Toward an understanding of the molecular level properties of ziegler-natta catalyst support with and without the internal electron donor - Thushara, K. S.; Gnanakumar, Edwin S.; Mathew, Renny; Jha, Ratnesh Kumar; Ajithkumar, Thalasseril G.; Rajamohanan, P. R.; Sarma, Krishna; Padmanabhan, Sudhakar; Bhaduri, Sumit; Gopinath, Chinnakonda S. (Journal of Physical Chemistry C, 2011)
Two Ziegler-Natta catalysts supported on molecular adducts, namely, MgCl2 center dot 6EtOH (ME) and MgCl2 center dot 5EtOH center dot EtOOCPh (Est-ME), have been prepared. A systematic effort has been made to unravel the molecular level structure property relationships of the catalysts and adducts. Ethylbenzoate is an internal electron donor, and its in situ formation through EtOH+PhCOCl coupling is successfully achieved. The above adduct has been treated with TiCl4, and the resultant catalyst (Ti/Est-ME) is evaluated for ethylene polymerization activity. Rand C-13 CP/MAS NMR of Est-ME (Ti/Est-ME) show carbonyl features at 1730 (1680) cm(-1) and 169 (170) delta, respectively, providing direct support for the presence of ester as an integral part. In spite of low surface area, Ti/Est-ME gives higher yield for ethylene polymerization than the one derived from ME. The results indicate that electronic environment is more important than surface area or any other single factor in determining the polymerization activity.

Adsorption induced enzyme denaturation: the role of protein surface in adsorption induced protein denaturation on allyl glycidyl ether (AGE)-ethylene glycol dimethacrylate (EGDM) copolymers - Thudi, Lahari; Jasti, Lakshmi Swarnalatha; Swarnalatha, Y.; Fadnavis, Nitin W.; Mulani, Khudbudin Baban; Deokar, Sarika Babasaheb; Ponrathnam, Surendra (Colloids and Surfaces B-Biointerfaces, 2012)
The effects of protein size on adsorption and adsorption-induced denaturation of proteins on copolymers of allyl glycidyl ether (AGE)-ethylene glycol dimethacrylate (EGDM) have been studied. Different responses were observed for the amount of protein adsorbed and denatured on the polymer surface for different proteins (trypsin, alchol dehydrogenase from baker's yeast (YADH), glucose dehydrogenase (GDH) from Gluconobacter cerinus, and alkaline phosphates from calf intestinal mucosa (CIAP). Protein adsorption on the copolymer with 25% crosslink density (AGE-25) was dependent not only on the size of the protein but also on the presence of glycoside residues on the protein surface. Adsorption and denaturation of proteins follows the order YADH > trypsin > GDH >> CIAP although the molecular weights of the proteins follow the order YADH > CIAP > GDH > trypsin. The lack of correlation between amount of adsorbed protein and its molecular weight was due to the presence of glycoside residues on CIAP and GDH which protect the enzyme surface from denaturation. Enzyme stabilities in aqueous solutions of 1-cyclohexyl-2-pyrrolidinone (CHP) correlate well with the trend in denaturation by the copolymer, strongly suggesting that hydrophobic interactions play a major role in protein binding and the mechanism of protein denaturation is similar to that for water-miscible organic solvents. (C) 2011 Elsevier B.V. All rights reserved.
Keywords: 1-Cyclohexyl-2-pyrrolidinone; Adsorption; Alcohol dehydrogenase; Alkaline phosphatase; allyl glycidyl ether; Denaturation; ethylene glycol dimethacrylate; Glucose dehydrogenase; Trypsin

