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

Conformational modulation of Ant-Pro oligomers using chirality alteration of proline residues - Kale, Sangram S.; Kotmale, Amol S.; Dutta, Achintya Kumar; Pal, Sourav; Rajamohanan, P. R.; Sanjayan, Gangadhar J. (Organic & Biomolecular Chemistry, 2012)
Structural modulation of Ant-Pro (anthranilic acid-proline) oligomers has been carried out by chirality alteration of the proline residues. The results suggest that the chirality altered oligomers show well-defined helical conformation featuring nine-membered hydrogen bonding interactions - without compromising conformational rigidity.

Conformational transitions of the catalytic domain of heme-regulated eukaryotic initiation factor 2 alpha kinase, a key translational regulatory molecule - Sreejith, R. K.; Suresh, C. G.; Bhosale, Siddharth H.; Bhavnani, Varsha; Kumar, Avinash; Gaikwad, Sushama M.; Pal, Jayanta K. (Journal of Fluorescence, 2012)
In mammalian cells, the heme-regulated inhibitor (HRI) plays a critical role in the regulation of protein synthesis at the initiation step through phosphorylation of a-subunit of the eukaryotic initiation factor 2 (eIF2). In this study we have cloned and performed biophysical characterization of the kinase catalytic domain (KD) of rabbit HRI. The KD described here comprises kinase 1, the kinase insertion domain (KI) and kinase 2. We report here the existence of an active and stable monomer of HRI (KD). The HRI (KD) containing three tryptophan residues was examined for its conformational transitions occurring under various denaturing conditions using steady-state and time-resolved tryptophan fluorescence, circular dichroism (CD) and hydrophobic dye binding. The parameter A and phase diagram analysis revealed multi-state unfolding and existence of three stable intermediates during guanidine hydrochloride (Gdn-HCl) induced unfolding of HRI (KD). The protein treated with 6 M Gdn-HCl showed collisional and static mechanism of acrylamide quenching and the constants (K-sv=3.08 M-1 and K-s=5.62 M-1) were resolved using time resolved fluorescence titration. Based on pH, guanidine hydrochloride and temperature mediated transitions, HRI (KD) appears to exemplify a rigid molten globule-like intermediate with compact secondary structure, altered tertiary structure and exposed hydrophobic patches at pH 3.0. The results indicate the inherent structural stability of HRI (KD), a member of the class of stress response proteins.
Keywords: Circular dichroism (CD); eIF2 alpha kinase; Heme-regulated inhibitor; Molten globule; Steady-state and time-resolved fluorescence

Constrained variational approach for energy derivatives in Intermediate hamiltonian fock-space coupled-cluster theory - Ghosh, Aryya; Gupta, Jitendra; Pal, Sourav; Vaval, Nayana (Chemical Physics, 2012)
Fock-space multi-reference coupled cluster theory is an efficient method for electronic structure of nearly degenerate cases. However, it suffers from the intruder state problem for large model space. The intermediate Hamiltonian formulation eliminates intruder state problem and helps in the convergence of equations. In this paper we have implemented intermediate Hamiltonian approach in Fock-space coupled cluster method for the response properties. We test our method for the dipole moments of doublet radicals. We report dipole moments of CN, SF and NS radicals. (C) 2011 Elsevier B. V. All rights reserved.
Keywords: Constrained variational approach; Fock-space multi-reference coupled cluster; Intermediate Hamiltonian theory; Response approach

Control of porosity by using isoreticular zeolitic imidazolate frameworks (IRZIFs) as a template for porous carbon synthesis - Pachfule, Pradip; Biswal, Bishnu P.; Banerjee, Rahul (Chemistry-A European Journal, 2012)
Herein, by using isoreticular zeolitic imidazolate frameworks (IRZIFs) as a template, we report the synthesis, morphology, and gas adsorption properties of porous carbon synthesized by a nanocasting method at 1000 degrees C, in which furfuryl alcohol (FA) was used as a carbon source. By using IRZIFs with variable porosity as templates, we could achieve control over the carbon porosity and H-2 and CO2 uptake. The resultant microporous carbon C-70, synthesized by using ZIF-70 as the template, is the most porous (Brunauer-Emmett-Teller (BET) surface area 1510 m(2)g(-1)). Carbon C-68, synthesized by using ZIF-68, has moderate porosity (BET surface area 1311 m(2)g(-1)), and C-69, synthesized by using ZIF-69, has the lowest porosity in this series (BET surface area 1171 m(2)g(-1)). The porous carbons C-70, C-68, and C-69, which have graphitic texture, have promising H2 uptake capacities of 2.37, 2.15, and 1.96 wt%, respectively, at 77 K and 1 atm. Additionally, C-70, C-68, and C-69 show CO2 uptake capacities of 5.45, 4.98, and 4.54 mmolg(-1), respectively, at 273 K and 1 atm. The gas uptake trends shown by C-70, C-68, and C-69 clearly indicate the dependence of carbon porosity on the host template. Moreover, the as-synthesized carbons C-70, C-68, and C-69 show variable conductivity.
Keywords: Carbon; Hydrogen storage; metal-organic frameworks; microporous materials; zinc

Controlled release of nutrients to mammalian cells cultured in shake flasks - Hegde, Swati; Pant, Tejal; Pradhan, Ketaki; Badiger, Manohar V.; Gadgil, Mugdha (Biotechnology Progress, 2012)
Though cell culture-based protein production processes are rarely carried out under batch mode of operation, cell line and initial process development operations are usually carried out in batch mode due to simplicity of operation in widely used scale down platforms like shake flasks. Nutrient feeding, if performed, is achieved by bolus addition of concentrated feed solution at different intervals, which leads to large transient increases in nutrient concentrations. One negative consequence is increased waste metabolite production. We have developed a hydrogel-based nutrient delivery system for continuous feeding of nutrients in scale down models like shake flasks without the need for manual feed additions or any additional infrastructure. Continuous delivery also enables maintaining nutrient concentrations at low levels, if desired. The authors demonstrate the use of these systems for continuous feeding of glucose and protein hydrolysate to a suspension Chinese Hamster Ovary (CHO) culture in a shake flask. Glucose feeding achieved using the glucose-loaded hydrogel resulted in a 23% higher integral viable cell density and an 89% lower lactate concentration at the end of the culture when compared with a bolus-feed of glucose. (c) 2011 American Institute of Chemical Engineers Biotechnol. Prog., 2012

Controlled synthesis of O-glycopolypeptide polymers and their molecular recognition by lectins - Pati, Debasis; Shaikh, Ashif Y.; Das, Soumen; Nareddy, Pavan Kumar; Swamy, Musti J.; Hotha, Srinivas; Sen Gupta, Sayam (Biomacromolecules, 2012)
The facile synthesis of high molecular weight water-soluble O-glycopolypeptide polymers by the ring-opening polymerization of their corresponding N-carboxyanhydride (NCA) in very high yield (overall yield > 70%) is reported. The per-acetylated-O-glycosylated lysine-NCA monomers, synthesized using stable glycosyl donors and a commercially available protected amino acid in very high yield, was polymerized using commercially available amine initiators. The synthesized water-soluble glycopolypeptides were found to be alpha-helical in aqueous solution. However, we were able to control the secondary conformation of the glycopolypeptides (alpha-helix vs nonhelical structures) by polymerizing raceznic amino acid glyco NCAs. We have also investigated the binding of the glycopolypeptide poly(alpha-manno-O-lys) with the lectin Con-A using precipitation and hemagglutination assays as well as by isothermal titration calorimetry (ITC). The ITC results clearly show that the binding process is enthalpy driven for both alpha-helical and nonhelical structures, with negative entropic contribution. Binding stoichiometry for the glycopolypeptide poly(alpha-manno-O-lys) having a nonhelical structure was slightly higher as compared to the corresponding polypeptide which adopted an alpha-helical structure.

Copper modified waste fly ash as a promising catalyst for glycerol hydrogenolysis - Rode, C. V.; Mane, R. B.; Potdar, A. S.; Patil, P. B.; Niphadkar, P. S.; Joshi, P. N. (Catalysis Today, 2012)
Several catalyst formulations using waste fly ash along with Cu were prepared and characterised by XRD, BET and TEM. These catalysts were also evaluated for the first time for hydrogenolysis of glycerol to 1,2 propanediol (1,2-PDO) in a batch reactor under 52 bar H-2 pressure in the temperature range of 473-513 K conditions. The fly ash pretreated by alkali using the fusion method and impregnated with Cu showed higher activity and stability for glycerol hydrogenolysis. Due to pretreatment with alkali at high temperature, transformation of alpha-quartz to the tridymite phase of SiO2 occurred. More importantly, use of alkali either during the pretreatment or the Cu loading step resulted in a high dispersion on the surface which was responsible for higher glycerol conversion and 1,2-PDO selectivity. The effects of temperature, Cu loading and solvent on glycerol conversion and product selectivities were also studied in this work. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: 1; 2-Propanediol; Alkali fusion; Cu loading; Fly ash; Glycerol hydrogenolysis

Crystallization and X-ray structure analysis of a thermostable penicillin G acylase from alcaligenes faecalis - Varshney, Nishant Kumar; Kumar, R. Suresh; Ignatova, Zoya; Prabhune, Asmita; Pundle, Archana; Dodson, Eleanor J.; Suresh, C. G. (Acta Crystallographica Section F-Structural Biology and Crystallization Communications, 2012)
{The enzyme penicillin G acylase (EC 3.5.1.11) catalyzes amide-bond cleavage in benzylpenicillin (penicillin G) to yield 6-aminopenicillanic acid, an intermediate chemical used in the production of semisynthetic penicillins. A thermostable penicillin G acylase from Alcaligenes faecalis (AfPGA) has been crystallized using the hanging-drop vapour-diffusion method in two different space groups: C2221, with unit-cell parameters a = 72.9
Keywords: calcium binding; disulfide bridges; Ntn hydrolases; orthorhombic form; tetragonal form; Thermostability

CVD synthesis of highly graphitized single-walled carbon nanotubes using nitrogen-pretreated Fe-Mo/MgO catalyst - Patil, Gaurav; Sarode, Chetan; Patil, Rahul; Gokhale, Suresh (Chemistry Letters, 2012)
Single-walled carbon nanotubes (SWNTs) with highly graphitized structure were synthesized by thermal chemical vapor deposition using an improved nitrogen-pretreated Fe-Mo/MgO catalyst. The effects of nitrogen pretreatment of Fe-Mo/MgO on the structure and properties of SWNTs were studied by TEM, Raman spectroscopy, and TGA. The investigations revealed that the nitrogen pretreatment of the catalyst promoted the growth of SWNTs. It also enhanced the structural features and thermal properties of SWNTs.

Descriptors as probes for inter-molecular interactions and external perturbation - Pal, Sourav (Applications of Density Functional Theory to Chemical Reactivity, 2012)
In this article, different reactivity descriptors have been reviewed. Conceptual density functional theory is an important area where a lot of interesting developments in terms of descriptors and molecule interactions have taken place in recent years. This review will highlight our own work on such development of descriptors and their applications to characterise stability and reactivity in molecule systems.
Keywords: Conceptual density functional theory; Electric field effect; Global reactivity descriptors; HSAB; Local HSAB; Local reactivity descriptors

Development of genomic simple sequence repeat markers for linseed using next-generation sequencing technology - Kale, Sandip M.; Pardeshi, Varsha C.; Kadoo, Narendra Y.; Ghorpade, Prakash B.; Jana, Murari M.; Gupta, Vidya S. (Molecular Breeding, 2012)
Linseed (Linum usitatissimum L.) is regarded as a cash crop of tomorrow because of the presence of nutraceutically important alpha-linolenic acid (ALA) and lignan. However, only limited breeding progress has been made in this crop, mainly due to the lack of sufficient genetic and genomic resources. Among these, simple sequence repeats (SSR) are useful DNA markers for diversity analysis, genetic mapping and tagging traits because of their co-dominant and highly polymorphic nature. In order to develop SSR markers for linseed, we used three microsatellite isolation methods, viz., PCR Isolation of Microsatellite Arrays (PIMA), 5'-anchored PCR method, and Fast Isolation by AFLP of Sequences COntaining repeats (FIASCO). The amplified products from these methods were pooled and sequenced using the 454 GS-FLX platform. A total of 36,332 reads were obtained, which assembled into 2,183 contigs and 2,509 singlets. The contigs and the singlets contained 1,842 microsatellite motifs, with dinucleotide motifs as the most abundant repeat type (54%) followed by trinucleotide motifs (44%). Based on this, 290 SSR markers were designed, 52 of which were evaluated using a panel of 27 diverse linseed genotypes. Among the three enrichment methods, the 5'-anchored PCR method was most efficient for isolation of microsatellites, while FIASCO was most efficient for developing SSR markers. We show the utility of next-generation sequencing technology for efficiently discovering a large number of microsatellite markers in non-model plants.
Keywords: Flax; Microsatellite isolation; Next-generation sequencing; SSR

Dimensionality reduction in computational demarcation of protein tertiary structures - Joshi, Rajani R.; Panigrahi, Priyabrata R.; Patil, Reshma N. (Journal of Molecular Modeling, 2012)
Predictive classification of major structural families and fold types of proteins is investigated deploying logistic regression. Only five to seven dimensional quantitative feature vector representations of tertiary structures are found adequate. Results for benchmark sample of non-homologous proteins from SCOP database are presented. Importance of this work as compared to homology modeling and best-known quantitative approaches is highlighted.
Keywords: Logistic regression; Principal component analysis; Protein structural classes; Quantitative features of tertiary folds; SCOP database

Dimethyl [(2R,3R,5S)-5-phenylmorpholine-2,3-diyl]diacetate as a designer substrate in the syntheses of important heterocyclic scaffolds - Pandey, Ganesh; Gaikwad, Amrut L.; Gadre, Smita R. (Asian Journal of Organic Chemistry, 2012)
Designed scaffold dimethyl [(2R,3R,5S)-5-phenylmorpholine-2,3-diyl]diacetate was synthesized in optically pure form by photoinduced one-electron reductive beta-activation of an alpha,beta-unsaturated carbonyl moiety for stereoselective C-C bond formation. Use of the morpholine derivative as a ``chemical multitalent'' is demonstrated by its easy transformation to valuable heterocyclic building blocks such as methyl [(2R,3S)-3-hydroxy-5-oxopyrrolidin-2-yl]acetate, methyl [(2R,3S)-3-amino-5-oxotetrahydrofuran-2-yl]acetate, (3R,4S)-4-aminohexane-1,3,6-triol, and 2-[(2R,3S)-3-aminotetrahydrofuran-2-yl]ethanol.
Keywords: Amino alcohols; butyrolactams; butyrolactones; morpholines; photoinduced electron transfer reactions

Discovering bisdemethoxycurcumin from curcuma longa rhizome as a potent small molecule inhibitor of human pancreatic alpha-amylase, a target for type-2 diabetes - Ponnusamy, Sudha; Smita S. Zinjarde; Bhargava, Shobha; Rajamohanan, P. R.; RaviKumar, Ameeta (Food Chemistry, 2012)
Curcuma longa rhizome is used extensively in culinary preparations in Far East and South-East Asia. Health benefits of curcuminoids from C. longa as antioxidants, anti-cancer and anti-inflammatory molecules have been well documented. We report here for the first time that Bisdemethoxycurcumin (BDMC) from C. longa, acts as an inhibitor to inactivate human pancreatic alpha-amylase, a therapeutic target for oral hypoglycemic agents in type-2 diabetes. Bioactivity guided isolation of rhizome isopropanol extract led to the identification by HPLC and NMR of BDMC as a lead small molecule inhibitor of porcine and human pancreatic alpha-amylase with an IC50 value of 0.026 and 0.025 mM, respectively. Kinetic analysis revealed that using starch as the substrate, HPA exhibited an uncompetitive mode of inhibition with an apparent K-i of 3.0 mu M. The study gains importance as BDMC could be a good drug candidate in development of new inhibitors of HPA and of functional foods for controlling starch digestion in order to reduce post-prandial hyperglycemia. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: BDMC; Curcuma longa; Human pancreatic amylase; kinetics; Type-2 diabetes

Distinctions in early stage unwinding mechanisms of zwitterionic, capped, and neutral forms of different alpha-helical homopolymeric peptides - Pandey, Prithvi Raj; Roy, Sudip (Journal of Physical Chemistry B, 2012)
Molecular dynamics simulations of alpha-helical polyalanine, polyleucine, polylysine, and poly(glutamic acid) with different forms of terminal groups in water at 300 K showed sharp distinctions in their unwinding mechanisms. Zwitterionic, capped, and neutral forms of polyalanine, polyleucine, and polylysine have been explored to elucidate their unwinding mechanism at very early stage, e.g., initial time window. Role of water in the unwinding mechanisms of the various helices has been envisaged. Also, it is evident from our calculations that the short- and long-range nonbonded interactions among the side chains is an important factor determining the unwinding mechanisms of the various homopolymeric alpha-helices. These findings can be helpful in constructing predictive models for understanding of the unwinding of alpha-helical proteins and peptides.

Dynamic proteome in enigmatic preeclampsia: an account of molecular mechanisms and biomarker discovery - Mary, Sheon; Patil, Gouri V.; Kulkarni, Asmita V.; Kulkarni, Mahesh J.; Joshi, Sadhana R.; Mehendale, Savita S.; Giri, Ashok P. (Proteomics Clinical Applications, 2012)
The coevolution of genomics and proteomics has led to advancements in the field of diagnosis and molecular mechanisms of disease. Proteomics is now stepping into the field of obstetrics, where early diagnosis of pregnancy complication such as preeclampsia (PE) is imperative. PE is a multifactorial disease characterized by hypertension with proteinuria, which is a leading cause of maternal and neonatal morbidity and mortality occurring in 5-7% of pregnancies worldwide. This review discusses the probable molecular mechanisms that lead to PE and summarizes the proteomics research carried out in understanding the pathogenicity of PE, and for identifying the candidate biomarker for diagnosis of the disease.
Keywords: Hypertension; Oxidative stress; Pregnancy complication; Proteinuria

Effect of addition of `carrier' DNA during transient protein expression in suspension CHO culture - Pradhan, Ketaki; Gadgil, Mugdha (Cytotechnology, 2012)
Transient protein expression using polyethyleneimine as a transfection agent is useful for the rapid production of small amounts of recombinant proteins. It is known that an increase in extracellular DNA concentration during transfection can lead to a nonlinear increase in intracellular DNA concentration. We present an approach that hypothesizes that this nonlinearity can be used to decrease the amount of plasmid required for productive transfections. Through addition of non coding `carrier' DNA to increase total DNA concentration during transfection, we report a statistically significant increase in protein (IgG) expression per unit plasmid used for transfection. This approach could be useful to increase protein yields for large scale transfections under conditions where plasmid availability is limited.
Keywords: Carrier DNA; Cell age; DNA: polyethyleneimine particle size; Medium equilibration with CO2; pH excursion; Salmon sperm DNA; Transient protein expression

Effect of digestive ripening agent on nanoparticle size in the digestive ripening process - Sahu, Puspanjali; Bhagavatula L. V. Prasad (Chemical Physics Letters, 2012)
Digestive ripening is an efficient method that leads to monodispersed nanoparticles from polydispersed ones. A systematic investigation of digestive ripening with different agents viz. dodecanethiol and dodecylamine on different metallic systems is presented. It is shown that both the metallic system involved and the digestive ripening agent have influences on the final size distribution. Further, it is demonstrated that the interaction strength between the different metals and the digestive ripening agents based on Hard Soft Acid Base principles could be invoked to explain the variation in nanoparticle size. (C) 2012 Elsevier B.V. All rights reserved.

