resulting in the formation of homo- or heterodimeric olefins. This “Michael umpolung” should become a valuable method for the formation of densely functionalized olefins.
Keywords: carbenes; Michael acceptors; nitrogen heterocycles; organocatalysis; umpolung

N-heterocyclic carbene-catalyzed cross-coupling of aromatic aldehydes with activated alkyl halides - Padmanaban, Mohan; Biju, Akkattu T.; Glorius, Frank (Organic Letters, 2011)
N-Heterocyclic carbene-catalyzed umpolung of aldehydes followed by their interception with diarylbromomethanes has been reported. This conceptually novel transition-metal-free cross-coupling of aldehydes with alkyl halides works well at low catalyst loadings and under mild reaction conditions leading to the formation of diaryl acetophenone derivatives in good yields. In addition, α-halo ketones and esters can also be used as aldehyde reaction partners.

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.

One-pot synthesis of 2,4,5-trisubstituted imidazoles using MoO3/SiO2, an efficient and recyclable catalyst - Bhosale, Sidhanath V.; Kalyankar, Mohan B.; Nalage, Santosh V.; Bhosale, Dattatry S.; Pandhare, Swati L.; Kotbagi, Trupti V.; Shubhangi B. Umbarkar; Dongare, Mohan K. (Synthetic Communications, 2011)
[image omitted] A simple one-pot synthesis has been developed for the synthesis of 2,4,5-trisubstituted imidazoles using an efficient and recyclable MoO3/SiO2 solid acid catalyst by condensation of benzil or benzoin, benzaldehyde, and ammonium acetate in acetonitrile as a solvent. Using this solid catalyst, the reactions could be carried out under mild reaction conditions with very good yield of imidazoles, up to 95%. This catalyst could be recycled very easily, which makes this methodology environmentally benign.
Keywords: benzil; benzoin; cyclocondensation; imidazoles; MoO3; One-pot; SiO2; solid acid