Alumina supported carbon composite material with exceptionally high defluoridation property from eggshell waste - Lunge, Sneha; Thakre, Dilip; Kamble, Sanjay; Labhsetwar, Nitin K.; Rayalu, Sadhana (Journal of Hazardous Materials, 2012)
A new alumina supported carbon composite material called ``Eggshell Composite'' (EC) was synthesized from eggshell waste as calcium source for selective fluoride adsorption from water. The effect of various synthesis parameters like eggshell (ES): Eggshell membrane (ESM) ratio, aluminium loading, mixing time and calcinations temperature to optimize the synthesis conditions for selective fluoride removal has been studied. It was observed that the synthesis parameters have significant influence on development of EC and in turn on fluoride removal capacity. EC synthesized was characterized for elemental composition, morphology, functionality and textural properties. Results showed that EC obtained from eggshell modified with alumina precursor is more selective and efficient for fluoride removal. Langmuir and Freundlich isotherm were used to obtain ultimate fluoride removal capacity. The calcium and alumina species in EC shows synergistic effect in fluoride adsorption process. Fluoride sorption studies were carried out in synthetic, groundwater and wastewater. EC proved to be a potential, indigenous and economic adsorbent for fluoride removal. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Composite material; Eggshell; Eggshell membrane; Fluoride adsorption; Langmuir

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

Andrographolide inhibits osteopontin expression and breast tumor growth through down regulation of PI3 Kinase/Akt signaling pathway - Kumar, S.; Patil, H. S.; Sharma, P.; Kumar, D.; Dasari, Sreekanth; Puranik, Vedavati G.; Thulasiram, H. V.; Kundu, G. C. (Current Molecular Medicine, 2012)
Breast cancer is one of the most common cancers among women in India and around the world. Despite recent advancement in the treatment of breast cancer, the results of chemotherapy to date remain unsatisfactory, prompting a need to identify natural agents that could target cancer efficiently with least side effects. Andrographolide (Andro) is one such molecule which has been shown to possess inhibitory effect on cancer cell growth. In this study, Andro, a natural diterpenoid lactone isolated from Andrographis paniculata has been shown to inhibit breast cancer cell proliferation, migration and arrest cell cycle at G2/M phase and induces apoptosis through caspase independent pathway. Our experimental evidences suggest that Andro attenuates endothelial cell motility and tumor-endothelial cell interaction. Moreover, Andro suppresses breast tumor growth in orthotopic NOD/SCID mice model. The anti-tumor activity of Andro in both in vitro and in vivo model was correlated with down regulation of PI3 kinase/Akt activation and inhibition of pro-angiogenic molecules such as OPN and VEGF expressions. Collectively, these results demonstrate that Andro may act as an effective anti-tumor and anti-angiogenic agent for the treatment of breast cancer.
Keywords: Andrographolide; angiogenesis and breast tumor; migration; osteopontin; PI 3 kinase

Aromatic aldehyde functionalized polycaprolactone and polystyrene macromonomers: synthesis, characterization and aldehyde-aminooxy click reaction - Sane, Prakash S.; Tawade, Bhausaheb V.; Palaskar, Dnyaneshwar V.; Menon, Shamal K.; Wadgaonkar, Prakash P. (Reactive & Functional Polymers, 2012)
New bis-aldehyde functionalized initiators, viz, 4,4'-(4,4'-(5-hydroxypentane-2,2-diyl)bis(4,1-phenylene))bis(oxy)dibenza ldehyde (1) and 4,4'-bis(4-(4-(formylphenoxy) phenyl) pentyl 2-bromopropanoate (2) were synthesized starting from commercially available 4,4'-bis(4-hydroxyphenyl) pentanoic acid. These initiators were utilized, respectively, for ring opening polymerization of E-caprolactone and atom transfer radical polymerization of styrene. Well-defined polycaprolactone macromonomers (M-n(GPC): 2600-19400, PDI: 1.37-1.47) and polystyrene macromonomers (M-n(GPC): 2800-28200, PDI: 1.11-1.16) with bis-aldehyde functionality were synthesized. The kinetic study of styrene polymerization showed controlled polymerization behaviour. The presence of aldehyde functionality in macromonomers was confirmed by H-1 NMR spectroscopy. The reactivity of aldehyde functionality was demonstrated by carrying out aldehyde-aminooxy click reaction of polycaprolactone macromonomer with O-(2-azidoethyl) hydroxylamine which proceeded in a quantitative manner without backbone degradation. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Aldehyde-terminated macromonomers; ATRP; Polycaprolactone; Polystyrene; ROP

Clare: cracking the language of regulatory elements - Taher, Leila; Narlikar, Leelavati; Ovcharenko, Ivan (Bioinformatics, 2012)
CLARE is a computational method designed to reveal sequence encryption of tissue- specific regulatory elements. Starting with a set of regulatory elements known to be active in a particular tissue/process, it learns the sequence code of the input set and builds a predictive model from features specific to those elements. The resulting model can then be applied to user-supplied genomic regions to identify novel candidate regulatory elements. CLARE's model also provides a detailed analysis of transcription factors that most likely bind to the elements, making it an invaluable tool for understanding mechanisms of tissue- specific gene regulation.