Effect of particle size on selective hydrogenation of cinnamaldehyde by Pt encapsulated in mesoporous silica - Prashar, Atul K.; Mayadevi, S.; Devi, R. Nandini (Catalysis Communications, 2012)
Pt nanoparticles of various sizes, viz. 8. 4.9, 3.6 and 1.8 nm were encapsulated in 2D hexagonal mesoporous silica by in-situ synthesis as well as post synthetic modifications so that the final catalyst composition was <= 1 wt.% Pt/SiO2. A kinetic analysis of the effect of particle size on selective hydrogenation of cinnamaldehyde was carried out on these catalysts. It was found that the materials, even at such low loading of Pt, were very active for the hydrogenation and selective for the desired product, cinnamyl alcohol. Among the different particle sizes, selectivity was found to be the highest on 8 nm particles. Kinetic analysis shows that the reaction follows a consecutive reaction pathway. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: alpha; beta-Unsaturated aldehydes; Cinnamaldehyde hydrogenation; Kinetic analysis; Mesoporous silica; Pt nanoparticles; Selective hydrogenation

Effect of preparation parameters of Cu catalysts on their physico-chemical properties and activities for glycerol hydrogenolysis - Mane, R. B.; Kondawar, S. E.; Niphadkar, P. S.; Joshi, P. N.; Patil, K. R.; Rode, C. V. (Catalysis Today, 2012)
Cu based catalysts were prepared by co-precipitation, alkali fusion followed by precipitation and direct solid state fusion methods. The changes in the phase formation, morphology, crystallite size, extent of aggregation, strength and nature of acid sites were observed due to variations in precipitating agents and also their order of addition. The catalyst prepared by co-precipitation using Na2CO3 showed the predominant presence of metallic Cu phase with a crystallite size of 5 nm, well segregated spherical morphology and highest acidity in the activated sample. These intrinsic properties contributed to achieve the highest glycerol conversion of 62% and 1,2-PDO selectivity of 88% in glycerol hydrogenolysis. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Co-precipitation; Cu catalysts; Glycerol hydrogenolysis; Physico-chemical properties; Solid state fusion

Effects of arsenite stress on growth and proteome of Klebsiella pneumoniae - Daware, Vandana; Kesavan, Suresh K.; Patil, Rajendra; Natu, Arvind; Kumar, Ameeta; Kulkarni, Mahesh J.; Gade, Wasudeo N. (Journal of Biotechnology, 2012)
In the present study an arsenite, As(III), tolerating bacterium, MR4, was isolated from Mulla River Pune, India, capable of reducing arsenate to arsenite and identified as Klebsiella pneumoniae (HQ857583). Comparative proteomic analysis using two-dimensional gel electrophoresis (2-DGE) and matrix assisted laser desorption ionization-time of flight-time of flight (MALDI-TOF/ TOF) was used to monitor the proteins undergoing changes in expression levels under 2.5 mM As(III) stress. The 2-DGE proteome map has shown that 60 proteins were differentially expressed under As(III) stress, of which 39 proteins were successfully identified with a MASCOT score greater than 70 (p < 0.05). Among the identified proteins, membrane transport/ binding proteins, porins, and amino acid metabolism enzymes were down-regulated while stress responsive proteins and antioxidant enzymes were up-regulated. Proteins involved in carbohydrate metabolism, particularly those in pentose phosphate pathway were also up-regulated while those involved in pyruvate metabolism were down-regulated. However, proteins involved in glycolysis and tricarboxylic acid cycle showed a mixed regulation response. These findings provide new insights into the probable mechanisms by which K. pneumoniae (HQ857583) could be adapting to As(III) stress. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: (2-DGE); Arsenite stress; Klebsiella pneumoniae; MALDI-TOF-TOF; Two dimensional gel electrophoresis

Efficient oxygen reduction electrocatalyst from graphene by simultaneously generating pores and nitrogen doped active sites - Palaniselvam, Thangavelu; Aiyappa, Harshitha Barike; Kurungot, Sreekumar (Journal of Materials Chemistry, 2012)
A simple way to simultaneously create pores and nitrogen doped active sites on graphene for the electrochemical oxygen reduction reaction (ORR) is developed. The key aspect of the process is the in-situ generation of Fe2O3 nanoparticles and their concomitant dispersion on graphene by pyrolyzing graphene oxide (GO) with the iron phenanthroline complex. Thus the deposited Fe2O3 nanoparticles act as the seeds for pore generation by etching the carbon layer along the graphene-Fe2O3 interface. Detection of the presence of Fe3C along with Fe2O3 confirms carbon spill-over from graphene as a plausible step involved in the pore engraving process. Since the process offers a good control on the size and dispersion of the Fe2O3 nanoparticles, the pore size and distribution also could be managed very effectively in this process. As the phenanthroline complex decomposes and gives Fe2O3 nanoparticles and subsequently the pores on graphene, the unsaturated carbons along the pore openings simultaneously capture nitrogen of the phenanthroline complex and provide very efficient active sites for ORR under alkaline conditions. The degree of nitrogen doping and hence the ORR activity could be further improved by subjecting the porous material for a second round of nitrogen doping using iron-free phenanthroline. This porous graphene enriched with the N-doped active sites effectively reduces oxygen molecule through a 3e(-) pathway, suggesting a preferential shift towards the more favourable 4e(-) route compared to the 2e(-) reaction as reported for many N-doped carbon nano-morphologies. The 90 mV onset potential difference for oxygen reduction as compared to the state-of-the art 20 wt% Pt/C catalyst is significantly low compared to the overpotentials in the range of 120-200 mV reported in the literature for few N-doped graphenes.

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

Efficient synthesis of a hydroxyethylamine (HEA) isostere and its alpha-aminophosphonate and phosphoramidate derivatives as potential anti-HIV agents - Bhattacharya, Asish K.; Rana, Kalpeshkumar C.; Pannecouque, Christophe; De Clercq, Eric (Chemmedchem, 2012)
HIV protease is a promising drug target for AIDS therapy, and several potent HIV-1 protease inhibitors have been reported to date. Although existing inhibitors exhibit high selectivity, they have also been associated with severe side effects and the possible emergence of therapeutic resistance. As HIV protease cleaves the peptide bond via a tetrahedral intermediate, various transition-state models such as hydroxyethylamine (HEA) have been designed. We therefore pursued an efficient synthesis of an HEA isostere; this was performed with a novel one-pot reductiontransiminationreduction reaction sequence as a key step. a-Aminophosphonate and phosphoramidate derivatives of the HEA isostere were designed and synthesized, and all of the synthesized derivatives were assayed for their anti-HIV activities against wild-type and mutant HIV strains. Phosphoramidate derivative 15?a was found to be the most active of all synthesized compounds against the IIIB and RES056 strains. As phosphonates are known to exhibit physiological stability, good cell permeability, and other promising pharmacokinetic characteristics, our newly synthesized compounds have the potential as alternatives to existing therapeutics and diagnostics.
Keywords: a-aminophosphonates; antiviral agents; hydroxyethylamine isosteres; phosphoramidates; synthesis

Efficient total synthesis of calothrixin B - Bhosale, Shrikar M.; Gawade, Rupesh L.; Puranik, Vedavati G.; Kusurkar, Radhika S. (Tetrahedron Letters, 2012)
An efficient synthesis of calothrixin B (2) is demonstrated starting from 9H-carbazol-4-ol, having two one-pot reaction sequences as key steps. As a novel observation, DMF-methanol was shown to be a hydride donor for reduction of aldehyde to alcohol. Unexpectedly, nucleophilic substitution of benzyloxy by methoxy group was observed. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Calothrixin B; CAN; DMF-methanol; Hydride donor

Electrochemical preparation of luminescent graphene quantum dots from multiwalled carbon nanotubes - Shinde, Dhanraj B.; Pillai, Vijayamohanan K. (Chemistry-A European Journal, 2012)
Green luminescent, graphene quantum dots (GQDs) with a uniform size of 3, 5, and 8.2(+/- 0.3) nm in diameter were prepared electrochemically from MWCNTs in propylene carbonate by using LiClO4 at 90?degrees C, whereas similar particles of 23(+/- 2) nm were obtained at 30?degrees C under identical conditions. Both these sets of GQDs displayed a remarkable quantum efficiency of 6.3 and 5.1?%, respectively. This method offers a novel strategy to synthesise size-tunable GQDs as evidenced by multiple characterisation techniques like transmission and scanning electron microscopy, atomic force microscopy, Raman spectroscopy and X-ray diffraction (XRD). Photoluminescence of these GQDs can be tailored by size variation through a systematic change in key process parameters, like diameter of carbon nanotube, electric field, concentration of supporting electrolyte and temperature. GQDs are promising candidates for a variety of applications, such as biomarkers, nanoelectronic devices and chemosensors due to their unique features, like high photostability, biocompatibility, nontoxicity and tunable solubility in water.
Keywords: electrochemical synthesis; graphene; Nanostructures; photoluminescence; quantum dots

Electrostatic grafting of a triphenylphosphine sulfonate on SBA-15: application in palladium catalyzed hydrogenation - Wang, Lei; Dehe, Daniel; Philippi, Thomas; Seifert, Andreas; Ernst, Stefan; Zhou, Zhou; Hartmann, Martin; Taylor, Robin N. Klupp; Singh, Anand Pal; Jia, Mingjun; Thiel, Werner R. (Catalysis Science & Technology, 2012)
A novel strategy for the immobilization of a sulfonate functionalized triphenylphosphine ligand by ion-ion interactions on an imidazolium modified SBA-15 is presented. A support containing electrostatically grafted triphenylphosphine as the ligand was reacted with PdCl2( CNPh)(2) and the resulting hybrid material catalyzed olefin hydrogenation under mild conditions. The catalyst exhibits excellent activity, selectivity and stability and it can be reused for at least ten times without any loss of activity. An analogous but covalently grafted palladium system does not show any hydrogenation activity under the same conditions. TEM images of the used catalyst clearly prove the absence of palladium nanoparticles. Additionally, XPS investigations prove that palladium( 0) is formed and the phosphine is oxidized. By AAS no palladium contamination down to 0.5 X 10(-4) mmol could be detected in the products and further leaching tests verified the reaction to be truly heterogeneous. This concept of non-covalent immobilization guarantees a tight bonding of the catalytically active species to the surface in combination with a high mobility, which should be favorable for other catalyses, too.

Enhanced permeation, leaf retention, and plant protease inhibitor activity with bicontinuous microemulsions - Tamhane, Vaijayanti A.; Dhaware, Deepika G.; Khandelwal, Neha; Giri, Ashok P.; Panchagnula, Venkateswarlu (Journal of Colloid and Interface Science, 2012)
Bicontinuous microemulsions (BCMEs) have excellent solubulizing properties along with low interfacial tension and aqueous content that can be controlled. In this work, water soluble plant protease inhibitor (PI), well characterized for its activity against insect pests, was incorporated into a BCME system and explored for permeation on hydrophobic leaf surfaces and protease inhibition activity. The bicontinuous nature of the microemulsion containing water:2-propanol:1-butanol (55:35:10 w/w) was characterized using conductivity and self-diffusion coefficient measurements. The PI was soluble in the water-rich bicontinuous domains, stable in the microemulsions, and protease inhibition activity was retained for a prolonged duration. The microemulsions ensured greater wettability and a wider spread of the PI on hydrophobic leaf surfaces as revealed by contact angle measurements. Significantly, trypsin inhibition activity assays of the PI recovered from the leaves after delivery from the microemulsion indicated a significant increase in the PI retention on the leaf. This BCME enabled greater leaf permeation and retention of the PI can be attributed to a temporary disruption of the waxy leaf surface followed by self-repair without causing any long term damage to the plant. (C) 2012 Elsevier Inc. All rights reserved.
Keywords: Bicontinuous microemulsion; Biopesticide; Microemulsion pesticide; protease inhibitor; Protein encapsulation; Protein permeation

Environmental pollution reduction in cement industry for cocombustion of waste tyre and coal as a fuel - Patil, R. K.; Garnaik, Baijayantimala; Khond, M. P.; Nawale, L. G. (International Journal of Modern Engineering Research, 2012)
In recent years, there are several problems encountered in waste management system particularly waste tyre as well as coals. The energy generation on incineration provides large amount of polycyclic aromatic hydrocarbon (PAH) emissions which is the cause of major environmental threat. Therefore, the combustion of coal and tyre were carried out in cement industry in order to generate heat energy at 1300oC and the only remaining residue (steel powder) to enhance the strength of the cement. At the outset, the particle size of coal and tyre was cut into 63-75 and 180-212 µm respectively. Combustion experiments were conducted using Nelson reactor under controlled conditions in presence of air and also in presence of nitrogen gas (INOX) atmosphere. The temperature range was varied from 300-13000C and several fuel mass loading in the furnace, expressed in terms of bulk equivalence ratios in the range of 0.7-2.4. At fixed bulk equivalence ratios, as the furnace gas (Air) temperature increased the polycyclic aromatic hydrocarbon yields from both fuels decreased drastically, while the CO2 yields increased. At the highest temperature around 13000C, the effluent of combustion of both (coal and tyre) fuels was practically devoid of polycyclic aromatic hydrocarbon (PAH) (at a detection limit of 0.3 µg of a PAH component/g of fuel burnt). In order to understand the rate of thermal effect and morphology of co combustion material (coal and tyre), the preliminary results are very essential to explore. Therefore, the thermo gravimetric analysis (TGA) and environmental scanning electron microscopy (ESEM) were carried out and results of coal and tyre mixture at various temperature conditions will be highlighted.

Enzyme immobilization on epoxy supports in reverse micellar media: prevention of enzyme denaturation - Thudi, Lahari; Jasti, Lakshmi Swarnalatha; Swarnalatha, Yalangi; Fadnavis, Nitin W.; Mulani, Khudbudin Baban; Deokar, Sarika Babasaheb; Ponrathnam, Surendra (Journal of Molecular Catalysis B-Enzymatic, 2012)
Immobilization of enzymes such as alpha-chymotrypsin (EC 3.4.21.1), yeast alcohol dehydrogenase (YADH) from Saccharomyces cerevisiae (EC 1.1.1.1) and glucose dehydrogenase (GDH) from Gluconobacter cerinus (EC 1.1.1.119) has been carried out. Copolymers of allyl glycidyl ether (AGE) crosslinked with 25% ethylene glycol dimethacrylate (EGDM) (25 mg, dry wt) were contacted with the enzymes solubilized in reverse micellar media (0.5-5 mg/mL)(overall) of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) salt in isooctane, and cetyl trimethylammonium bromide (CTAB) in chloroform-isooctane (50:50, v/v). Although the enzymes are readily denatured (>90%) after adsorption on the copolymer in aqueous buffers, no such adsorption-induced denaturation takes place in reverse micelles. alpha-Chymotrypsin is remarkably stable in AOT reverse micelles when 0.025 M citrate buffer of pH 9.0 containing 2 mM CaCl2 is used in the water pools instead of Tris-HCl buffer of pH 8.5. It was possible to achieve enzyme concentration of 5 mg/mL in 0.3 M AOT at molar ratio of water to surfactant, (W-0), 30 and to obtain alpha-chymotrypsin loading of 20 mg/g of copolymer. The recovered enzyme solution can be reused with a fresh batch of polymer after supplementing the depleted solution. The immobilized enzyme exhibits excellent stability in aqueous buffers at room temperature and can be recycled several times. YADH is stable in both AOT and CTAB reverse micelles while GDH is stable only in CTAB reverse micelles containing 0.05 M Tris-HCI buffer of pH 8.5. Interestingly, the combination of YADH (2.5 mg/g) and GDH (0.5 mg/g) co-immobilized on the copolymer using CTAB-chloroform-isooctane system can be used for regeneration and recycle of NADPH at least 50 times as exemplified by complete reduction of a prochiral ketoester, ethyl 4-phenyl-2,4-dioxobutyrate (10 mM) to ethyl (R)-2-hydroxy-4-phenylbutyrate (HPB ester) using NADPH (0.2 mM). (C) 2011 Elsevier B.V. All rights reserved.
Keywords: allyl glycidyl ether; alpha-Chymotrypsin; ethylene glycol dimethacrylate; Glucose dehydrogenase; Reverse micelles; Yeast alcohol dehydrogenase

Equation-of-motion coupled-cluster method for the study of shape resonance - Ghosh, Aryya; Vaval, Nayana; Pal, Sourav (Journal of Chemical Physics, 2012)
The equation-of-motion coupled-cluster method (EOM-CC) is applied for the first time to calculate the energy and width of a shape resonance in an electron-molecule scattering. The procedure is based on inclusion of complex absorbing potential with EOM-CC theory. We have applied this method to investigate the shape resonance in e(-)N(2), e(-)CO, and e(-)C(2)H(2). (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4729464]

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

Expanding the structural repertoire of beta/alpha Ant-Pro (anthranilic acid-proline) oligomers into gamma/alpha 2-Amb-Pro (2-aminomethyl benzoic acid-proline) oligomers - Ramesh, Veera V. E.; Priya, Gowri; Rajamohanan, P. R.; Hofmann, Hans-Joerg; Sanjayan, Gangadhar J. (Tetrahedron, 2012)
In this article, we report a novel class of heterogeneous synthetic oligomers featuring the conformationally constrained amino acid residues - 2-aminomethyl benzoic acid (2-Amb) and proline (Pro) in repeating sequences. Oligomers as large as hexadecamers featuring the conformationally restricted gamma/alpha 2-Amb-Pro motif have been assembled using solution-phase Boc strategy, following multi-step synthetic sequences starting from the commercially available O-toluic acid. EDC-mediated peptide coupling has been found to be optimum for the assembly of the relatively non-polar oligomers, which could be readily purified by the standard column chromatographic purification procedures. This study offers considerable prospects of expanding the structural repertoire of beta/alpha Ant-Pro motif, which has been described earlier to assume right-handed helical architecture displaying robust nine-membered-ring closed network of hydrogen-bonding interactions, into gamma/alpha 2-Amb-Pro motif. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Amino acids; Foldamer; Peptides; Proline; Synthetic oligomers

Extended coupled cluster for Raman and infrared spectra of small molecules - Joshi, Sayali P.; Dutta, Achintya Kumar; Pal, Sourav; Vaval, Nayana (Chemical Physics, 2012)
In this paper we study the harmonic vibrational frequencies, infrared (IR) intensities, Raman intensities and depolarization ratio using extended coupled cluster method. Raman and IR intensities are mixed derivatives of energy with respect to the electric field and geometric perturbation whereas vibrational frequencies are derivatives of energy with respect to geometry. We use semi-numerical approach to obtain these derivatives. We have studied the effect of electron correlation and basis set for the above properties. We compare our results with non-variational coupled cluster and experimental values, wherever available. We have studied HF, BH, CH+, CO and H2CO molecules in different basis sets. For HF molecule, benchmarking is done with full CI values and basis set convergence is studied for this molecule. Effect of triples is studied for all the molecules. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Extended coupled cluster; IR and Raman spectroscopy; Mixed derivatives

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

Fine-tuning the balance between crystallization and gelation and enhancement of CO2 uptake on functionalized calcium based MOFs and metallogels - Mallick, Arijit; Schoen, Eva-Maria; Panda, Tamas; Sreenivas, K.; Diaz, David Diaz; Banerjee, Rahul (Journal of Materials Chemistry, 2012)
The synthesis, structure, gas adsorption and catalytic properties of a new 3D porous, crystalline metal-organic framework (Ca-5TIA-MOF) as well as stable viscoelastic metallogels (Ca-5TIA-Gel) are reported. Remarkably, the preparation of both types of materials can be carried out starting from the same organic ligand (i.e. 5-(1,2,4-triazoleyl) isophthalic acid (5TIA)), divalent metal ion (i.e. Ca(II)) and organic solvent (i.e. DMF). In this particular case, the presence of water in the solvent system favors the formation of a crystalline MOF, whereas a pure organic solvent induces gelation. The characterization of the materials was carried out using a series of techniques including XRD, FT-IR, TGA, TEM, SEM, SAXS and dynamic rheology. Experimental PXRD peaks of both Ca-5TIA-xerogel and Ca-5TIA-MOF matched reasonably well with simulated PXRD, suggesting the presence of, at least, some common structural elements in the 3D networks of both xerogel and crystalline phases. Moreover, the nature of the metal counteranion was found to have a critical influence on the gelation phenomenon. To the best of our knowledge, this report describes unprecedented Ca-based LMW-metallogels, as well as the first porous Ca-based MOF, which shows adsorption capacity for CO2 at 1 atm pressure. Interestingly, Ca-5TIA-xerogel presented 20% higher CO2-uptake than the crystalline Ca-5TIA-MOF at 1 atm and 298 K. Both Ca-5TIA-MOF and Ca-5TIA-Gel also displayed a modest catalytic activity towards the hydrosilylation of benzaldehyde, with slightly better performance for the gel phase material.