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.

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

Covalently anchored ruthenium-phosphine complex on mesoporous organosilica: catalytic applications in hydrogenation reactions - Sisodiya, Sheetal; Lazar, Anish; Shylesh, Sankaranarayanapillai; Wang, Lei; Thiel, Werner R.; Singh, Anand Pal (Catalysis Communications, 2012)
New heterogeneous catalysts for alkene hydrogenation reactions were prepared by the immobilization of trimethoxysilane functionalized triphenylphosphine eta(6)-p-cymene ruthenium complex on mesoporous organosilica (PMO-Ru). Characterization techniques confirmed the structural integrity of the organosilica material and proved the successful anchoring of ruthenium complex. Catalytic activity and stability of PMO-Ru sample investigated in the hydrogenation of various olefins showed higher activity than a neat and MCM-41 supported ruthenium catalyst. High catalytic activity and stability of organosilica supported ruthenium catalyst are attributed to the hydrophobic environments and to the unique structural features imparted from the presence of organic groups in the framewall positions. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: Heterogenization; Hydrogenation; Organosilica; ruthenium; Triphenyl phosphine

Developmental and digestive flexibilities in the midgut of a polyphagous pest, the cotton bollworm, helicoverpa armigera - Sarate, P. J.; Tamhane, V. A.; Kotkar, H. M.; Ratnakaran, N.; Susan, N.; Gupta, Vidya S.; Giri, Ashok P. (Journal of Insect Science, 2012)
Developmental patterns and survival of the cotton bollworm, Helicoverpa armigera Hubner (Lepidoptera: Noctuidae), a polyphagous insect pest, have been studied with reference to the effect of diet on major gut digestive enzymes (amylases, proteases, and lipases). Significant correlations between nutritional quality of the diet and larval and pupal mass were observed when H. armigera larvae were fed on various host plants viz. legumes (chickpea and pigeonpea), vegetables (tomato and okra), flowers (rose and marigold), and cereals (sorghum and maize). Larvae fed on diets rich in proteins and/or carbohydrates (pigeonpea, chickpea, maize, and sorghum) showed higher larval mass and developed more rapidly than larvae fed on diets with low protein and carbohydrate content (rose, marigold, okra, and tomato). Low calorific value diets like rose and marigold resulted in higher mortality (25-35%) of H. armigera. Even with highly varying development efficiency and larval/pupal survival rates, H. armigera populations feeding on different diets completed their life cycles. Digestive enzymes of H. armigera displayed variable expression levels and were found to be regulated on the basis of macromolecular composition of the diet. Post-ingestive adaptations operating at the gut level, in the form of controlled release of digestive enzymes, might be a key factor contributing to the physiological plasticity in H. armigera.
Keywords: amylases; larval performance; Lipases; Proteases

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.

Engineered glucose to generate a spectroscopic probe for studying carbohydrate biology - Tripathi, Ashish; Singh, Vibha; Aishwarya, K. G.; Aradhyam, Gopala Krishna; Hotha, Srinivas (Advances in Experimental Medicine and Biology, 2012)

Enhanced magnetic parameters in the morphotropic phase boundary region of nanocrystalline multiferroic Bi1-xLaxFeO3 - Thakuria, P.; Joy, Pattayil Alias (Solid State Communications, 2012)
Antiferromagnetic multiferroic BiFeO3 shows ferromagnetic characteristics by simultaneous substitution of Bi by La and decrease in the particle size to nanometer dimensions. Large changes in saturation and remnant magnetization, magnetic susceptibility at low and high fields, along with some anomalous changes in the magnetic transition temperature are observed in nanocrystalline Bi1-xLaxFeO3 system for 0.1 <= x <= 0.2. This compositional region corresponds to the morphotropic phase boundary (MPB) region separating the rhombohedral and orthorhombic phases, and the effect is similar to that observed in many ferroelectric systems. The present observation of enhanced ferromagnetic parameters in the MPB region of the nanocrystalline multiferroic La substituted BiFeO3 system, combined with the known ferroelectric characteristics, is suitable for future device applications. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords: Bismuth ferrite; magnetic properties; Multiferroics; Nanocrystalline materials

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

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

Formal synthesis of tetrahydrolipstatin and tetrahydroesterastin - Tripathi, Divya; Kumar, Pradeep (Tetrahedron-Asymmetry, 2012)
A versatile and efficient approach to (3.5,5R)-methyl 3-(benzyloxy)-5-(methoxymethoxy)hexadecanoate, a key chiral building block and a common polyol fragment of the anti-tumor and anti-obesity agents tetrahydrolipstatin 3 and tetrahydroesterastin 4 using both hydrolytic kinetic resolution (HKR) and proline catalyzed sequential alpha-aminoxylation, followed by HWE-olefination reaction is described. (c) 2012 Elsevier Ltd. All rights reserved.

From small aromatic molecules to functional nanostructured carbon by pulsed laser-induced photochemical stitching - Gokhale, R. R.; Thakare, V. P.; Warule, S.; Lefez, Benoit; Hannoyer, Beatrice; Jog, Jyoti Prakash; Ogale, S. B. (AIP Advances, 2012)
A novel route employing UV laser pulses (KrF Excimer, 248 nm) to cleave small aromatic molecules and stitch the generated free radicals into functional nanostructured forms of carbon is introduced. The process differs distinctly from any strategies wherein the aromatic rings are broken in the primary process. It is demonstrated that this pulsed laser-induced photochemical stitching (PLPS) process when applied to routine laboratory solvents (or toxic chemical wastes when discarded) Chlorobenzene and o-Dichlorobenzene yields Carbon Nanospheres (CNSs) comprising of graphene-like sheets assembled in onion-like configurations. This room temperature process implemented under normal laboratory conditions is versatile and clearly applicable to the whole family of haloaromatic compounds without and with additions of precursors or other nanomaterials. We further bring out its applicability for synthesis of metal-oxide based carbon nanocomposites. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. [http://dx.doi.org/10.1063/1.4721268]

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

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

Inheritance of resistance to root-lesion nematodes (Pratylenchus thornei and P. neglectus) in five doubled-haploid populations of wheat - Thompson, John P.; Rebecca S. Zwart; Butler, David (Euphytica, 2012)
Nematode species Pratylenchus thornei and P. neglectus are the two most important root-lesion nematodes affecting wheat (Triticum aestivum L.) and other grain crops in Australia. For practical plant breeding, it will be valuable to know the mode of inheritance of resistance and whether the same set of genes confer resistance to both species. We evaluated reactions to P. thornei and P. neglectus of glasshouse-inoculated plants of five doubled-haploid populations derived from five resistant synthetic hexpaloid wheat lines, each crossed to the susceptible Australian wheat cultivar Janz. For each cross we determined genetic variance, heritability and minimum number of effective resistance genes for each nematode species. Distributions of nematode numbers for both species were continuous for all doubled-haploid populations. Heritabilities were high and the resistances were controlled by 4-7 genes. There was no genetic correlation between resistance to P. thornei and to P. neglectus in four of the populations and a significant but low correlation in one. Therefore, resistances to P. thornei and to P. neglectus are probably inherited quantitatively and independently in four of these synthetic hexaploid wheat populations, with the possibility of at least one genetic factor contributing to resistance to both species in one of the populations. Parents with the greatest level of resistance will be the best to use as donor parents to adapted cultivars, and selection of resistance to both species in early generations will be optimal to carry resistance through successive cycles of inbreeding to produce resistant cultivars for release.
Keywords: Aegilops tauschii; Disease resistance; Durum wheat; Germplasm development; Triticum aestivum; Wheat breeding