First principle investigation on the thermal stability of a golden fullerene: a case study of Au-32 - De, Himadri Sekhar; Krishnamurty, Sailaja; Pal, Sourav (Catalysis Today, 2012)
Structural and electronic properties of Au-32 cluster are analyzed using relativistic density functional theory (DFT) based methods. Further, DFT based molecular dynamical (MD) simulations are performed on Au-32 golden fullerene with an aim of understanding its thermal stability at various working temperatures. Various conformations being populated at different temperatures of a cluster are analyzed. The study shows that the ground state icosahedral conformation is stable only up to 300 K and structure remains in a hollow conformation only up to 400 K. This clearly explains the reasons for failure by experimentalists in trapping the unique fullerene conformation in spite of the theoretical predictions of it being a very stable one. The above MD study also indicates that the bare fullerene Au-32 cluster (without any stabilizing ligands) can be used for potential catalytic applications only around room temperatures. (C) 2012 Elsevier B. V. All rights reserved.
Keywords: Au-32 cluster; Born-Oppenheimer molecular dynamics; Density functional theory; Golden fullerenes; Relativistic effects

Fluorescent superparamagnetic iron oxide core-shell nanoprobes for multimodal cellular imaging - Smitha, Sasidharan; Haseena, Vadakkenchery S.; Narayanan, Tharangattu N.; Mary, Antony P. Reena; Ajayan, Pulickel M.; Puthumana, Jayesh; Aziz, Anas A.; Aburto, Rebeca R.; Mani, Sendurai A.; Joy, Pattayil Alias; Anantharaman, Maliemadom R. (Materials Express, 2012)
Multimodal imaging agents that combine magnetic and fluorescent imaging capabilities are desirable for the high spatial and temporal resolution. In the present work, we report the synthesis of multifunctional fluorescent ferrofluids using iron oxide as the magnetic core and rhodamine B as fluorochrome shell. The core-shell structure was designed in such a way that fluorescence quenching due to the inner magnetic core was minimized by an intermediate layer of silica. The intermediate passive layer of silica was realized by a novel method which involves the esterification reaction between the epoxy group of prehydrolysed 3-Glyidoxypropyltrimethoxysilane and the surfactant over iron oxide. The as-synthesized ferrofluids have a high saturation magnetization in the range of 62-65 emu/g and were found to emit light of wavelength 640 nm (lambda(excitation) = 446 nm). Time resolved life time decay analysis showed a bi-exponential decay pattern with an increase in the decay life time in the presence of intermediate silica layer. Cytotoxicity studies confirmed the cell viability of these materials. The in vitro MRI imaging illustrated a high contrast when these multimodal nano probes were employed and the R2 relaxivity of these sample was found to be 334 mM(-1)s(-1) which reveals its high potential as a T2 contrast enhancing agent.
Keywords: GPTMS; MRI Imaging; Multimodal Imaging; SPION; T2 Contrast Agent

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

Foam based synthesis of metal carbonates: establishing the role of spatial confinement for obtaining interesting morphologies - Bala, Tanushree; Sanyal, Ambarish; Pant, Jayashree; Bhagavatula L. V. Prasad (Journal of Computational and Theoretical Nanoscience, 2012)
The crystallization of different carbonates namely lead carbonate, cadmium carbonate and strontium carbonate in aqueous foam stabilized by the surfactant sodium dodecyl sulphate (SDS) by a method of cation entrapment is described. Reaction of ammonium carbonate with the respective cations electrostatically entrapped in the foam results in the formation of minerals, possibly in the Plateau border and Plateau junction regions of the foam. The unusual morphology of the crystals obtained from foam based synthetic method as compared to the crystals prepared in aqueous solution shows the utility of the template for the growth of crystals with an unusual morphology due to constrained environment. The materials are well characterized using TEM, SEM, EDAX and FTIR techniques. The large interfacial area of the liquid lamellae in the foam provides a striking possibility for the large-scale synthesis for not only minerals but also other nanoscale materials.

Fock-space multi-reference coupled-cluster response with the effect of triples on dipole moment of ClO and SF radicals - Ravichandran, Lalitha; Bhattacharya, Debarati; Vaval, Nayana; Pal, Sourav (Journal of Chemical Sciences, 2012)

Foldamers: they're not just for biomedical applications anymore - Prabhakaran, Panchami; Priya, Gowri; Sanjayan, Gangadhar J. (Angewandte Chemie-International Edition, 2012)
Keywords: Foldamers; foldaxanes; molecular shuttles; nanotechnology

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

Gellan gum capped silver nanoparticle dispersions and hydrogels: cytotoxicity and in vitro diffusion studies - Dhar, Sheetal; Murawala, Priyanka; Shiras, A.; Pokharkar, V.; Bhagavatula L. V. Prasad (Nanoscale, 2012)
The preparation of highly stable water dispersions of silver nanoparticles using the naturally available gellan gum as a reducing and capping agent is reported. Further, exploiting the gel formation characteristic of gellan gum silver nanoparticle incorporated gels have also been prepared. The optical properties, morphology, zeta potential and long-term stability of the synthesized silver nanoparticles were investigated. The superior stability of the gellan gum-silver nanoparticle dispersions against pH variation and electrolyte addition is revealed. Finally, we studied the cytotoxicity of AgNP dispersions in mouse embryonic fibroblast cells (NIH3T3) and also evaluated the in vitro diffusion of AgNP dispersions/gels across rat skin.

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

Gold nanoparticle embedded hydrogel matrices as catalysts: better dispersibility of nanoparticles in the gel matrix upon addition of N-bromosuccinimide leading to increased catalytic efficiency - Ramtenki, Vilas; Anumon, V. D.; Badiger, Manohar V.; Bhagavatula L. V. Prasad (Colloids and Surfaces A-Physicochemical and Engineering Aspects, 2012)
A simple and convenient method for generating and immobilizing gold NPs into polyethylene glycol-polyurethane (PEGPU) matrices is presented. The gold NP immobilized PEGPU (Au NP-PEGPU) hydrogel matrices are easy to handle and can be used as catalysts. The efficiency, reusability and durability of the Au NP-PEGPU catalyst matrices were investigated using the reduction of 4-nitroaniline (4NA) to p-phenylenediamine (p-PDA) by sodium borohydride in the presence of the catalyst as a test reaction. The Au NPs in the PEGPU matrix got aggregated after 3 cycles of catalysis but dispersion could be regenerated by the addition of N-bromosuccinimide (NBS). After this regeneration process the Au NPs-PEGPU matrix showed excellent efficiency without any aggregation, leaching or degradation. The reusability of the catalyst for 28 cycles yielding a total turnover number of 3220 and turn over frequency of 0.152 s(-1) is demonstrated. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: catalysis; hydrogels; Immobilization; Nanoparticles; Turn over numbers

Green approach towards size controlled synthesis of biocompatible antibacterial metal nanoparticles in aqueous phase using lysozyme - Kumar, Umesh; Ranjan, Amaresh K.; Sharan, Chandrashekhar; Hardikar, Anandwardhan A.; Pundle, Archana; Poddar, Pankaj (Current Nanoscience, 2012)
Inspired by array of proteins present in nature, we choose lysozyme (hen egg protein) as a model system to synthesize nanoparticles of noble metals to understand the mechanism of interaction as well as to use them for potential applications such as potent antibacterial agents. Lysozyme is a very well studied biomolecule containing aromatic amino acids like tryptophan and tyrosine. Tyrosine has phenoxy group which is considered to be responsible for interacting with the metal ions. Lysozyme can be suitably modified by treatment with N-bromosuccinimide/N-acetylimidazole to obtain tight control over size distribution of nanoparticles. Here we report the direct synthesis of nanocrystals of gold and silver at controlled pH and light conditions without using any known reducing agents. Out of these, synthesis of gold nanoparticles is assisted by the presence of low concentration of Ag+ ions through the galvanic exchange. It is remarkable to note that the structure of protein is not changed drastically as seen by the FTIR studies. As-synthesized lysozyme capped nanoparticles prepared by this method are biocompatible and retain antibacterial property.
Keywords: Antibacterial; Biocompatible; Gold; lysozyme; Nanoparticles; Silver

Helical folding in heterogeneous foldamers without inter-residual backbone hydrogen-bonding - Priya, Gowri; Kotmale, Amol S.; Gawade, Rupesh L.; Mishra, Deepti; Pal, Sourav; Puranik, Vedavati G.; Rajamohanan, Pattuparambil R.; Sanjayan, Gangadhar J. (Chemical Communications, 2012)
This communication describes a set of hybrid foldamers that do not feature inter-residual, but intra-residual backbone hydrogen-bonding, yet adopt a preferentially folded conformation displaying right-handed helical architecture. Conformational ordering is apparently due to the combined conformational restrictions imposed by the conformationally restricted individual amino acid residues with which the oligomers are made of.

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

High viscosity of ionic liquids causes rate retardation of Diels-Alder reactions - Kumar, Anil; Pawar, Sanjay S. (Science China-Chemistry, 2012)
Second order rate constants, k (2) have been determined for three bi-molecular Diels-Alder reactions to demonstrate that the high viscosity of ionic liquids can be a detrimental property in carrying out Diels-Alder reactions, if ionic liquids are employed as solvent media. It is possible to enhance the reaction rates of the reaction if a co-solvent is mixed in pure ionic liquid used as a solvent.
Keywords: Diels-Alder reactions; ionic liquids; kinetics; viscosity

Highly efficient (R-X-R)-type carbamates as molecular transporters for cellular delivery - Patil, Kiran M.; Naik, Rangeetha J.; Rajpal; Fernandes, Moneesha; Ganguli, Munia; Kumar, Vaijayanti A. (Journal of the American Chemical Society, 2012)
The (R-X-R) motif-containing arginine-rich peptides are among the most effective cell-penetrating peptides. The replacement of amide linkages in the (R-X-R) motif by carbamate linkages as in (r-ahx-r)(4) or (r-ahx-r-r-apr-r)(2) increases the efficacy of such oligomers several-fold. Internalization of these oligomers in mammalian cell lines occurs by an energy-independent process. These oligomers show efficient delivery of biologically active plasmid DNA into CHO-K1 cells.

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

Hydrous RuO2-carbon nanofiber electrodes with high mass and electrode-specific capacitance for efficient energy storage - Vellacheri, Ranjith; Pillai, Vijayamohanan K.; Kurungot, Sreekumar (Nanoscale, 2012)
We demonstrate a new strategy for the fabrication of supercapacitor electrodes possessing high mass and area-specific capacitance for efficient charge storage, which can be extremely useful for the development of light, compact and high performance supercapacitors for a variety of high power demanding applications. High mass and electrode area specific capacitances were attained by using Hydrous Ruthenium Oxide (HRO)-Carbon Nanofiber (CNF) hybrid electrodes prepared by the deposition of HRO (similar to 31% Ru content) on both the outer and inner surfaces of a cylindrical hollow CNF having open tips. Electrochemical studies of the uniformly deposited HRO nanoparticles on the CNF surface showed a mass specific capacitance of 645 F g(-1) and an electrode specific capacitance of 1.29 F cm(-2) with a HRO-CNF material loading of 2 mg cm(-2) in the supercapacitor electrodes. The mass specific capacitance of pure HRO is 301 F g(-1), whereas the mass specific capacitance of HRO in the HRO-CNF electrode is similar to 1300 F g(-1), which is very close to the theoretical capacitance of HRO. This enhanced charge storage ability, high rate capability, better cyclic stability and low ESR of the HRO-CNF will be useful for the development of high performance supercapacitors.

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

Improved inhibition of telomerase by short twisted intercalating nucleic acids under molecular crowding conditions - Agarwal, Tani; Pradhan, Devranjan; Geci, Imrich; El-Madani, Amro M.; Petersen, Michael; Pedersen, Erik B.; Maiti, Souvik (Nucleic Acid Therapeutics, 2012)
Human telomeric DNA has the ability to fold into a 4-stranded G-quadruplex structure. Several G-quadruplex ligands are known to stabilize the structure and thereby inhibit telomerase activity. Such ligands have demonstrated efficient telomerase inhibition in dilute conditions, but under molecular crowding conditions mimicking physiological milieu, stabilization of the telomeric G-quadruplex is often lost. We attempted to demonstrate the enhanced G-quadruplex stabilizing ability under molecular conditions by using twisted intercalating nucleic acids (TINA)-modified oligonucleotides. We have shown using circular dichroism and ultraviolet spectroscopic methods that these TINA-modified short oligonucleotides function as G-quadruplex, inducing agents and participate in the formation of stabilized 3:1 G-quadruplex with the human telomeric oligonucleotide. Using enzyme-linked immunosorbent assay-based telomerase repeat amplification assay (TRAP) assay as well as nondenaturing polyacrylamide gel electrophoresis-based TRAP, we demonstrate remarkable enhancement in their anti-telomerase activity even under molecular crowding conditions. This is the first time in which a G-quadruplex stabilizing agent has demonstrated enhanced activity even under molecular crowding conditions.

In situ electrochemical organization of CdSe nanoclusters on graphene during unzipping of carbon nanotubes - Debgupta, Joyashish; Shinde, Dhanraj B.; Pillai, Vijayamohanan K. (Chemical Communications, 2012)
In situ decoration of very small CdSe quantum dots on graphene nanoribbons (GNRs) has been achieved during the electrochemical unzipping of single walled carbon nanotubes. Critical parameters like the width of the GNRs, size distribution of quantum dots and their organization on GNRs have been shown to be strongly dependent on the electric field and time.

In situ pH maintenance for mammalian cell cultures in shake flasks and tissue culture flasks - Pradhan, Ketaki; Pant, Tejal; Gadgil, Mugdha (Biotechnology Progress, 2012)
pH in animal cell cultures decreases due to production of metabolites like lactate. pH control via measurement and base addition is not easily possible in small-scale culture formats like tissue-culture flasks and shake flasks. A hydrogel-based system is reported for in situ pH maintenance without pH measurement in such formats, and is demonstrated to maintain pH between 6.8 and 7.2 for a suspension CHO cell line in CD CHO medium and between 7.3 and 7.5 for adherent A549 cells in DMEM:F12 containing 10% FBS. This system for pH maintenance, along with our previous report of hydrogels for controlled nutrient delivery in shake flasks can allow shake flasks to better mimic bioreactor-based fed batch operation for initial screening during cell line and process development for recombinant protein production in mammalian cells. (C) 2012 American Institute of Chemical Engineers Biotechnol. Prog., 2012
Keywords: high throughput screening; pH control for cell culture; pH control in shake flask; pH control in tissue culture flasks; small scale platforms for cell culture

In vitro morphogenic response in cotyledon explants of semecarpus anacardium L. - Panda, Bhuban Mohan; Hazra, Sulekha (Plant Biotechnology Reports, 2012)
Three different morphogenic responses-caulogenesis, direct somatic embryogenesis, and callusing-were noted in cotyledon explants of Semecarpus anacardium L. cultured in woody plant medium (WPM) containing thidiazuron (TDZ). Thidiazuron, at all concentrations tested, induced organogenic as well as embryogenic responses. The organogenic buds differentiated to shoots and the embryogenic mass (EM) gave rise to globular embryos which differentiated up to cotyledon-stage embryos on repeated culture in growth regulator (GR)-free WPM medium containing 0.2% activated charcoal after the removal of TDZ. The organogenic and embryogenic responses were optimal in 9.08 mu M TDZ after the removal of TDZ. Elongated shoots rooted in half-strength liquid WPM medium with 2.46 mu M indole butyric acid. Plants were successfully acclimatized and transferred to soil. Histological studies confirmed the direct origin of the organogenic buds from the cotyledon explants. The EMs produced somatic embryos on repeated culture in charcoal incorporated GR-free medium. Morphogenic callus formation from the cotyledon explants was also noted. This callus on repeated culture in WPM medium with charcoal differentiated into somatic embryos. Repetitive somatic embryogenesis was evident from direct and indirectly formed primary embryos. The somatic embryos did not convert into plantlets, though sporadic germination of embryos was observed through the emergence of roots.
Keywords: callus; Caulogenesis; Globular embryos; Growth regulator; Histology; somatic embryogenesis