MgCl2 center dot 4((CH3)(2)CHCH2OH): a new molecular adduct for the preparation of TiClx/MgCl2 catalyst for olefin polymerization - Thushara, K. S.; Gnanakumar, Edwin S.; Mathew, Renny; Ajithkumar, Thalasseril G.; Rajamohanan, P. R.; Bhaduri, Sumit; Gopinath, Chinnakonda S. (Dalton Transactions, 2012)
A new molecular adduct of MgCl2 with isobutanol, namely MgCl2 center dot 4((CH3)(2)CHCH2OH) (MgiBOH), has been prepared as a precursor to the supporting material for an olefin polymerization catalyst. The MgiBOH adduct and final titanated Ziegler-Natta catalysts have been thoroughly characterized by powder XRD, thermal analysis, Raman spectroscopy and solid-state NMR for structural and spectroscopy aspects. A peak observed at 712 cm(-1) in the Raman spectra of MgiBOH indicates the characteristic Mg-O-6 breathing mode and the formation of the adduct. The diffraction feature at 2 theta = 7.8 degrees (d = 11.223 angstrom) in the XRD confirms the adduct formation and the layered structure. The aim of the present article is to study how the insertion of a bulky isobutanol moiety affects the structural and electronic properties of the MgCl2 isobutanol molecular adduct. Indeed, the focus of the present study is to explore how the presence of isobutanol, in the initial molecular adduct, influences the final Z-N catalyst properties and its activity.

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

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

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.

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

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)

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.).

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

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

Stress inducible proteinase inhibitor diversity in capsicum annuum - Mishra, Manasi; Mahajan, Neha S.; Tamhane, Vaijayanti A.; Kulkarni, Mahesh J.; Baldwin, Ian T.; Gupta, Vidya S.; Giri, Ashok P. (BMC Plant Biology, 2012)
Background: Wound-inducible Pin-II Proteinase inhibitors (PIs) are one of the important plant serine PIs which have been studied extensively for their structural and functional diversity and relevance in plant defense against insect pests. To explore the functional specialization of an array of Capsicum annuum (L.) proteinase inhibitor (CanPIs) genes, we studied their expression, processing and tissue-specific distribution under steady-state and induced conditions. Inductions were performed by subjecting C. annuum leaves to various treatments, namely aphid infestation or mechanical wounding followed by treatment with either oral secretion (OS) of Helicoverpa armigera or water. Results: The elicitation treatments regulated the accumulation of CanPIs corresponding to 4-, 3-, and 2-inhibitory repeat domains (IRDs). Fourty seven different CanPI genes composed of 28 unique IRDs were identified in total along with those reported earlier. The CanPI gene pool either from uninduced or induced leaves was dominated by 3-IRD PIs and trypsin inhibitory domains. Also a major contribution by 4-IRD CanPI genes possessing trypsin and chymotrypsin inhibitor domains was specifically revealed in wounded leaves treated with OS. Wounding displayed the highest number of unique CanPIs while wounding with OS treatment resulted in the high accumulation of specifically CanPI-4, -7 and -10. Characterization of the PI protein activity through two dimensional gel electrophoresis revealed tissue and induction specific patterns. Consistent with transcript abundance, wound plus OS or water treated C. annuum leaves exhibited significantly higher PI activity and isoform diversity contributed by 3- and 4-IRD CanPIs. CanPI accumulation and activity was weakly elicited by aphid infestation yet resulted in the higher expression of CanPI-26, -41 and -43. Conclusions: Plants can differentially perceive various kinds of insect attacks and respond appropriately through activating plant defenses including regulation of PIs at transcriptional and post-translational levels. Based on the differentially elicited CanPI accumulation patterns, it is intriguing to speculate that generating sequence diversity in the form of multi-IRD PIs is a part of elaborative plant defense strategy to obtain a diverse pool of functional units to confine insect attack.
Keywords: CanPI; Herbivory; Oral secretions; Pin-II type proteinase inhibitors; Plant-insect interaction

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:

Thermal, mechanical, and rheological characterization of polypropylene/layered double hydroxide nanocomposites - Lonkar, Sunil P.; Therias, Sandrine; Leroux, Fabrice; Gardette, Jean Luc; Singh, Raj Pal (Polymer Engineering and Science, 2012)
Polypropylene (PP)/organomodified layered double hydroxide (LDH) nanocomposites were prepared in order to examine the influence of LDH content on thermal, mechanical, and rheological properties. The nanostructure examinations by X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the exfoliated/intercalated dispersion of LDH. Incorporation of the LDH resulted in a noteworthy improvement in the thermal stability of PP. It was shown that the addition of LDH contributed to the reinforcement effect by increasing the elastic modulus. The mechanical performance, as evaluated by stressstrain curves, reveal that PP/LDH hybrid materials showed significant contribution toward increment in elastic modulus, tensile strength but at the expense of impact strength. The rheological response showed a strong influence of LDH particles on the flow behavior of the PP/LDH melt which resulted in enhancement of storage, loss of moduli, and complex viscosity of nanocomposites. Therefore, the nanocomposites have higher moduli but better processibility compared with pure PP. Overall, the results indicated that the LDH particles in nanometer size might act as potential reinforcing agent for polypropylene. POLYM. ENG. SCI., 52:20062014, 2012. (c) 2012 Society of Plastics Engineers

Toward understanding the redox properties of model chromophores from the greenfluorescent protein family: an interplay between conjugation, resonance stabilization, and solvent effects - Ghosh, Debashree; Acharya, Atanu; Tiwari, Subodh C.; Krylov, Anna I. (Journal of Physical Chemistry B, 2012)
The redox properties of model chromophores from the green fluorescent protein family are characterized computationally using density functional theory with a long-range corrected functional, the equation-of-motion coupled-cluster method, and implicit solvation models. The analysis of electron-donating abilities of the chromophores reveals an intricate interplay between the size of the chromophore, conjugation, resonance stabilization, presence of heteroatoms, and solvent effects. Our best estimates of the gas-phase vertical/adiabatic detachment energies of the deprotonated (i.e., anionic) model red, green, and blue chromophores are 3.27/3.15, 2.79/2.67, and 2.75/2.35 eV, respectively. Vertical/adiabatic ionization energies of the respective protonated (i.e., neutral) species are 7.64/7.35, 7.38/7.15, and 7.70/7.32 eV, respectively. The standard reduction potentials (E-red(0)) of the anionic (Chr(center dot)/Chr(-)) and neutral (Chr(+center dot)/Chr) model chromophores in acetonitrile are 0.34/1.40 V (red), 0.22/1.24 V (green), and -0.12/1.02 V (blue), suggesting, counterintuitively, that the red chromophore is more difficult to oxidize than the green and blue ones (in both neutral and deprotonated forms). The respective redox potentials in water follow a similar trend but are more positive than the acetonitrile values.

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

Transformation of (+/-)-lavandulol and (+/-)-tetrahydrolavandulol by a fungal strain Rhizopus oryzae - Daramwar, Pankaj P.; Rincy, Raju; Niloferjahan, Siddiqui; Krithika, Ramakrishnan; Gulati, Arvind; Yadav, Amit; Sharma, Rakesh; Thulasiram, Hirekodathakallu V. (Bioresource Technology, 2012)
Biotransformation of an irregular monoterpene alcohol, (+/-)-lavandulol [(+/-)-5-methyl-2-(1-methylethenyl)-4-hexen-1-ol] (I) and its tetrahydro derivative, (+/-)-tetrahydrolavandulol [(+/-)-2-isopropyl-5-methylhexan-1-ol] (II) were studied using a soil isolated fungal strain Rhizopus oryzae. Five metabolites, 2-((3,3-dimethyloxiran-2-yl)methyl)-3-methylbut-3-en-1-ol (Ia), 2-methyl-5-(prop-1-en-2-yl)hex-2ene-1,6-diol (Ib), 2-methyl-5-(prop-1-en-2-yl)hexane-1,6-diol (Ic), 2-(3-methylbut-2-enyl)-3-methylenebutane-1,4-diol (Id), 5-methyl-2-(2-methyloxiran-2-yl)hex-4-en-1-01 (Ie) have been isolated from the fermentation medium and characterized with lavandulol as a substrate. When tetrahydrolavandulol used as a substrate, two metabolites 2-isopropyl-5-methylhexane-1,5-diol (IIa) and 2-isopentyl-3-methylbutane-1,3-diol (lib) have been isolated from the fermentation medium. Biotransformation studies with R. oryzae clearly indicate that the organism initiates the transformation either by hydroxylation at allylic methyl groups or epoxidation of double bond. GC and GCMS analyses indicated that both (R)and (S)-enantiomers of I and II have been transformed into corresponding hydroxylated or epoxy derivatives, when racemic I and II were used as substrates. (C) 2011 Elsevier Ltd. All rights reserved.
Keywords: Biotransformation; Fungus; Lavandulol; Rhizopus oryzae; Tetrahydrolavandulol