InCl3-mediated addition of indole to isatogens: an expeditious synthesis of 13-deoxy-isatisine A - Kumar, Chepuri V. Suneel; Puranik, Vedavati G.; Ramana, Chepuri V. (Chemistry-A European Journal, 2012)
A strategy directed towards the total synthesis of isatisine A that involves several late-stage metal-catalyzed transformations that address the key carboncarbon and carbonheteroatom bond formations has been developed. As a part of this strategy, methods for the addition of indoles to isatogens that lead selectively to either 2,2-disubstituted N-hydroxyindolin-3-one or 2,2-disubstituted indolin-3-one compounds have been developed by employing InCl3 as a catalyst or as the reagent. The present methods provide the first examples of the additions of indoles to the isatogen nucleus. To demonstrate its viability, the synthesis of 13-deoxy-isatisine A has been completed in ten steps from a known and easily available lactone.
Keywords: indium; indoles; isatogens; Natural products; Total synthesis

Influence of Pd-loading on gas sensing characteristics of SnO2 thick films - Bagal, L. K.; Patil, J. Y.; Mulla, Imtiaz S.; Suryavanshi, S. S. (Ceramics International, 2012)
Nanocrystalline pristine and 0.5, 1.5 and 3.0 wt% Pd loaded SnO2 were synthesized by a facile co-precipitation route. These powders were screen-printed on alumina substrates to form thick films to investigate their gas sensing properties. The crystal structure and morphology of different samples were characterized by using X-ray diffraction, scanning electron microscopy and transmission electron microscopy techniques. The 3.0 wt% Pd:SnO2 showed response of 85% toward 100 ppm of LPG at operating temperature of 250 degrees C with fast response (8 s) and quick recovery time (24 s). The high response toward LPG on Pd loading can be attributed to lowering of crystallite size (9 nm) as well as the role of Pd particles in exhibiting spill-over mechanism on the SnO2 surface. Also selectivity of 3.0 wt% Pd:SnO2 toward LPG was confirmed by measuring its response to other reducing gases like acetone (CH3COCH3), ethanol (C2H5OH) and ammonia (NH3) at optimum operating temperature. (C) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: LPG sensor; Palladium; SnO2; Thick film

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

Larvicidal potential of mimusops elengi against aedes aegypti (L) and Culex quinquefasciatus (Say) - Ruikar, Anjali D.; Pawar, Pushpa V.; Sen, Avalokiteswar; Phalgune, Usha D.; Puranik, Vedavati G.; Deshpande, Nirmala R. (Journal of Vector Borne Diseases, 2012)
Keywords: Aedes aegypti; Culex quinquefasciatus; larvicidal activity; Mimusops elengi

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

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

Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): finding the border of metal and metal oxides - Das, Raja; Pachfule, Pradip; Banerjee, Rahul; Poddar, Pankaj (Nanoscale, 2012)
Herein, for the first time, we report a generalized strategy for the successful synthesis of highly crystalline metal and metal oxide nanoparticles embedded in a carbon matrix by the controlled thermolysis of metal organic frameworks (MOFs). The rationalized synthesis strategy of a broad range of metal and metal oxides nanoparticles, such as Cu/CuO, Co/Co3O4, ZnO, Mn2O3, MgO and CdS/CdO, by thermolysis of MOFs demonstrates for the first time that metal ions with a reduction potential of -0.27 volts or higher present in MOFs always form pure metal nanoparticles during thermolysis in N-2, whereas metal ions with a reduction potential lower than -0.27 volts form metal oxide nanoparticles during thermolysis in N-2. Another point of interest is the fact that we have found a unique relationship between the nanoparticle size and the distance between the secondary building units inside the MOF precursors. Interestingly, the crystallinity of the carbon matrix was also found to be greatly influenced by the environment (N-2 and air) during thermolysis. Moreover, these nanoparticles dispersed in a carbon matrix showed promising H-2 and CO2 adsorption properties depending on the environment used for the thermolysis of MOFs.

Metal [Zn(II), Cd(II)], 1,10-phenanthroline containing coordination polymers constructed on the skeleton of polycarboxylates: synthesis, characterization, microstructural, and CO2 gas adsorption studies - Yadav, Pramod Kumar; Kumari, Niraj; Pachfule, Pradip; Banerjee, Rahul; Mishra, Lallan (Crystal Growth & Design, 2012)
{Four new coordination polymers have been obtained by the reaction of metal [Zn(II), Cd(II)], 1,10-phenanthroline separately with two carboxylic acids, [biphenyl-4,4'-dicarboxylic acid (4,4'-H(2)BDA),and 4,4'-azodibenzoic acid (4,4'-H(2)ADA)]. The crystal structures of the resulting complexes of type {[Zn(4,4'-BDA)(Phen)(2)center dot HCON(CH3)(2)}(n) (1), {[Cd(4,4'-BDA)(Phen)](2)center dot H2O\

Micropropagation of semecarpus anacardium L.: a medicinally important tree species - Panda, Bhuban Mohan; Hazra, Sulekha (Plant Biosystems, 2012)
Semecarpus anacardium L., a deciduous forest tree, is a source of medicinal compounds. Poor seed-viability restricts the conventional propagation. Micropropagation protocol is standardized for this species. Shoot culture-derived nodal explants were cultured in woody plant media supplemented with thidiazuron (TDZ). Shoot differentiation from meristem was limited. Meristems swelled to form meristematic mass in higher concentrations of TDZ. Swelling of meristem was attributed to the proliferation of meristematic cells. Development of shoots from meristematic mass on withdrawal of TDZ in culture medium indicated the inhibitory influence of TDZ on differentiation of buds to form shoots. Harvesting the primary shoot, leads to appearance of additional shoot buds which elongated on repeated transfer of explants in a medium devoid of growth regulator every four weeks. Optimum (17) number of shoots obtained from each meristem in explants pre-cultured in TDZ 2.27 mu M and re-cultured in growth regulator free medium for seven cycles (28 weeks). This confirms the stimulatory influence of TDZ on proliferation of meristem and inhibitory influence on shoot differentiation. All shoots, rooted in the medium with Indole butyric acid 2.46 mu M. Plantlets survived on transfer to sand: soil (1: 1) mixture and acclimatized. This is the first report on micropropagation of S. anacardium from seedling derived nodal buds using TDZ.
Keywords: Meristematic; micropropagation; Semecarpus anacardium L.; thidiazuron

Microstructural elucidation of self-emulsifying system: effect of chemical structure - Patil, Sharvil S.; Venugopal, Edakkal; Bhat, Suresh K.; Mahadik, Kakasaheb R.; Paradkar, Anant R. (Pharmaceutical Research, 2012)
Self-emulsifying systems (SES) emulsify spontaneously to produce fine oil-in-water emulsion when introduced into aqueous phase. The self-emulsification process plays an important role during formation of emulsion. The objective of current work was to understand and explore the inner structuration of SES through controlled hydration and further to study the influence of additive on the same which ultimately governs performance of final formulation in terms of droplet size. Droplet size of final formulations containing structural analogues of ibuprofen was determined. Microstructural properties of intermediate hydrated regimes of SES were investigated using techniques such as small angle X-ray scattering, differential scanning calorimetry and rheology. The current work established inverse relationship between droplet size of the formulations containing structural analogues of ibuprofen and their Log P values. Microstructural analysis of intermediate hydrated regimes of the prepared samples showed formation of local lamellar structure. Structural analogues of ibuprofen significantly altered microstructure of lamellae which was well correlated with the droplet size of final formulations. In vitro drug release study showed increase in dissolution rate of lipophillic drugs when formulated as SES. The current work emphasizes the fact that tailor-made formulations can be prepared by controlling the properties of intermediate regimes.
Keywords: emulsion; flurbiprofen; ibuprofen; ketoprofen; lamellar structure; self-emulsifying system; structural analogues

Modeling of liquid propellant combustion chamber - Pandit, Ajinkya V.; Kumar, Ashok; Rao, G. Srinivasa; Kedarnath, C.; Srihari, R.; Ranade, Vivek V. (Chemical Engineering Journal, 2012)
Liquid propellants are fuels which do not require external supply of oxygen for combustion. These fuels are widely used for propulsion applications in oxygen rare environments (underwater, space). We had previously presented a model for solid propellant decomposition in a combustion chamber. In this study we extend the model for the case of combined solid and liquid propellant combustion. Sub-models relating to solid propellant combustion and outlet flow-rate in the present study are borrowed from the previous study. The combustion chamber is assumed to be a `well-mixed reactor'. A model is developed to characterize the liquid propellant spray assuming the spray is a collection of individually burning droplets. A single droplet decomposition model was developed and used along-with the spray model to solve for the liquid propellant burning rate. Appropriate numerical methods and computer programs were developed to solve the model equations. The model predictions were compared with the experimental data obtained in earlier studies. Appropriate methodology for calibrating the model parameters was developed and its usefulness was demonstrated by comparing the simulated pressure profiles with the experimental pressure profiles. The presented model and results will be useful for selecting appropriate liquid propellants for propulsion systems and for the development of a system level model of propulsion systems. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Liquid propellant; Single droplet decomposition; Spray combustion

MOF with hydroxynaphthoquinone as organic linker: molecular structure of [Zn(Chlorolawsone)(2)(H2O)(2)] and thermogravimetric studies - Salunke-Gawali, Sunita; Kathawate, Laxmi; Puranik, Vedavati G. (Journal of Molecular Structure, 2012)
Zinc complexes as MOF with hydroxynaphthoquinone as organic linkers are synthesized and characterized. The complexes Zn-1; [Zn(lawsone)(2)(H2O)(2)]center dot 3H(2)O and Zn-2; [Zn(chlorolawsone)(2)(H2O)(2)]center dot H2O, where lawsone is 2-hydroxy-1,4-naphthoquinone and chlorolawsone is 3-chloro-2-hydroxy-1,4-naphthoquinone, serve as hosts for adsorbed water molecules. nu(c=O) shows shift towards lower frequencies similar to 25 cm(-1) in Zn-1 and similar to 35 cm(-1) in Zn-2 in FTIR spectra. (HNMR)-H-1 shows upfield shift in Zn-1 and downfield shift in Zn-2 to the benzenoid ring protons. Bathochromic shift has been observed to the charge transfer band in UV-visible spectra of both complexes. The mass loss of adsorbed water molecules have been observed <100 degrees C in thermogravimetric (TG) studies. Three adsorbed water molecules are present in Zn-1, while one in Zn-2. X-ray diffraction studies of Zn-2 show, distorted octahedral geometry around Zn(II). The two chlorolawsone ligands are in plane with the metal, while water molecules are trans to this plane. Formation of MOF has been observed in the synthesis of Zn-2 with chlorolawsone as organic linkers. The structure is stabilized by O-H center dot center dot center dot O, C-H center dot center dot center dot O hydrogen bonding H-bonding along with Cl center dot center dot center dot pi interactions to form a beautiful MOF architecture. Zn(II) atoms along with organic ligand form a tetramer via O-H center dot O interactions. The shortest Zn center dot center dot center dot Zn distance is 5.04 angstrom. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: 3-Chloro-2-hydroxy-1; 4-naphthoquinone; MOF; Naphthoquinone; O-H center dot center dot center dot O hydrogen bonding; Vapochromic behavior; Zinc complexes

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

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

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

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

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

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

Nitrogen-rich porous covalent imine network (CIN) material as an efficient catalytic support for C-C coupling reactions - Bhunia, Manas K.; Das, Swapan K.; Pachfule, Pradip; Banerjee, Rahul; Bhaumik, Asim (Dalton Transactions, 2012)
In an effort to expand the realm of possibilities of nitrogen-rich porous materials that could be used in catalysis, herein we report the synthesis of a new highly nitrogen rich (ca. 45%) porous covalent imine network (CIN-1) material employing simple Schiff base chemistry and further grafting its surface with palladium. Pd-loaded CIN-1 support acts as a truly heterogeneous catalyst towards Suzuki C-C coupling reaction between aryl halides with arylboronic acids. High surface area and excellent accessibility of the catalytic sites make it very efficient for heterogeneous catalysis. The stability of the catalyst due to intimate contact between nitrogen-rich organic support and metal allows several reuses with only a minor loss in catalytic activity.

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

Novel microwave assisted sol-gel synthesis (MW-SGS) and electrochromic performance of petal like h-WO3 thin films - Kharade, Rohini R.; Patil, K. R.; Patil, P. S.; Bhosale, Popatrao N. (Materials Research Bulletin, 2012)
Use of domestic microwave oven is first time employed for chemical deposition of nanocrystalline hexagonal WO3 (h-WO3) thin films. Low cost precursors like sodium tungstate, hydrochloric acid, oxalic acid and potassium sulfate signifies cost effectiveness of this thin film fabrication route. Scanning electron microscopy images reveal formation of petal like nanodisks. A number of analytical techniques were used to characterize the WO3 petal like nanodisks, including X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX). X-ray photoelectron spectroscopy, FT-IR spectroscopy, Raman scattering spectroscopy, UV-visible spectrophotometry and cyclic voltammetry (CV). The X-ray photoelectron spectroscopic studies revealed 2.89 O/W atomic ratio. The electrical transport studies on WO3 thin films show semiconducting behavior with n-type semiconductivity. The value of determined coloration efficiency is 57.90 cm(2)/C. The mechanism of Li+ intercalation and deinercalation in h-WO3 matrix is proposed for enhanced electrochromism. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Chemical synthesis; Electrochemical properties; Oxides; photoelectron spectroscopy

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

NOx catalyzed pathway of stratospheric ozone depletion: a coupled cluster investigation - Dutta, Achintya Kumar; Vaval, Nayana; Pal, Sourav (Journal of Chemical Theory and Computation, 2012)
We report a theoretical investigation on the NOx catalyzed pathways of stratospheric ozone depletion using highly accurate coupled cluster methods. These catalytic reactions represent a great challenge to state-of-the-art ab initio methods, while their mechanisms remain unclear to both experimentalists and theoreticians. In this work, we have used the so-called ``gold standard of quantum chemistry,'' the CCSD(T) method, to identify the saddle points on NOx-based reaction pathways of ozone hole formation. Energies of the saddle points are calculated using the multireference variants of coupled cluster methods. The calculated activation energies and rate constants show good agreement with available experimental results. Tropospheric precursors to stratospheric NOx radicals have been identified, and their potential importance in stratospheric chemistry has been discussed. Our calculations resolve previous conflicts between ab initio and experimental results for a trans nitro peroxide intermediate, in the NOx catalyzed pathway of ozone depletion.

Observation of enhanced dielectric coupling and room-temperature ferromagnetism in chemically synthesized BiFeO3@SiO2 core-shell particles - Shirolkar, Mandar M.; Das, Raja; Maity, Tuhin; Poddar, Pankaj; Kulkarni, Sulabha K. (Journal of Physical Chemistry C, 2012)
We report the effect of SiO2 coating on the structural, magnetic, and dielectric properties of chemically synthesized high-purity BiFeO3 particles. The assynthesized BiFeO3 particles demonstrate properties comparable with those reported for bulk BiFeO3. On the other hand, the structural measurement on BiFeO3@SiO2 shows that the SiO2 coating has anisotropically compressed the lattice of BiFeO3 particles and stimulates the variation in the electron density. This affects magnetic and dielectric behavior of material. Frequency-dependent dielectric constant study at low temperature (20-325 K) revealed slight reduction (8-10%) in the dielectric constant of BiFeO3@SiO2 particles compared to uncoated BiFeO3 particles. The study reveals five anomalies at 234, 206, 146, 84, and 25 K located in close proximity to the linear magnetodielectric coupling and spin reorientation transitions. The loss tangent (approximate to 10(-3)) and alternating current (ac) conductivity (approximate to 10(-8) Omega(-1)cm(-1)) of BiFeO3@SiO2 particles are orders of magnitude lower than those observed for the BiFeO3 particles. The magnetic measurement shows the existence of room-temperature ferromagnetism in BiFeO3@SiO2 particles with average value of magnetic moment per Fe atom approximate to 0.030 mu(B) and appreciable coercivity as high as 120 Oe. The canted spin structure in the surface shell of BiFeO3@SiO2 particles show an enhanced magnetic property and shifted hysteresis loop. The magnetic measurement in close proximity to dielectric transitions revealed enhanced magnetization, suggesting the presence of anisotropies. It has been observed that SiO2 coating alters the properties of BiFeO3 particles. Our dielectric and magnetic measurements show enhanced coupling among the electric and magnetic ordered parameters in BiFeO3@SiO2 core-shell particles compared to uncoated BiFeO3 particles. The magnetic and dielectric properties of SiO2-coated BiFeO3 are similar to nanoparticles of BiFeO3 where interface plays a significant role.

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

One-dimensional confinement of a nanosized metal organic framework in carbon nanofibers for improved gas adsorption - Pachfule, Pradip; Balan, Beena K.; Kurungot, Sreekumar; Banerjee, Rahul (Chemical Communications, 2012)
The loading of a Zn-terephthalate based MOF in the inner cavity as well as on the outer walls of a hollow carbon nanofiber (CNF) creates MOF@CNF hybrids. This hybrid ``MOF@CNF'' displayed improved thermal stability as well as gas adsorption compared to the individual counterparts.

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

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

Organocatalytic dynamic kinetic resolution via conjugate addition: synthesis of chiral trans-2,5-dialkylcyclohexanones - Pandey, Ganesh; Adate, Priyanka A.; Puranik, Vedavati G. (Organic & Biomolecular Chemistry, 2012)
A novel strategy of initiating an organocatalysed dynamic kinetic resolution (dr up to 99 : 1 and er up to 94 : 6) for the synthesis of chiral trans-2,5-dialkylcyclohexanones by an asymmetric conjugate addition of dimethyl malonate on to 6-substituted cyclohexenones is reported.

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

Overview on the cellulose based conducting composites - Pandey, Jitendra Kumar; Takagi, Hitoshi; Nakagaito, Antonio Norio; Saini, Daulat Ram; Ahn, Sung-Hoon (Composites Part B-Engineering, 2012)
Biopolymer based composites have been employed in numerous applications with increasing interest not only due to renewable, eco-friendly nature, but also because of the flexibility in processing conditions and competitive cost of their end products. The conductive materials from biopolymers have been found applicable in robots, medical imaging, sensitive membranes, actuators, visual displays, electronic wiring and shielding, and components in batteries. Cellulose is one of the most abundant biopolymers in the nature, which has received special attention for development of conducting materials due to biocompatibility for protein and drug immobilization and ability to form the composites with synthetic polymers. The present review is aimed to provide concisely the current status in this field of conducting composites from cellulose, with brief discussions of associated problems and future applications. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Fibres; mechanical properties; Nano-structures; Polymer-matrix composites (PMCs)

Photocatalytic degradation of Azo dyes using Au:TiO2, gamma-Fe2O3:TiO2 functional nanosystems - Jagadale, Tushar C.; Kulkarni, Manjusha; Pravarthana, D.; Ramadan, Wegdan; Thakur, Pragati (Journal of Nanoscience and Nanotechnology, 2012)
We report photocatalytic degradation studies on Navy Blue HE2R (NB) dye on significant details as a representative from the class of azo dyes using functional nanosystems specifically designed to allow a strong photocatalytic activity. A modified sol-gel route was employed to synthesize Au and gamma-Fe2O3 modified TiO2 nanoparticles (NPs) at low temperature. The attachment strategy is better because it allows clear surface of TiO2 to remain open for photo-catalysis. X-ray diffraction, Raman and UV-VIS spectroscopy studies showed the presence of gold and iron oxide phases along-with the anatase TiO2 phase. TEM studies showed TiO2 nanocomposite particles of size similar to 10-12 nm. A detailed investigation on heterogeneous photocatalytic performance for Navy Blue HE2R dye was done using the as-synthesized catalysts Au:TiO2 and gamma-Fe2O3:TiO2 in aqueous suspension under 8 W low-pressure mercury vapour lamp irradiation. Also, the photocatalytic degradation of Amranth and Orange G azo dyes were studied. The surface modified TiO2 NPs showed significantly improved photocatalytic activity as compared to pure TiO2. Exposure of the dye to the UV light in the presence of pure and gold NPs attached TiO2 catalysts caused dye degradation of about similar to 20% and similar to 80%, respectively, in the first couple of hours. In the presence of gamma-Fe2O3 NPs attached TiO2, a remarkable similar to 95% degradation of the azo dye was observed only in the first 15 min of UV exposure. The process parameters for the optimum catalytic activity are established which lead to a complete decoloration and substantial dye degradation, supported by the values of the Chemical Oxygen Demand (COD) similar to 93% and Total Organic Carbon (TOC) similar to 65% of the treated dye solution after 5 hours on the employment of the UV/Au:TiO2/H2O2 photocatalytic process.
Keywords: Azo Dye; COD; H2O2; Photocatalysis; TiO2

Photopatternable nano-composite (SU-8/ZnO) thin films for piezo-electric applications - Kandpal, Manoj; Sharan, Chandrashekhar; Poddar, Pankaj; Prashanthi, K.; Apte, Prakash R.; Rao, V. Ramgopal (Applied Physics Letters, 2012)
Photo-curable nanocomposite material was formulated by embedding ZnO nanoparticles into a SU-8 matrix and studied for its piezoelectric properties for low cost fabrication of self-powered nanodevices. The piezoelectric coefficient of ZnO nanoparticles was observed to be ranging between 15 and 23 pm/V, which is the highest reported. These experimental studies support the recent theoretical predictions where the piezoelectric coefficients in ZnO nanoparticles were found to be higher compared to the thin films because of the surface relaxation induced volume reductions in the nanometer scale. The photo-curable property of these polymer composite films is exploited to demonstrate fabrication of a micro-cantilever test structure. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4748575]

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

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

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

Poly(allyl glycidyl ether-co-ethylene glycol dimethacrylate) copolymer beads as support for covalent immobilization of L-aminoacylase - Vaidya, Bhalchandra K.; Ingavle, Ganesh C.; Ponrathnam, S.; Nene, Sanjay N. (Reactive & Functional Polymers, 2012)
Porous epoxy-activated copolymer beads were synthesized as support for the covalent immobilization of Aspergillus melleus L-aminoacylase. Here, a series of copolymer bead were synthesized using either glycidyl methacrylate (GMA) or ally] glycidyl ether (AGE) as monomer units and ethylene glycol dimethacrylate (EGDM) as cross-linking agent. The effect of monomer used and the effect of amount of cross-linking agent on covalent immobilization of aminoacylase were studied. Furthermore, the effect of porogen on immobilization of aminoacylase was also evaluated. AGE-co-EGDM copolymer beads gave higher binding of aminoacylase than GMA-co-EGDM copolymer beads. AGE-co-EGDM copolymer beads synthesized with lauryl alcohol as porogen and having 150% cross-linked density (i.e. AGE-(L)-150) gave maximum enzyme binding. Under optimum conditions, AGE-(L)-150 copolymer beads gave about 130 U/g of aminoacylase activity which corresponds to 72.24% of activity yield. Immobilized aminoacylase showed a broader pH, higher temperature and extended storage stability. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Enzyme immobilization; Epoxy-activated support; L-Aminoacylase

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

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

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

Practical and highly efficient protocol for multicomponent synthesis of beta-phosphonomalononitriles and 2-amino-4H-chromen-4-yl phosphonates using diethylamine as a novel organocatalyst - Kulkarni, M. A.; Pandurangi, V. R.; Desai, Uday V.; Wadgaonkar, P. P. (Comptes Rendus Chimie, 2012)
Diethylamine has been demonstrated for the first time to be a highly efficient organocatalyst in the solvent-free synthesis of beta-phosphonomalononitriles by a three component condensation of aldehyde, malononitrile and dialkyl phosphite at ambient temperature. The applicability of the same catalyst in the synthesis of diethyl (2-amino-3-cyano-chromene-4-yl) phosphonic acid esters has also been described. (c) 2012 Published by Elsevier Masson SAS on behalf of Academie des sciences.
Keywords: 2-amino-4H-chromenes; beta-phosphonomalononitriles; diethylamine; multicomponent reactions; organocatalyst; Phospha-Michael reaction

Preparation of spherical particles of 1,1-diamino-2,2-dinitroethene (FOX-7) using a micellar nanoreactor - Mandal, Alok Kumar; Thanigaivelan, U.; Pandey, Raj Kishore; Asthana, Srinandan; Khomane, Ramdas B.; Kulkarni, Bhaskar Dattatraya (Organic Process Research & Development, 2012)
The need and preparation of spherical 1,1-diamino-2,2-dinitroethene (FOX-7) particles to meet certain special applications in high explosives and propellant formulation have been illustrated. Preparation of spherical FOX-7 particles by using a microemulsion technique has not been reported in the literature. In the present study, the preparation of spherical FOX-7 particles has been described using the novel concept of a micelle-based nanoreactor. Micelle-based nanoreactors have been prepared using a microemulsion of Triton X-100, cyclohexane, and water. Formation of spherical FOX-7 particles in the reverse micelle reactors have been described in the subsequent sections of this article. It is observed that spherical particles of FOX-7 are formed within 2 h in the microemulsion media. Analysis of the experimental results revealed that the particle size and shape of FOX-7 can be varied by changing the water/surfactant molar ratio in the microemulsion. Spherical particles synthesized by this method have diameters that are generally in the submicrometer to nanometer range. Impact sensitivity (h(50)) of the spherical particles obtained by the fall-hammer method is around 45 cm compared to regular synthesized FOX-7 (i.e., 50 +/- 5 cm) without any change in friction sensitivity, i.e. 36 kg. Loadability of the explosive charges can be enhanced by using these spherical particles of FOX-7.

Preparative separation of alpha- and beta-santalenes and (Z)-alpha- and (Z)-beta-santalols using silver nitrate-impregnated silica gel medium pressure liquid chromatography and analysis of sandalwood oil - Daramwar, Pankaj P.; Srivastava, Prabhakar Lal; Priyadarshini, Balaraman; Thulasiram, Hirekodathakallu V. (Analyst, 2012)
The major sesquiterpene constituents of East-Indian sandalwood oil (Z)-alpha- and (Z)-beta-santalols have shown to be responsible for most of the biological activities and organoleptic properties of sandalwood oil. The work reported here describes the strategic use of medium pressure liquid chromatography (MPLC) for the separation of both alpha- and beta-santalenes and (Z)-alpha- and (Z)-beta-santalols. Silver nitrate impregnated silica gel was used as the stationary phase in MPLC for quantitative separation of alpha- and beta-santalenes and (Z)-alpha- and (Z)-beta-santalols with mobile phases hexane and dichloromethane, respectively. The purities of alpha-santalene and (Z)-alpha-santalol obtained were >96%; however, beta-santalene and (Z)-beta-santalol were obtained with their respective inseparable epi-isomers. Limits of quantification (LoQ) relative to the FID detector were measured for important sesquiterpene alcohols of heartwood oil of S. album using serial dilutions of the standard stock solutions and demonstrated that the quality of the commercial sandalwood oil can be assessed for the content of individual sesquiterpene alcohols regulated by Australian Standard (AS2112-2003), International Organization for Standardization ISO 3518: 2002 (E) and European Union (E. U.).

Probing influence of mesophasic transformation on performance of self-emulsifying system: effect of ion - Patil, Sharvil S.; Venugopal, Edakkal; Bhat, Suresh K.; Mahadik, Kakasaheb R.; Paradkar, Anant R. (Molecular Pharmaceutics, 2012)
Self-emulsifying systems are mixtures of oils and surfactants, ideally isotropic, sometimes including cosolvents, which emulsify under conditions of gentle agitation, similar to those which would be encountered in the gastrointestinal tract. The process of self-emulsification has remained the center of attraction for most researchers. Controlled hydration of self-emulsifying systems shows formation of an intermediate gel phase which upon rupture forms an emulsion. Current work was undertaken to understand and explore the microstructural properties of intermediate gel phase which are believed to influence the performance (droplet size) of the final formulation. The effect of additives on microstructural properties of intermediate gel phase has also been investigated. Microstructural elucidation of hydrated samples of intermediate regimes was done by using techniques such as small angle X-ray scattering, differential scanning calorimetry and rheology. Samples from intermediate regimes showed formation of local lamellar structure which swelled with hydration. In the present work, the effect of addition of salt form of naproxen (sodium and potassium) and naproxen (base) on microstructural properties of intermediate regimes was investigated. Systems containing naproxen salts formed larger droplets whereas naproxen base formed smaller ones. Microstructural properties of intermediate lamellar structures were well correlated with performance of the final formulation. The current studies indicate that by controlling the properties of intermediate regimes optimized formulations with desired performance can be tailor-made.
Keywords: emulsion; lamellar structure; liquid crystal; Microstructure; Naproxen; self-emulsifying system

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

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

Purification and biochemical characterization of endoglucanase from Penicillium pinophilum MS 20 - Pol, Dipali; Laxman, Ryali Seeta; Rao, Mala (Indian Journal of Biochemistry & Biophysics, 2012)
Cellulases find increasing prominence in sustainable production of fuel and feedstock from lignocellulosic biomass. The purification and biochemical characterization of individual components of cellulase complex is important to understand the mechanism of their action for the solubilization of crystalline cellulose. In this study, an extra-cellular endoglucanase isolated from culture filtrate of Penicillium pinophilum MS 20 was purified to homogeneity by ammonium sulphate precipitation, ion-exchange chromatography and gel filtration. The purified endoglucanase (specific activity 69 U/mg) was a monomeric protein with molecular mass of 42 kDa, as determined by SDS-PAGE. The endoglucanase was active over a broad range of pH (4-7) with maximum activity at pH 5 and showed optimum temperature of 50 degrees C. It retained 100% activity at 50 degrees C for 6 h and half- lives of 4 h and 3 h at 60 degrees C and 70 degrees C, respectively. The kinetic constants for the endoglucanase determined with carboxymethyl cellulose as substrate were V-max of 72.5 U/mg and apparent K-m of 4.8 mg/ml. The enzyme also showed moderate activity towards H3PO4 swollen cellulose and p-nitrophenyl beta-D-glucoside, but no activity towards filter paper, Avicel and oat spelt xylan. The activity was positively modulated by 47, 32 and 25% in the presence of Co2+, Zn2+ and Mg2+, respectively to the reaction mixture. The wide pH stability (4-7) and temperature stability up to 50 degrees C of endoglucanase makes the enzyme suitable for use in cellulose saccharification at moderate temperature and pH.
Keywords: Biochemical properties; Carboxymethyl cellulose; Endoglucanase; Penicillium pinophilum MS 20; Purification

Purification and characterization of an antioxidant protein (similar to 16 kDa) from Terminalia chebula fruit - Srivastava, Pratibha; Raut, Hema N.; Wagh, Renuka S.; Puntambekar, Hemalata M.; Kulkarni, Mahesh J. (Food Chemistry, 2012)
Terminalia chebula fruit is used as folk medicine in India and Southeast Asia. An antioxidant protein was isolated by bioassay guided fractionation of T. chebula fruit by homogenizing in the citrate phosphate buffer. The isolated protein (TCP-III) obtained from fruit was purified by gel chromatography and preparative HPLC, showed apparent molecular weight of 16 kDa by SDS-PAGE and MALDI-TOF/MS analyses. Amino acid sequence obtained by LC-MSE analysis showed homology with the predicted protein fragments of Populus trichocarpa, putative uncharacterized protein fragments from Oryza sativa and with fragments of 17 kDa thylakoid lumenal protein from Spinacia oleracea. TCP-III exhibited significant radical scavenging in DPPH, NO, H2O2 and ABTS assays. In addition, TCP-III inhibited oxidation of linoleic acid in beta-carotene bleaching assay, reduced ferric ions and chelated ferrous ions. The present finding demonstrates uniquely, for the first time, characterization of an antioxidant protein from T. chebula fruit. (C) 2011 Elsevier Ltd. All rights reserved.
Keywords: 16 kDa protein molecule of T. chebula; Antioxidant and free radical scavenging activity; Characterization; Purification; Terminalia chebula fruit

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

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

Rapid self-healing hydrogels - Phadke, Ameya; Zhang, Chao; Arman, Bedri; Hsu, Cheng-Chih; Mashelkar, Raghunath Anant; Lele, Ashish K.; Tauber, Michael J.; Arya, Gaurav; Varghese, Shyni (Proceedings of the National Academy of Sciences of the United States of America, 2012)
Synthetic materials that are capable of autonomous healing upon damage are being developed at a rapid pace because of their many potential applications. Despite these advancements, achieving self-healing in permanently cross-linked hydrogels has remained elusive because of the presence of water and irreversible cross-links. Here, we demonstrate that permanently cross-linked hydrogels can be engineered to exhibit self-healing in an aqueous environment. We achieve this feature by arming the hydrogel network with flexible-pendant side chains carrying an optimal balance of hydrophilic and hydrophobic moieties that allows the side chains to mediate hydrogen bonds across the hydrogel interfaces with minimal steric hindrance and hydrophobic collapse. The self-healing reported here is rapid, occurring within seconds of the insertion of a crack into the hydrogel or juxtaposition of two separate hydrogel pieces. The healing is reversible and can be switched on and off via changes in pH, allowing external control over the healing process. Moreover, the hydrogels can sustain multiple cycles of healing and separation without compromising their mechanical properties and healing kinetics. Beyond revealing how secondary interactions could be harnessed to introduce new functions to chemically crosslinked polymeric systems, we also demonstrate various potential applications of such easy-to-synthesize, smart, self-healing hydrogels.
Keywords: adhesives; biomimetic materials; Hydrophobicity; molecular dynamics; smart materials

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

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

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

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

Reply to the ``comments to CFD simulation of stirred tanks: comparison of turbulence models. part I: radial flow impellers and part II: axial flow impellers, multiple impellers and multiphase dispersions'' - Joshi, J. B.; Nere, N. K.; Rane, C. V.; Murthy, B. N.; Mathpati, Channamallikarjun S.; Patwardhan, A. W.; Ranade, V. V. (Canadian Journal of Chemical Engineering, 2012)

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

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

Segmented flow synthesis of Ag nanoparticles in spiral microreactor: role of continuous and disperzsed phase - Kumar, D. V. Ravi; Bhagavatula L. V. Prasad; Kulkarni, Amol A. (Chemical Engineering Journal, 2012)
This work focuses on understanding the effect of segmented flow on the nanoparticle size distribution in a unidirectionally expanding spiral microreactor, where secondary flows are prevalent in the absence of segmentation. Stearic acid sophorolipid reduced/capped Ag NPs were synthesized in the aqueous phase and air or kerosene was used as inert phases for creating the gas-liquid and liquid-liquid segmented flow, respectively. While, in one case the reactant phase is in the form of dispersed phase slugs, in the other case it is in the form of continuous phase, each exhibiting a different behavior. The slug sizes and the slip velocity, both of which govern the nature of internal mixing in the reactant phase slug controlled the nanoparticle size distribution. This observation was consistent for both, gas-liquid and liquid-liquid segmented flows. The micromixer having smaller orifice diameter yielded smaller slugs and also a narrow particle size distribution. In general, the particle sizes were much smaller for gas-liquid flow rather than for liquid-liquid flow. Because of the unidirectionally expanding spiral geometry of the channel, at any given condition, unsteady behavior of slugs due to continuously varying radius of curvature results in variation in the slip velocity along the length of microchannel. This effect was seen to further narrow the particle size distribution than alone by the segmented flow. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Ag nanoparticles; Segmented flow synthesis; Sophorolipid; Spiral microreactor

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

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

Selectivity tuning options in hydrogenation of m-chloronitrobenzene to m-chloroaniline over mono- and bimetallic supported Pt catalysts - Mane, Rasika B.; Potdar, Aparna S.; Nadgeri, Jayprakash M.; Biradar, Narayan S.; Rode, Chandrashekhar V. (Industrial & Engineering Chemistry Research, 2012)
Supported monometallic (Pt, Ni,) and bimetallic (Ni-Pt) catalysts were prepared for the selective liquid phase hydrogenation of m-chlronitrobenzene to m-chloroaniline (m-CAN). It was found that the use of sodium carbonate as an additive substantially reduced the extent of dehydrohalogenation in the case of monometallic, 1% Pt/C catalyst, to give the highest selectivity of 96% to m-CAN. Ni-Pt bimetallic catalyst although showed almost complete selectivity (>99%) to m-chloroaniline; its activity was several fold lower than that of 1% Pt/C Na2CO3 system. However, compared with Ni monometallic catalyst, bimetallic Ni-Pt showed higher activity and selectivity due to the presence of electron rich surface metallic Pt stabilized by Ni having lower ionization potential compared with Pt.

Self-assembled one dimensional functionalized metal-organic nanotubes (MONTs) for proton conduction - Panda, Tamas; Kundu, Tanay; Banerjee, Rahul (Chemical Communications, 2012)
Two self-assembled isostructural functionalized metal-organic nanotubes have been synthesized using 5-triazole isophthalic acid (5-TIA) with In(III) and Cd(II). In-and Cd-5TIA possess one-dimensional (1D) nanotubular architecture and show proton conductivity along regular 1D channels, measured as 5.35 x 10(-5) and 3.61 x 10(-3) S cm(-1) respectively.

SHI irradiation induced effects in functionalized MWCNTs - Saikiran, V.; Pathak, A. P.; Rao, N. Srinivasa; Devaraju, G.; Debgupta, Joyashish; Kyriakou, I.; Emfietzoglou, D. (Radiation Effects and Defects in Solids, 2012)
Multi-walled carbon nanotubes (MWCNTs) have attracted extensive attention globally due to their applications in modern nanotechnology. It is very important to study the effects on these MWCNTs under swift heavy ion (SHI) irradiation since ion irradiation has been recognized as one of the best tools for nanostructuring of materials, in general. Here, we present the effects of 80MeV Ni ions with a fluence ranging from 3 x 10(12) to 3 x 10(13) ions/cm(2) on functionalized MWCNT mats. The properties of pristine and irradiated samples were studied using X-ray diffraction, Raman spectroscopy and transmission electron microscopy. The effects of SHI irradiation on these samples are discussed in detail.
Keywords: CNT; Raman; SHI; TEM

Single crystal X-ray structure of lawsone anion: evidence for coordination of alkali metal ions and formation of naphthosemiquinone radical in basic media - Salunke-Gawali, Sunita; Kathawate, Laxmi; Shinde, Yogesh; Puranik, Vedavati G.; Weyhermueller, Thomas (Journal of Molecular Structure, 2012)
2-hydroxy-1,4-naphthoquinone; Lawsone (Lw) is a natural compound found in henna leaves. The reaction of lawsone with `Na' metal (Lw-1), CH3COONa (Lw-2), NaOH (Lw-3), KOH (Lw-4), K2CO3 (Lw-5) and Tris(hydroxymethyl)aminomethane (Lw-6) were studied. Red orange solids obtained for Lw-1 to Lw-6 are characterized by Elemental Analysis, FTIR, (HNMR)-H-1 and EPR studies. The results reveal the coordination of alkali metals `Na' and `K' to lawsone anion. The single crystal X-ray structure of Lw-6 was solved and it crystallizes in triclinic space group P-1 with extensive hydrogen bonding network of C-H center dot center dot center dot O, N-H center dot center dot center dot O and O-H center dot center dot center dot O between cations and anions. Polycrystalline powder X-band EPR spectra of Lw-1 to Lw-5 shows signals similar to 2.004 at 133 K, while Lw-6 is EPR silent. The naphthosemiquinone (NSQ) radical formed in Lw-2 to Lw-5, is due to disproportion reaction of catechol and naphthoquinone. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: 2-Hydroxy-1; 4-naphthoquione; EPR; hydrogen bonding; Lawsone; Naphthosemiquinone radicals

Smart wireless temperature monitor & control system - Patil, Rohit; Joshi, Dnyanesh; More, Rahul; Iyer, Neelima (UACEE International Journal of Computer Science and its Application, 2012)

Solid phase morphological diversity of a rare vanadium cubane (V4O16) based metal organic framework - Dey, Chandan; Das, Raja; Poddar, Pankaj; Banerjee, Rahul (Crystal Growth & Design, 2012)
A Cu(II) connected V4O16-cubane based metal organic framework, Cu-2(phen)(2)(V4O8) (PO4)(4) [Cu2V4O16-2D] was synthesized under hydrothermal conditions. This is the first example of transition metal connected V4O16-cubane based MOF. X-ray single crystal data shows the alternate arrangement V4O16-cubane and Cu(phen)(O)(3) square pyramidal unit in two dimensions. These two-dimensional sheets are stacked on top of each other to form a three-dimensional architecture. Cu2V4O16-2D shows two types of solid state morphologies of the same phase, which was confirmed by scanning electron microscopy. It is noteworthy that this type of morphological difference of the solid phase in an extended metal organic hybrid material is rare and has not been perceived in the polyoxovanadate based MOFs literature. Cu2V4O16-2D was further characterized by powder X-ray diffraction (PXRD), thermal gravimetric analysis (TGA), IR-spectroscopy, scanning electron microscopy (SEM), and elemental analysis. We also studied the static magnetic and gas adsorption properties for Cu2V4O16-2D.

Solution mediated phase transformation (RHO to SOD) in porous Co-imidazolate based zeolitic frameworks with high water stability - Biswal, Bishnu P.; Panda, Tamas; Banerjee, Rahul (Chemical Communications, 2012)
Here we report a highly porous, water stable Co based ZIF [CoNIm (RHO)] and its solution mediated phase transformation to a less porous and water unstable ZIF [CoNIm (SOD)]. CoNIm (RHO) has high Langmuir surface area [2087 m(2) g(-1)] as well as high water adsorption [200 cm(3) (STP) g(-1)] capacity.

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

Stereospecific synthesis of C-arabinofuranosides and carba-disaccharide analogues of Motif C of cell wall AG complex of Mtb - Patil, Rahul S.; Ahire, Ketan M.; Ramana, C. V. (Tetrahedron Letters, 2012)
A simple strategy for the synthesis of alpha- and beta-C-arabinofuranosides featuring a furan ring transposition reaction has been developed. A novel double furan ring transposition reaction has proposed and executed for the synthesis of the carba-disaccharide analogue of Motif C of the cell wall AG complex of Mtb. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Arabinose; C-Glycosides; Carba-disaccharide; Cell wall AG complex; Ring transposition

Strong metal-metal coupling in mixed-valent intermediates [Cl(L)Ru(mu-tppz)Ru(L)Cl](+), L = beta-diketonato ligands, tppz=2,3,5,6-tetrakis(2-pyridyl)pyrazine - Kundu, Tanaya; Schweinfurth, David; Sarkar, Biprajit; Mondal, Tapan Kumar; Fiedler, Jan; Mobin, Shaikh M.; Puranik, Vedavati G.; Kaim, Wolfgang; Lahiri, Goutam Kumar (Dalton Transactions, 2012)
Five diruthenium(II) complexes [Cl(L)Ru(mu-tppz)Ru(L)Cl](1-5) containing differently substituted beta-diketonato derivatives (1: L = 2,4-pentanedionato; 2: L = 3,5-heptanedionato; 3: L = 2,2,6,6-tetramethyl-3,5-heptanedionato; 4: L = 3-methyl-2,4-pentanedionato; 5: L = 3-ethyl-2,4-pentanedionato) as ancillary ligands (L) were synthesized and studied by spectroelectrochemistry (UV-Vis-NIR, electron paramagnetic resonance (EPR)). X-ray structural characterisation revealed anti (1, 2, 5) or syn (3) configuration as well as non-planarity of the bis-tridentate tppz bridge and strong d pi(Ru-II) -> pi*(pyrazine, tppz) back-bonding. The widely separated one-electron oxidation steps, (RuRuII)-Ru-II/(RuRuIII)-Ru-II and (RuRuIII)-Ru-II/(RuRuIII)-Ru-III, result in large comproportionation constants (K-c) of >= 10(10) for the mixed-valent intermediates. The syn-configurated 3(n) exhibits a particularly high K-c of 10(12) for n = 1+, accompanied by density functional theory (DFT)-calculated minimum Ru-N bond lengths for this (RuRuIII)-Ru-II intermediate. The electrogenerated mixed-valent states 1(+)-5(+) exhibit anisotropic EPR spectra at 110 K with average values < g > of 2.304-2.234 and g anisotropies Delta g = g(1)-g(3) of 0.82-0.99. Metal-to-metal charge transfer (MMCT) absorptions occur for 1(+)-5(+) in the NIR region at 1660 nm-1750 nm (epsilon approximate to 2700 dm(3) mol(-1) cm(-1), Delta nu(1/2) approximate to 1800 cm(-1)). DFT calculations of 1(+) and 3(+) yield comparable Mulliken spin densities of about 0.60 for the metal ions, corresponding to valence-delocalised situations (Ru-2.5)(2). Rather large spin densities of about -0.4 were calculated for the tppz bridges in 1(+) and 3(+). The calculated electronic interaction values (V-AB) for 1(+)-5(+) are about 3000 cm(-1), comparable to that for the Creutz-Taube ion at 3185 cm(-1). The DFT calculations predict that the (RuRuIII)-Ru-III forms in 12(+)-52(+) prefer a triplet (S = 1) ground state with Delta E (S = 0 - S = 1) similar to 5000 cm(-1). One-electron reduction takes place at the tppz bridge which results in species [Cl(L)Ru-II(mu-tppz(.-)) Ru-II(L)Cl](-) (1(.-)-3(.-), 5(.-)) which exhibit free radical-type EPR signals and NIR transitions typical of the tppz radical anion. The system 4(n) is distinguished by lability of the Ru-Cl bonds.

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

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

Studies on the resistive response of nickel and cerium doped SnO2 thick films to acetone vapor - Bagal, L. K.; Patil, J. Y.; Mulla, Imtiaz S.; Suryavanshi, S. S. (Ceramics International, 2012)
Undoped and Ni, Ce-doped nanocrystalline tin oxide were synthesized by co-precipitation route. Doped as well as undoped SnO2 compositions revealed single phase structure without any impurity. The lattice constant of SnO2 increases and the grain size decreases with doping of Ni and Ce. The responses of the sensing elements are evaluated by measuring the resistance change upon exposure to various test gases such as liquid petroleum gas (LPG), acetone, ethanol and ammonia. In comparison to LPG, ethanol, and ammonia the response towards acetone vapor increases markedly on simultaneous doping of Ni and Ce. For acetone vapors with 500 ppm at 300 degrees C, the undoped SnO2 shows 31% response, while with individual Ni or Ce doping it increases to 38 and 60%, respectively, however with simultaneous doping of Ni and Ce there is a significant enhancement up to 92%. The results of gas sensing measurements reveal that the thick films deposited on alumina substrates using screen printing technique give selectively a high response of (87%) with fast recovery (similar to 1 min) towards 100 ppm acetone at 300 degrees C. (c) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: (Ni plus Ce)-doping; Acetone vapor; Screen-printing; SnO2

Supported copper triflate as an efficient catalytic system for the synthesis of highly functionalized 2-naphthol Mannich bases under solvent free condition - Dindulkar, Someshwar D.; Puranik, Vedavati G.; Jeong, Yeon Tae (Tetrahedron Letters, 2012)
Various heterogeneous catalysts (Lewis acid) have been prepared and screened for the synthesis of Betti bases in an attempt to reduce the environmental hazards associated with the conventional homogeneous Lewis acid system. And we found especially Cu(OTf)(2)center dot SiO2 catalyzes the three-component coupling of aldehyde, 2-naphthol, and alicyclic amine to generate Betti base with high efficiency under neat conditions without additional co-catalyst or additive in air. The reaction is not sensitive to water and occurs smoothly in water as well. (c) 2012 Elsevier Ltd. All rights reserved.
Keywords: Betti bases; single-crystal XRD; Solvent-free; Supported copper triflate; Three-component coupling

Supramolecular synthon transferability and gelation by diprimary ammonium monocarboxylate salts - Das, Uttam Kumar; Puranik, Vedavati G.; Dastidar, Parthasarathi (Crystal Growth & Design, 2012)
Earlier studies revealed that primary ammonium dicarboxylate (PAD) salts possessed gelling ability, and many such salts displayed a 1D columnar hydrogen bonded network (observed in primary ammonium monocarboxylate (PAM) salts) on either side of the dicarboxylate end of the anion. In the present study, a new series of diprimary ammonium monocarboxyate (DPAM) salts have been prepared with the aim of achieving supramolecular synthon transferability (the same 1D columnar hydrogen PAM bonded network on either side of the diammonium cation) in these salts. Single crystal X-ray diffraction studies revealed that, in 47% of the DPAM salts, such supramolecular synthon transferability indeed took place. Some of the DPAM salts also showed gelation ability. The gels were characterized by DSC, rheology, electron microscopy, and atomic force microscopy. Structure property correlation using single crystal and powder X-ray diffraction data on a selected gel was also attempted.

Surface characterization of Au-ZnO nanowire films - Jamali-Sheini, Farid; Yousefi, Ramin; Patil, K. R. (Ceramics International, 2012)
Au-ZnO nanowire films have been synthesized by annealing Zn foils coated with a thin layer of gold. An X-ray diffraction study found that the synthesized ZnO consists mainly of a hexagonal wurtzite structure along with a small amount of AuZn3 phase. Scanning electron images showed that the ZnO wires extend to several microns in length. X-ray photoelectron spectroscopy studies confirmed the oxidation states of Au and Zn. An asymmetric O ls peak indicates the presence of oxygen in an oxide layer and O H groups on the films surfaces. Photoluminescence (PL) spectra showed different visible peaks for pre-annealed films, while for annealed films an UV peak appeared. In addition, the PL analysis showed that the overall intensity of photoluminescence decreased significantly after the films were annealed. Raman spectroscopy results also indicated that the crystalline quality of the films improved with annealing. This could be attributed to a decrease in oxygen vacancies and/or absorption of O-H groups on the surface of ZnO film. The highly hydrophilic surface with a water contact angle of similar to 155 degrees was obtained after annealing in air. (c) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: Au-ZnO; Highly hydrophilic; Nanowires; XPS

Syntheses, crystal structures, and magnetic properties of metal-organic hybrid materials of Co(II) using flexible and rigid nitrogen-based ditopic ligands as spacers - Ahmad, Musheer; Sharma, Mamsh K.; Das, Raja; Poddar, Pankai; Bharadwaj, Parimal K. (Crystal Growth & Design, 2012)
{A carboxylate-based flexible ligand, 5-(4-carboxybenzyloxy)isophthalic acid (p-cbiaH(3)), readily reacts with Co(II) salts in the presence of different pyridine-based coligands such as 4-bis(4-pyridinylmethyl)piperazine (bpmp) or 1,2-di(4-pyridyl)ethylene (dpe) under hydrothermal conditions to afford two different three-dimensional (3D) coordination polymers, {[Co-4(OH)(2)(p-cbia)(2)(bpmp)-(H2O)(3)]center dot 2H(2)O}(n) (1) and {[Co-4(OH)(2)(p-cbia)(2)(dpe)(H2O)(4)]center dot 2H(2)O\

Synthesis and antifungal activity of 1,5-disubstituted-1,2,3-triazole containing fluconazole analogues - Pore, Vandana S.; Jagtap, Manisha A.; Agalave, Sandip G.; Pandey, Atindra K.; Siddiqi, Mohammad I.; Kumar, Vikash; Shukla, Praveen K. (Medchemcomm, 2012)
Fluconazole based novel mimics containing 1,5-disubstituted 1,2,3-triazoles were synthesized by using Ru catalysed 1,3 dipolar cycloaddition. All the newly synthesized compounds and pure enantiomers were more potent than fluconazole against Candida albicans. Docking of 9A and 9B showed different conformation in the active site of Cyp51 of Candida albicans. The more active compounds 2 and 2A did not exhibit any toxicity up to 3.12 mu g mL(-1) against mammalian cell line L929.

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

Synthesis and stereochemistry of highly crowded N-benzylpiperidones - Dindulkar, Someshwar D.; Parthiban, Paramasivam; Puranik, Vedavati G.; Jeong, Yeon Tae (Journal of Molecular Structure, 2012)
A series of N-benzylated 3,5-diakyl-2,6-diarylpiperidin-4-ones 4-8 were conveniently synthesized in significant yields of 68-88% by N-benzylation of the corresponding 2,6-diaryl-3,5-dimethylpiperidin-4-ones 1-3 using different benzyl bromides. Initially, the new piperidone 2,6-bis(4-ethoxypheny1)-3,5-dimethylpiperidin-4-one 3 was synthesized by the condensation of 1:1:2 M ratio of 3-pentanone, ammonium acetate and para-ethoxybenzaldehyde in ethanolic medium. All the synthesized new compounds 3-8 were characterized by their analytical and spectral (IR, H-1 and C-13 NMR) interpretations. The stereochemistry of the new piperidone 3 was elucidated as chair conformation with an equatorial orientation of all substituents, suggested by its vicinal couplings from H-1 NMR spectrum. To investigate the impact on piperidone stereochemistry as well as NMR chemical shifts, all the N-benzylated products 4-8 were compared with their corresponding precursors, and as a result, it is clearly established that all the synthesized N-benzyl piperidones exist in the chair conformation with an equatorial orientation of all the substituents at C-2, C-3, C-5, C-6 and N. Contrary to the probability all N-benzylated compounds retain the same conformation and configuration as their precursors, however, a remarkable change on the chemical shifts are observed. For the further unambiguous confirmation of stereochemistry, the 1-benzyl-3,5-dimethyl-2,6-diphenylpiperidin-4-one 4 was examined by single-crystal X-ray diffraction. The compound 4, C26H27NO, crystallized in a P-1 space group under triclinic system with unit cell dimensions a, b, c (angstrom) and alpha, beta, gamma (degrees) of 10.156(2), 11.002(2), 11.348(4) and 116.74(4), 100.81(3), 100.17(3), respectively. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: Chair conformation; Configuration; crystal structure; N-benzylation; NMR; Piperidin-4-one

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

Synthesis, characterization, and magnetic studies of coordination polymers with Co(II) and Mn(II) ions - Ahmad, Musheer; Das, Raja; Lama, Prem; Poddar, Pankaj; Bharadwaj, Parimal K. (Crystal Growth & Design, 2012)
{An ether bridged tricarboxylic acid ligand, 5-(4-carboxybenzyloxy)isophthalic acid (p-cbiaH(3)) has been used to construct three coordination polymers with Co(II) salts in presence of different nitrogen donor ligands such as 1,4-bis(4-pyridinylmethyl)piperazine (bpmp), dipyridine-4-yl-diazene (dpd), and 4,4'-bipyridine (bpy). The products formed under hydrothermal conditions are formulated as {[Co-3(p-cbia)(2)(bpmp)(2)(H2O)(6)]center dot 10H(2)O}(n) (1), {[Co-2(p-cbiaH)(2)(dpd)(H2O)(2)]\

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

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

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

Synthesis, spectroscopy, and electrochemical investigation of new conjugated polymers containing thiophene and 1,3,4-thiadiazole in the main chain - Patil, Prashant S.; Haram, Nanda S.; Pal, Ravindra R.; Periasamy, N.; Wadgaonkar, Prakash P.; Salunkhe, Manikrao M. (Journal of Applied Polymer Science, 2012)
Novel photoluminescent donoracceptor poly(p-phenylenevinylene)-type conjugated polymers containing thiophene and 1,3,4-thiadiazole units in the main chain were synthesized from 2,5-bis(5-bromomethyl-2-thienyl)-1,3,4-thiadiazole and 1,3/1,4-benzenedialdehyde by WittigHorner reaction. The synthesized polymers were characterized by the use of thermal analysis and spectroscopic (infrared, UV-visible absorption, and photoluminescence) measurement. The resultant material exhibited bluish green, green, and orange fluorescence in their solution and thin film and solid forms, respectively. The redox property of the polymers has also been studied by cyclic voltammetry. The optical and electrochemical studies reveal that these novel polymers are new promising materials for the development of efficient polymer light-emitting diodes. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Keywords: conjugated polymers; photoluminescence; thiophene and thiadiazole-containing polymer

Temperature-dependent spectroscopic evidences of curcumin in aqueous medium: a mechanistic study of its solubility and stability - Jagannathan, Ramya; Abraham, Priya Mary; Poddar, Pankaj (Journal of Physical Chemistry B, 2012)
In curcumin, keto-enol-enolate equilibrium of the heptadiene-dione moiety determines its physiochemical and antioxidant properties. However, its poor solubility in water at neutral pH and room temperature decreases its bioavailability. Potential therapeutic applications have triggered an interest in manipulating the solubility of curcumin in water as its stability and solubility in water remains poorly understood. Here, the mechanism behind its solubility at various temperatures and the influence of interplay of temperature, intramolecular H-bonding, and intermolecular forces is reported, which leads to aggregation-disaggregation at various temperatures. Remarkable change is observed in temperature-dependent electronic transition behavior of curcumin, however, the absorption spectra after cooling and heating cycles remain unchanged, hinting much better thermal stability of curcumin in water than previously thought. This study indicates that it is perhaps the breaking of intramolecular hydrogen bonding which leads to exposure of polar groups and hence responsible for the dissolution of curcumin at higher temperature. The formation of intermolecular aggregates might be responsible behind a better room temperature stability of the molecules after cooling its aqueous suspension from 90 to 25 degrees C. These curcumin solubility studies have great application in biological research with reference to bioavailability and to understand target oriented mode of action of curcumin.

Theoretical study of frequency and temperature dependence of dipole-quadrupole polarizability of P-4 and adamantane - Shedge, Sapana V.; Pal, Sourav; Koester, Andreas M. (Chemical Physics Letters, 2012)
The frequency and temperature dependence of dipole-quadrupole polarizability of tetrahedral P-4 and adamantane molecules have been studied using first-principle all-electron density functional theory calculation. The recently developed time-dependent auxiliary density functional theory is extended for the calculation of dynamic dipole-quadrupole polarizabilities. Temperature effects are incorporated by Born-Oppenheimer molecular dynamics (BOMD) simulations recorded up to 100 ps. The dynamic dipole-quadrupole polarizabilities are calculated along these trajectories. The frequency and temperature effects can be significant for the accurate calculation of dipole-quadrupole polarizability. We have also identified the main reason for the observed discrepancy between experiment and theory in the case of adamantane. (c) 2012 Elsevier B.V. All rights reserved.

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

Total synthesis and structural revision of stagonolide D - Vadhadiya, Paresh M.; Puranik, Vedavati G.; Ramana, Chepuri V. (Journal of Organic Chemistry, 2012)
The total synthesis of the putative structure of stagonolide D has been completed. The relative and absolute configuration of stagonolide D was established by synthesizing its optical antipode. The adopted strategy involves the construction of the central macrolide employing ring-closing metathesis (RCM), followed by selective protecting group manipulations and a final concomitant −OTBS deprotection and displacement of an −OMs placed next to it, resulting in the formation of the epoxide ring.

Total synthesis of (-)-isatisine A - Patel, Pitambar; Ramana, C. V. (Journal of Organic Chemistry, 2012)
A modular total synthesis of (-)-isatisine A is described in which four consecutive metal-mediated transformations have been employed at the final stage. These include [Pd]-catalyzed Sonogashira coupling, [Pd]-catalyzed nitroalkyne cycloisomerization leading to isatogens, and addition of indoles to isatogens using InCl3- and [Rh]-catalyzed oxidative N-heterocyclization of amino alcohol to form the key amide bond. In addition to these, the removal of the protecting groups has also been carried out in a selective fashion employing either catalytic or stoichiometric metal/metal-based reagents.

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

Tuberculosis drug streptomycin as a potential cancer therapeutic: inhibition of miR-21 function by directly targeting its precursor - Bose, Debojit; Jayaraj, Gopal Gunanathan; Suryawanshi, Hemant; Agarwala, Prachi; Pore, Subrata Kumar; Banerjee, Rajkumar; Maiti, Souvik (Angewandte Chemie-International Edition, 2012)
Keywords: Apoptosis; drug discovery; Gene expression; inhibitors; RNA

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

Ultra-low level optical detection of mercuric ions using biogenic gold nanotriangles - Singh, Amit; Pasrichax, Renu; Sastry, Murali (Analyst, 2012)
Mercury is a serious environmental pollutant known to have detrimental health effects in all life forms. Here, we report the use of biologically synthesized aqueous gold nanotriangles for sensitive and selective optical detection of femto-molar levels of mercury ions by exploiting the high amalgamation tendency of mercury metal towards gold. Aqueous chloroaurate ions were reduced using lemongrass (Cymbopogon flexuosus) leaf extract at room temperature to form gold nanotriangles. Mercuric (Hg2+) ions were reduced in the presence of these triangles to facilitate amalgamation and the optical properties were monitored. We observe a significant change in the longitudinal plasmon absorption band of the nanotriangles even at femto-molar concentrations of mercuric ions. High-resolution transmission electron microscopy confirms changes in particle morphology at such low concentrations. This protocol shows no sensitivity to other environmentally relevant metal ions, including Pb2+, Zn2+, Cd2+, Fe2+, Ni2+, Sr2+, Ca2+, Mn2+, and Cu2+, confirming further that change in the optical properties of gold nanotriangles in the presence of reduced mercuric ions is solely due to the strong amalgamation tendency of mercury metal.

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

Unusual conformational similarity of two peptide folds featuring sulfonamide and carboxamide on the backbone - Vijayadas, Kuruppanthara N.; Davis, Hilda C.; Kotmale, Amol S.; Gawade, Rupesh L.; Puranik, Vedavati G.; Rajamohanan, Pattuparambil R.; Sanjayan, Gangadhar J. (Chemical Communications, 2012)
Two folded peptides featuring carboxamide and sulfonamide at the core of the peptide fold have been shown to possess almost similar conformational features, despite the well-known fact that carboxamides and sulfonamides have strikingly different hydrogen-bonding and geometrical preferences.

Vibrational multi-reference coupled cluster theory in bosonic representation - Banik, Subrata; Pal, Sourav; Prasad, M. Durga (Journal of Chemical Physics, 2012)
The vibrational multi-reference coupled cluster method is developed to calculate the vibrational excitation energies of polyatomic molecules. The method is implemented on ozone and formaldehyde molecules and the results are compared with full vibrational configuration interaction (FVCI) method. A good agreement is found between the vibrational multi-reference coupled cluster method and converged FVCI method for lower lying vibrational states. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4753422]

Visible light photoredox catalysis: generation and addition of N-aryltetrahydroisoquinoline-derived alpha-amino radicals to michael acceptors - Kohls, Paul; Jadhav, Deepak; Pandey, Ganesh; Reiser, Oliver (Organic Letters, 2012)
The photoredox-catalyzed coupling of N-aryltetrahydroisoquinoline and Michael acceptors was achieved using Ru(bpy)(3)Cl-2 or [Ir(ppy)(2)-(dtb-bpy)]PF6 in combination with irradiation at 455 nm generated by a blue LED, demonstrating the trapping of visible light generated alpha-amino radicals. While intermolecular reactions lead to products formed by a conjugate addition, in intramolecular variants further dehydrogenation occurs, leading directly to 5,6-dihydroindolo[2,1-a]tetrahydroisoquinolines, which are relevant as potential immunosuppressive agents.

3-Dimensionally self-assembled single crystalline platinum nanostructures on few-layer graphene as an efficient oxygen reduction electrocatalyst - Unni, SreeKuttan M.; Pillai, Vijayamohanan K.; Kurungot, Sreekumar (RSC Advances, 2013)
Here, we report for the first time the synthesis of a 3-D self-assembled single crystalline platinum nanostructure directly on the graphene surface (PtNAGE) without using any harmful structural directing agents. A slow reduction method is used to prepare the desired platinum morphology. Initial formation of platinum nanoparticles and their homogenous dispersion on the surface of graphene have been observed 10 h after the commencement of the reduction using formic acid as the reducing agent. From these initially deposited seed particles, the growth starts on the {111} facets along the < 111 > direction and the nanostructure formation is completed within 72 h of the commencement of the reaction. The individual assembly has a diameter of similar to 80 nm. PtNAGE shows superior electrocatalytic activity towards oxygen reduction compared to graphene supported platinum (PtGE) and commercial carbon supported platinum (PtC) catalysts. PtNAGE is less vulnerable to strong hydroxyl adsorption compared to PtC and PtGE. Specific activity and mass activity of the catalyst are high compared to PtC by a factor of 6.50 and 1.80, respectively, and 4.00 and 3.05, respectively, compared to PtGE. The limiting current density of PtNAGE is 1.28 and 1.20 times higher than PtGE and PtC, respectively. Kinetic analysis of PtNAGE shows that the oxygen reduction reaction follows first order kinetics involving a four electron transfer mechanism with the direct formation of water. In addition to this, it has been observed that PtNAGE also prevents surface area degradation better than the commercial platinised carbon under potential induced conditions.

Acetone vapour sensing characteristics of undoped and Zn, Ce doped SnO2 thick film gas sensor - Bagal, L. K.; Patil, J. Y.; Bagal, K. N.; Mulla, Imtiaz S.; Suryavanshi, S. S. (Materials Research Innovations, 2013)
The nanocrystalline materials of zinc and ceria doped tin oxide [(Zn+Ce)-SnO2] powders were synthesised by coprecipitation method and investigated for their sensing properties towards liquid petroleum gas (LPG), ethanol, ammonia and acetone vapour. The crystal structure and phase of the as synthesised and sintered powders were characterised by X-ray diffractometer and the microstructure by scanning electron microscopy. All the doped and undoped SnO2 compositions revealed single phase solid solution formation. Transmission electron microscope results indicated that well crystallised (Zn+Ce) doped SnO2 particles of size similar to 7 nm were obtained at the annealing temperature of 650 degrees C. The reduction in grain size of the metal oxide is a key factor to enhance the gas sensing properties. The doping of zinc, ceria in SnO2 has reduced the grain size and improved the gas response. The results of gas sensing measurements showed that the thick films deposited on alumina substrates using screen printing technique exhibited high response to acetone at an operating temperature of 300 degrees C. Further, the selectivity of the sensor towards acetone with respect to other reducing gases (LPG, ethanol and ammonia) was studied.
Keywords: Gas; Screen printing; Sensor; SnO2

Alishewanella solinquinati sp nov., isolated from soil contaminated with textile dyes - Kolekar, Yogesh M.; Pawar, Shrikant P.; Adav, Sunil S.; Zheng, Liu-Qiang; Li, Wen-Jun; Shouche, Yogesh S.; Dastager, Syed Gulam; Kodam, Kisan M. (Current Microbiology, 2013)
A novel Gram-negative, motile, rod-shaped, facultative anaerobic bacterial strain, KMK6(T), was isolated from soil contaminated with textile dyes from an industrial estate located at Ichalkaranji, Maharashtra, India, and its taxonomical position was established by using a polyphasic approach. The major cellular fatty acids included C-17:1 omega 8c, summed feature 3 (C-16:1 omega 7c and/or iso-C-15:0 2-OH), C-17:0, C-16:0,C- and C-18:1 omega 7c. The DNA G+C content of strain KMK6(T) was 48.8 mol %. 16S rRNA gene sequence analysis confirmed its placement in the genus Alishewanella, and exhibited sequence similarity levels of below 97 % to the type strains of validly published Alishewanella species. On the basis of genotypic and phenotypic evidence, strains KMK6(T) is considered to be a novel species of the genus Alishewanella, for which we propose that strain KMK6(T) (=NCIM 5295(T) =BCRC 17848(T)) is assigned to a novel species, Alishewanella solinquinati sp. nov.

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

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

Antimycobacterial labdane diterpenes from leucas stelligera - Kulkarni, Roshan R.; Shurpali, Ketaki; Puranik, Vedavati G.; Sarkar, Dhiman; Joshi, Swati P. (Journal of Natural Products, 2013)
Phytochemical investigation of the acetone extract of the aerial parts of Leucas stelligera afforded four new compounds (1-4) belonging to the labdane diterpene series as well as two known flavones, velutin (5) and chrysoeriol (6). Structure elucidation of the new compounds was carried out using ID and 2D NMR spectroscopic data and single-crystal X-ray crystallography of compound 1. Compounds 1-4 exhibited selective antimycobacterial activity against Mycobacterium tuberculosis with IC50 values in the range 5.02-9.80 mu g/mL.

Ant-pro reverse-turn motif. structural features and conformational characteristics - Thorat, Vijaykumar H.; Ingole, Tukaram S.; Vijayadas, Kuruppanthara N.; Nair, Roshna V.; Kale, Sangram S.; Ramesh, Veera V. E.; Davis, Hilda C.; Prabhakaran, Panchami; Gonnade, Rajesh G.; Gawade, Rupesh L.; Puranik, Vedavati G.; Rajamohanan, Pattuparambil R.; et al. (European Journal of Organic Chemistry, 2013)
This article details the characteristic conformational features of the Ant-Pro reverse turn ? a folded pseudo -turn motif that displays a closed nine-membered-ring hydrogen-bonded network involving just two amino acid residues, namely anthranilic acid (Ant; a constrained -amino acid), and proline (Pro; a constrained -amino acid). The results from the extensive investigation of ten crystal structures and their NMR conformations in the solution state provide a clear idea about the conformational characteristics of the Ant-Pro reverse turn. The Ant and Pro residues, which form the turn segment, maintain a perfect antiperiplanar orientation throughout, leaving little possibility for the formation of the otherwise possible six-membered hydrogen-bonding that requires a coplanar disposition of the two amino acid residues, as clearly evident from investigation of several crystal structures. The closed hydrogen-bonded network observed in the Ant-Pro reverse turn motif, formed in the forward direction of the sequence (12 amino acid interactions) involving only two amino acid residues, is in stark contrast to the native -turns that involve four residues to form hydrogen-bonded network featuring backward 14 amino acid interactions. The readily available two-residue Ant-Pro motif raises the possibility of a practical utility, particularly in the application of rigidifying flexible peptide backbones by inserting the robust Ant-Pro reverse turn motifs into their backbone.
Keywords: Peptides; Peptidomimetics; Protein folding; Protein structures

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

Ascertaining universal features of yielding of soft materials - Kamble, Samruddhi; Pandey, Anurag; Rastogi, Sanjay; Lele, Ashish K. (Rheologica Acta, 2013)
Many metastable complex fluids, when subjected to oscillatory shear flow of increasing strain amplitude at constant frequency, are known to show a characteristic nonlinear rheological response which consists of a monotonic decrease in the elastic modulus and a nonmonotonic change in the loss modulus. In particular, the loss modulus increases from its low strain value, crosses the elastic modulus, and then decreases with further increase in the strain amplitude. Miyazaki et al. (Europhys Lett 75:915-921, 2006) proposed a qualitative argument to explain the origin of the nonmonotonic nature of the loss modulus and suggested that in fact this response could be universal to all complex fluids if they are probed in a certain frequency window in which the fluid is dominantly elastic in the small strain limit. In this letter, we confirm their hypothesis by showing that a wide variety of complex fluids, irrespective of their thermodynamic state under quiescent conditions, indeed show the aforementioned characteristic nonlinear response. We also show that the maximum relative dissipation during yielding occurs when the imposed frequency resonates with the characteristic beta relaxation frequency of the fluid.
Keywords: Colloidal suspensions; Entangled melts; Gels; Glasses; Microgels; Rheology; Yielding

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

Biochemical correlate of dimorphism in a zygomycete benjaminiella poitrasii: characterization of purified NAD-dependent glutamate dehydrogenase, a target for antifungal agents - Joshi, C. V.; Pathan, E. K.; Punekar, N. S.; Tupe, S. G.; Kapadnis, B. P.; Deshpande, Mukund V. (Antonie Van Leeuwenhoek International Journal of General and Molecular Microbiology, 2013)
The fungal organisms, especially pathogens, change their vegetative (Y, unicellular yeast and H, hypha) morphology reversibly for survival and proliferation in the host environment. NAD-dependent glutamate dehydrogenase (NAD-GDH, EC 1.4.1.2) from a non-pathogenic dimorphic zygomycete Benjaminiella poitrasii was previously reported to be an important biochemical correlate of the transition process. The enzyme was purified to homogeneity and characterized. It is a 371 kDa native molecular weight protein made up of four identical subunits. Kinetic studies showed that unlike other NAD-GDHs, it may act as an anabolic enzyme and has more affinity towards 2-oxoglutarate than l-glutamate. Chemical modifications revealed the involvement of single histidine and lysine residues in the catalytic activity of the enzyme. The phosphorylation and dephosphorylation study showed that the NAD-GDH is present in active phosphorylated form in hyphal cells of B. poitrasii. Two of the 1,2,3 triazole linked beta-lactam-bile acid conjugates synthesized in the laboratory (B18, B20) were found to be potent inhibitors of purified NAD-GDH which also significantly affected Y-H transition in B. poitrasii. Furthermore, the compound B20 inhibited germ tube formation during Y-H transition in Candida albicans strains and Yarrowia lipolytica. The possible use of NAD-GDH as a target for antifungal agents is discussed.
Keywords: Antifungal agent; Benjaminiella poitrasii; Biochemical correlate of dimorphism; Candida albicans; NAD-GDH activity regulation; Yarrowia lipolytica; Yeast-hypha reversible transition

Biodegradation of phenol by the yeast candida tropicalis: an investigation by NMR spectroscopy - Phalgune, U. D.; Rajamohanan, P. R.; Gaikwad, B. G.; Varma, R. J.; George, S. (Applied Biochemistry and Biotechnology, 2013)
The process of phenol biodegradation by the yeast Candida tropicalis NCIM 3556 in aqueous medium was studied by H-1, C-13, and DOSY NMR techniques. Samples at regular intervals were centrifuged to separate the cells, and H-1 spectral data were collected at 400 MHz. Though a gradual decrease in the concentration of phenol was observed, after an incubation period of similar to 8 h, formation of any intermediate products could not be detected. Experiments carried out with uniformly C-13-labeled phenol also failed to detect formation of any carboxylic acid intermediates during degradation. The studies indicated that the phenol was completely degraded to carbon dioxide and water in approximately 20 h. Self-diffusion coefficient measurements showed that the lifetime of phenol in the bound form is too small to impart any change in its diffusion behavior and the intermediates formed are converted to carbon dioxide and water at a very fast rate.
Keywords: biocatalysis; Carboxylic acid; Diffusion; Enzyme; NMR spectroscopy; phenol

Biosurfactant-sophorolipid acts in synergy with antibiotics to enhance their efficiency - Joshi-Navare, Kasturi; Prabhune, Asmita (Biomed Research International, 2013)
Sophorolipids (SLs), biosurfactants with antimicrobial properties, have been tried to address the problem of antibiotic resistance. The synergistic action of SL and antibiotics was checked using standard microdilution and spread plate methods. With Staphylococcus aureus, SL-tetracycline combination achieved total inhibition before 4 h of exposure while tetracycline alone couldnot achieve total inhibition till the end of 6 h. The inhibition caused by exposure of bacterium to SL-tetracycline mixture was similar to 25% more as compared to SL alone. In spite of known robustness of gram-negative bacteria, SL-cefaclor mixture proved to be efficient against Escherichia coli which showed similar to 48% more inhibition within 2 h of exposure as compared to cefaclor alone. Scanning electron microscopy of the cells treated with mixture revealed bacterial cell membrane damage and pore formation. Moreover, SLs being a type of asymmetric bola, they are expected to form self-assemblies with unique functionality. This led to the speculation that SLs being amphiphilic in nature can span through the structurally alike cell membrane and facilitate the entry of drug molecules.

Biosynthesis of Se nanoparticles and its effect on UV-induced DNA damage - Prasad, Kumar Suranjit; Patel, Hirnee; Patel, Tirtha; Patel, Khusbu; Selvaraj, Kaliaperumal (Colloids and Surfaces B-Biointerfaces, 2013)
This paper reports, an environmentally benign procedure of synthesis and characterizations of selenium nanoparticles and their protective effect against UV-induced DNA damage activities. An aqueous leaf extract of lemon plant was used as a precursor for synthesis of colloidal selenium nanoparticles. Resulting nanoparticles were characterized using UV-vis spectrophotometer, photoluminescence, TEM, EDAX, FT-IR and XRD, respectively. Selenium colloidal solution exhibited an absorption maximum at 395 nm and produced an emission maximum at 525 nm. Transmission electron microscopy followed by selected area electron diffraction pattern analysis indicated the formation of spherical, polydispersed, crystalline, selenium nanoparticles of diameter ranging from (similar to 60 to 80 nm). X-ray diffraction studies showed the formation of 111, 2 0 0 and 220 planes of face-centered cubic (fcc) selenium. EDAX analysis confirmed the presence of selenium in nanosphere. Fourier transformed infrared spectroscopic investigation reveled the involvement of carboxyl (-C=0), hydroxyl (-OH), amine (-NH) functional group of lemon plant extract in preparation of selenium nano particles. MU assay as well single cell gel electrophoresis assay or comet assay revealed that synthesized selenium nanoparticles, caused less cell death of lymphocytes and prevented DNA damage, when cells were exposed to UVB. The fluorescent property of selenium nanopartides can be used as diagnostic agent. Further, their anti DNA damaging property can be investigated as a chemotherapeutic agent in cancer therapy. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Comet assay; EDAX; FT-IR; MTT assay; Selenium nanoparticles; UV-vis spectrophotometer

Bulk and surface structure characterization of nanoscopic silver doped lanthanum chromites - Desai, P. A.; Joshi, P. N.; Patil, K. R.; Athawale, Anjali A. (Applied Surface Science, 2013)
Crystalline state of lanthanum chromites with silver as a dopant has been studied by X-ray diffraction and transmission electron microscopy reveals microscopic properties of grain boundaries. X-ray photoelectron spectroscopy has been used to analyze surface states with atomic ratio of La, Cr, O and Ag as a dopant. LaCrO3 shows mixed valence states of chromium while the silver doped samples exhibit differences in chromium concentration with the oxidation of Cr3+ to Cr6+ in presence of chromium nitrate as a precursor salt. Trivalent stable state of chromium is observed for samples synthesized by chromic acetate as a precursor salt. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Energy dispersive analysis of X-rays; Microwave combustion synthesis; Perovskite nanostructures; transmission electron microscopy; X-ray diffraction; X-ray photoelectron spectroscopy

CAP/EOM-CCSD method for the study of potential curves of resonant states - Ghosh, Aryya; Karne, Anagha S.; Pal, Sourav; Vaval, Nayana (Physical Chemistry Chemical Physics, 2013)
The equation-of-motion coupled-cluster (EOM-CC) method along with the complex absorbing potential (CAP) is used for the study of resonance in e(-)-N-2 and e(-)-CO. Resonance position and width are studied as a function of bond length. We report the potential curves (PC) of the resonance states.

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

Carrier free co-immobilization of alpha amylase, glucoamylase and pullulanase as combined cross-linked enzyme aggregates (combi-CLEAs): a tri-enzyme biocatalyst with one pot starch hydrolytic activity - Talekar, Sachin; Pandharbale, Amol; Ladole, Mayur; Nadar, Shamraja; Mulla, Mosin; Japhalekar, Kshitija; Pattankude, Kishori; Arage, Devika (Bioresource Technology, 2013)
A tri-enzyme biocatalyst ``combi-CLEAs'' with starch hydrolytic activity was prepared from commercially available alpha amylase, glucoamylase and pullulanase preparations by aggregating enzymes with ammonium sulphate followed by cross-linking formed aggregates for 4.5 h with 40 mM glutaraldehyde. The effects of precipitant type and cross-linking were studied and the biocatalyst was characterized. Scanning electron microscopy analysis showed that tri-enzyme biocatalyst was of spherical structure. For one pot starch hydrolytic activity, shift in optimum pH from 6 to 7 and temperature from 65 to 75 degrees C were observed after co-immobilization of enzymes. After one pot starch hydrolysis reaction in batch mode, 100%, 60% and 40% conversions were obtained with combi-CLEAs, separate CLEAs mixture and free enzyme mixture, respectively. Co-immobilization also enhanced the thermal stability of enzymes. Finally, the catalytic activity of enzymes in combi-CLEAs during one pot starch hydrolysis was well maintained up to five cycles without performance changes. (C) 2013 Elsevier Ltd. All rights reserved.
Keywords: Alpha amylase; Combined cross-linked enzyme aggregates (combi-CLEAs); Glucoamylase; One pot starch hydrolysis; Pullulanase

Catalytic and DFT study of selective ethylene oligomerization by nickel(II) oxime-based complexes - Tayade, Kamlesh N.; Mane, Manoj V.; Sen, Suman; Murthy, C. N.; Tembe, Gopal L.; Pillai, S. Muthukumaru; Vanka, Kumar; Mukherjee, Soumen (Journal of Molecular Catalysis A-Chemical, 2013)
The reactivity of nickel(II) thiophenealdoxime complex (3) toward oligomerization of ethylene in the presence of an alkylaluminum co-catalyst has been studied. The complex was found to be a selective ethylene dimerization catalyst in the presence of co-catalysts such as methylalumoxane (MAO) and diethylaluminum chloride (DEAC). With DEAC, the productivity was considerably higher than with MAO. Under optimum conditions the productivity reaches 388 kg/mol catalyst/h/bar with DEAC whereas for MAO this value was 119 kg/mol catalyst/h/bar. Complex 3 displays good ethylene conversions of up to a maximum of 90% with exceptionally high alpha-selectivity for 1-butene (>99.5%) amongst C-4 products. Computational studies using density functional theory (DFT) were also carried out to ascertain the decomposition pathway for 3 as well as that for Ni(II) complex of the pyridine ketoxime ligand 2. The results suggest that loss of one of the two bidentate oxime ligands attached to the metal center through reaction with DEAC is likely for both 2 and 3. Further, calculations indicate that the subsequent decomposition step was significantly more probable for 3 than for 2 thus explaining why the pyridine ketoxime ligand bound nickel complex 2 was experimentally found to be more stable than the thiophene aldoxime bound nickel complex 3. Calculations also show that the proton of the -OH group (oxime) plays a major role in the stability of the molecules. This was confirmed experimentally by synthesizing the Ni(II) dichloro complex of Pyridine-2-carbaldehyde O-methyloxime 5 and reacting it with ethylene under similar conditions. 5 was found to be highly active even at low co-catalyst concentrations. (c) 2012 Elsevier B.V. All rights reserved.
Keywords: Butene-1; Ethylene dimerization; Ni(II) complex; Thiophene aldoxime

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

Catalytic upgrading of renewable levulinic acid to ethyl levulinate biodiesel using dodecatungstophosphoric acid supported on desilicated H-ZSM-5 as catalyst - Nandiwale, Kakasaheb Y.; Sonar, Shilpa K.; Niphadkar, Prashant S.; Joshi, Praphulla N.; Deshpande, Shilpa S.; Patil, Vilas S.; Bokade, Vijay V. (Applied Catalysis A-General, 2013)
Levulinic acid (LA) is considered as a renewable platform chemical and can be used for the synthesis of variety of important fuels and chemicals. In particular, its esterification with ethanol produces ethyl levulinate (EL) would be green process, as it can be used as diesel miscible biofuel (DMB), preventing global warming by decreasing atmospheric CO2. This study explores the use of modified H-ZSM-5 by desilication viz.; DH-ZSM-5 and dodecatungstophosphoric acid (DTPA) loaded on DH-ZSM-5 for esterification of LA with ethanol aiming to EL. Different degree of desilication of H-ZSM-5 was performed by using aq. NaOH (0.2-1.5 M) at 338 K for 30 min and then DTPA was loaded on these desilicated H-ZSM-5 (DH-ZSM-5) support. H-ZSM-5, DH-ZSM-5 and DTPA on these DH-ZSM-5 samples were characterized by powder x-ray diffraction (XRD), N-2 adsorption-desorption, pyridine chemisorbed IR spectroscopy, Temperature Programmed Ammonia Desorption (TPAD). The increase in conversion of levulinic acid was observed from 28% to 94% with increase of DTPA loading from 0% to 15%. The increased LA conversion may be due to increase in total acidity from 43.14% to 84.31%. The use of DH-ZSM-5 as support for deposition of DTPA may be reported for the first time. The present work also extended to optimize process parameters such as DTPA loading on DH-ZSM-5, catalyst to LA ratio, LA to ethanol molar ratio, speed of agitation, particle size reaction temperature and catalyst reusability. Kinetic study based on pseudo-homogeneous (P-H) model is also presented. The experimental results follow second order kinetics. (C) 2013 Elsevier B.V. All rights reserved.
Keywords: desilicated H-ZSM-5; DTPA on desilicated H-ZSM-5; Esterification; ethyl levulinate; levulinic acid

Characterization of the structures and dynamics of phosphoric acid doped benzimidazole mixtures: a molecular dynamics study - More, Minal; Pahari, Swagata; Roy, Sudip; Venkatnathan, Arun (Journal of Molecular Modeling, 2013)
Benzimidazole-based polymer membranes like poly(2,5-benzimidazole) (ABPBI) doped with phosphoric acid (PA) are electrolytes that exhibit high proton conductivity in fuel cells at elevated temperatures. The benzimidazole (BI) moiety is an important constituent of these membranes, so the present work was performed in order to achieve a molecular understanding of the BI-PA interactions in the presence of varying levels of the PA dopant, using classical molecular dynamics (MD) simulations. The various hydrogen-bonding interactions, as characterized based on structural properties and hydrogen-bond lifetime calculations, show that both BI and PA molecules exhibit dual proton-acceptor/donor functionality. An examination of diffusion coefficients showed that the diffusion of BI decreases with increasing PA uptake, whereas the diffusion of PA slightly increases. The hydrogen-bond lifetime calculations pointed to the existence of competitive hydrogen bonding between various sites in BI and PA.
Keywords: Diffusion coefficient; Hydrogen bond; molecular dynamics; Radial distribution functions

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

Charge storage and electron transport properties of gold nanoparticles decorating a urethane-methacrylate comb polymer network - Patil, Sumati; Datar, Suwarna; Rekha, N.; Asha, S. K.; Dharmadhikari, C. V. (Nanoscale, 2013)
We propose enhanced charge storage capacity of nanoparticles based polymer films. A flat band voltage window varying from 5-7 V is obtained leading to a trapped charge density of the order of 10(13) cm(-2). These results vary for two distinct morphologies obtained due to decoration of a urethane-methacrylate comb polymer (UMCP) network by gold nanoparticles (AuNPs). Films have been further investigated for morphology, optical, charge storage, and electron transport properties using techniques like scanning electron microscopy (SEM), atomic force microscopy (AFM), absorption spectroscopy (UV-Vis), scanning tunneling microscopy/spectroscopy (STM/STS) and capacitance versus voltage (C-V) measurements. SEM and AFM confirm either the deposition of AuNPs inside the UMCP network or the formation of ring like structures depending on the deposition sequence. STS measurements performed on both films are compared with bare UMCP and AuNPs films. Current versus voltage (I-V) characteristics so obtained are discussed in the light of electron transport mechanisms in such materials.

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

Cinnamate 4-hydroxylase (C4H) genes from leucaena leucocephala: a pulp yielding leguminous tree - Kumar, Santosh; Omer, Sumita; Patel, Krunal; Khan, Bashir Mohammad (Molecular Biology Reports, 2013)
Leucaena leucocephala is a leguminous tree species accounting for one-fourth of raw material supplied to paper and pulp industry in India. Cinnamate 4-Hydroxylase (C4H, EC 1.14.13.11) is the second gene of phenylpropanoid pathway and a member of cytochrome P450 family. There is currently intense interest to alter or modify lignin content of L. leucocephala. Three highly similar C4H alleles of LlC4H1 gene were isolated and characterized. The alleles shared more than 98 % sequence identity at amino acid level to each other. Binding of partial promoter of another C4H gene LlC4H2, to varying amounts of crude nuclear proteins isolated from leaf and stem tissues of L. leucocephala formed two loose and one strong complex, respectively, suggesting that the abundance of proteins that bind with the partial C4H promoter is higher in stem tissue than in leaf tissue. Quantitative Real Time PCR study suggested that among tissues of same age, root tissues had highest level of C4H transcripts. Maximum transcript level was observed in 30 day old root tissue. Among the tissues investigated, C4H activity was highest in 60 day old root tissues. Tissue specific quantitative comparison of lignin from developing seedling stage to 1 year old tree stage indicated that Klason lignin increased in tissues with age.
Keywords: Cinnamate 4-Hydroxylase (C4H); Leucaena leucocephala; lignin; Phenylpropanoid

Cobalt-catalyzed C–H bond functionalizations with aryl and alkyl chlorides - Punji, Benudhar; Song, Weifeng; Shevchenko, Grigory A.; Ackermann, Lutz (Chemistry - A European Journal, 2013)
Inexpensive cobalt catalysts derived from N-heterocylic carbenes (NHC) allowed efficient catalytic C[BOND]H bond arylations on heteroaryl-substituted arenes with widely available aryl chlorides, which set the stage for the preparation of sterically hindered tri-ortho-substituted biaryls. Likewise, challenging direct alkylations with β-hydrogen-containing primary and even secondary alkyl chlorides proceeded on pyridyl- and pyrimidyl-substituted arenes and heteroarenes. The cobalt-catalyzed C[BOND]H bond functionalizations occurred efficiently at ambient reaction temperature with excellent levels of site-selectivities and ample scope. Mechanistic studies highlighted that electron-deficient aryl chlorides reacted preferentially, while the arenes kinetic C[BOND]H bond acidity was found to largely govern their reactivity.

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

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

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

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

Crystalline xylitol production by a novel yeast, pichia caribbica (HQ222812), and its application for quorum sensing inhibition in gram-negative marker strain chromobacterium violaceum CV026 - Mukherji, Ruchira; Joshi-Navare, Kasturi; Prabhune, Asmita (Applied Biochemistry and Biotechnology, 2013)
Xylitol, a sugar alcohol, is fast gaining ground over other artificial sugar substitutes owing to its advantageous properties. Xylitol is a safer alternative for diabetics because of insulin-independent metabolism. It has beneficial properties suitable to form an important part of odontological formulations. Conventional commercial production of xylitol involves harsh chemical method operating at high temperature and pressure. Thus, microbial production of xylitol is preferred over chemical method, and yeasts have been extensively exploited for this purpose. In the present manuscript, quantitative production of xylitol from d-xylose with the yield of 0.852 gm/gm and volumetric productivity of 1.83 gm/l/h in crystalline form, using novel yeast Pichia caribbica is reported. Also, a mild, safe procedure for product extraction is described. The ability of xylitol to act as a quorum sensing antagonist in gram-negative marker strain Chromobacterium violaceum CV026 has been demonstrated for the first time.
Keywords: Crystallization; CV026; Pichia caribbica; Quorum sensing antagonist; xylitol

Crystallisation of ferrous sulphate heptahydrate: experiments and modelling - Shaikh, Latif; Pandit, Aniruddha; Ranade, Vivek (Canadian Journal of Chemical Engineering, 2013)
Crystallisation is an industrially important unit operation for purifying and separating chemical mixtures. A generic crystallisation modelling framework has been implemented in the general process modelling system (gPROMS) software (of PSE, UK). This framework can be used to model the batch cooling crystallisation of ferrous sulphate heptahydrate (FSH). The parameter estimation and sensitivity of the predicted results with various numerical parameters was studied for batch crystalliser. An Excel front-end to the gPROMS model was developed to facilitate the interactive use of the model. (c) 2011 Canadian Society for Chemical Engineering
Keywords: batch crystallisation; ferrous sulphate heptahydrate; gPROMS; MSExcel-linking; parameter estimation

CuCN-Mediated cascade cyclization of 4-(2-bromophenyl)-2-butenoates: a high-yield synthesis of substituted naphthalene amino esters - Reddy, R. Santhosh; Prasad, Pragati K.; Ahuja, Brij Bhushan; Sudalai, Arumugam (Journal of Organic Chemistry, 2013)
A new method of CuCN-mediated one-pot cyclization of 4-(2-bromophenyl)-2-butenoates leading to efficient synthesis of substituted naphthalene amino esters including phenanthrene aromatic structural units is described. Deuterium labeling studies establish that this one-pot cascade cyclization proceeds through isomerization of olefin, intramolecular C-C bond cyclization, and aromatization as the key intermediates, all occurring in a single step.

Defluoridation of drinking water using pural (R) MG-20 mixed hydroxide adsorbent - Patankar, Gaurang V.; Tambe, Amruta S.; Kulkarni, Bhaskar D.; Malyshew, Alexander; Kamble, Sanjay P. (Water Air and Soil Pollution, 2013)
The potential ofmixed alumina-magnesia hydroxide adsorbent (PURAL (R) MG-20) for defluoridation of drinking water using batch and continuous mode of operations has been reported in the present article. Systematic adsorption experiments were carried out to elucidate the effects of different process parameters such as adsorbent dose, initial fluoride concentration, pH of the solution and effect of other ions (usually present in groundwater). These studies were aimed to understand the adsorption behaviour of the PURAL (R) MG-20 adsorbents. Fluoride adsorption by PURAL (R) MG-20 sorbent was found pH dependent. Maximum fluoride removal efficiency was observed in the range of pH 5-7. Langmuir isotherm described the data better than Freundlich and Temkin isotherm models and the adsorption capacity was found to be 5.62 mg g(-1) at initial fluoride concentration of 5.13 mg L-1, pH 7 and contact time 24 h. The kinetic result shows that the fluoride sorption follows pseudo-second-order kinetics. Column breakthrough studies were performed to test the performance of the adsorbent media at continuous mode of operation. Thus, it can be concluded that PURAL (R) MG-20 adsorbent can be used directly for field applications since it shows high fluoride uptake capacity under simulated drinking water conditions and it is also commercially available.
Keywords: Breakthrough studies; Defluoridation of drinking water; Kinetic modelling; Mixed hydroxide adsorbent

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

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

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

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

Diethylamine: a smart organocatalyst in eco-safe and diastereoselective synthesis of medicinally privileged 2-amino-4H-chromenes at ambient temperature - Kulkarni, Makarand A.; Pandit, Kapil S.; Desai, Uday V.; Lad, Uday P.; Wadgaonkar, Prakash P. (Comptes Rendus Chimie, 2013)
Diethylamine has been demonstrated to be an efficient organocatalyst in the diastereoselective synthesis of Bcl-2 protein antagonist (HA-14-1) and of its structural analogues by one-pot condensation between salicylaldehyde and three different C-H acids, viz, ethyl cyanoacetate, phenylsulfonyl acetonitrile, and malononitrile. Easy commercial availability of the catalyst at extremely low cost and avoidance of conventional work-up as well as purification procedures qualifies this scalable protocol for a ``near-ideal synthesis''. (c) 2013 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Keywords: 2-amino-4H-chromenes; Active methylene compounds (C-H acids); diethylamine; multicomponent reactions; organocatalyst

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