Trehalose as an indicator of desiccation stress in Drosophila melanogaster larvae: a potential marker of anhydrobiosis (vol 419, pg 638, 2012) - Thorat, Leena J.; Gaikwad, Sushama M.; Nath, Bimalendu B. (Biochemical and Biophysical Research Communications, 2012)

Trehalose as an indicator of desiccation stress in Drosophila melanogaster larvae: a potential marker of anhydrobiosis - Thorat, Leena J.; Gaikwad, Sushama M.; Nath, Bimalendu B. (Biochemical and Biophysical Research Communications, 2012)
In the current scenario of global climate change, desiccation is considered as one of the major environmental stressors for the biota exposed to altered levels of ambient temperature and humidity. Drosophila melanogaster, a cosmopolitan terrestrial insect has been chosen as a humidity-sensitive bioindicator model for the present study since its habitat undergoes frequent stochastic and/or seasonally aggravated dehydration regimes. We report here for the first time the occurrence of anhydrobiosis in D. melanogaster larvae by subjecting them to desiccation stress under laboratory conditions. Larvae desiccated for ten hours at <5% relative humidity could enter anhydrobiosis and could revive upon rehydration followed by resumption of active metabolism. As revealed by FIR and HPLC analyzes, our findings strongly indicated the synthesis and accumulation of trehalose in the desiccating larvae. Biochemical measurements pointed out the desiccation-responsive trehalose metabolic pathway that was found to be coordinated in concert with the enzymes trehalose 6-phosphate synthase and trehalase. Further, an inhibitor-based experimental approach using deoxynojirimycin, a specific trehalase inhibitor, demonstrated the pivotal role of trehalose in larval anhydrobiosis of D. melanogaster. We therefore propose trehalose as a potential marker for the assessment of anhydrobiosis in Drosophila. The present findings thus add to the growing list of novel biochemical markers in specific bioindicator organisms for fulfilling the urgent need of environmental biomonitoring of climate change. (C) 2012 Elsevier Inc. All rights reserved.
Keywords: Anhydrobiosis; biomarker; Deoxynojirimycin; Desiccation; Drosophila melanogaster; trehalose

Viscosity dependence of intra- and intermolecular diels-alder reactions - Tiwari, Shraeddha; Kumar, Anil (Journal of Physical Chemistry A, 2012)
The kinetics of the bimolecular Die Is Alder reaction between anthracene-9-carbinol and N-ethyl maleimide have been studied in a series of pyridinium-based ionic liquids with the tetrafluoroborate ([BF4](-)) and the bis(trifluorosulfonimide) ([NTf2](-)) anions and the viscosity dependence of the rate constants have been compared with the results for the intramolecular Diels Alder reaction of (E)-1-phenyl-4-[2-(3-methyl-2-butenyloxy)benzylidene]-5-pyrazolone. The comparison leads to the surprising observation that the intermolecular reaction is less susceptible to viscosity variations of the ionic liquids as compared to the intramolecular reaction. The observed similarities and differences emphasize the complicated nature of solvent friction on the kinetics of cycloaddition reactions. The results are explained by considering the bimolecular and intramolecular processes as cases of translational and rotational diffusion, respectively. Plausible indicators of microviscosity consistent with the kinetic data for the Diels-Alder reactions are briefly discussed along with the constraints involved in designing a general microviscosity scale.

VUV Photoionization and Ab initio determination of the ionization energy of a gas-phasesugar (deoxyribose) - Ghosh, Debashree; Golan, Amir; Takahashi, Lynelle K.; Krylov, Anna I.; Ahmed, Musahid (Journal of Physical, 2012)
The ionization energy of gas-phase deoxyribose was determined using tunable vacuum ultraviolet synchrotron radiation coupled to an effusive thermal source. Adiabatic and vertical ionization energies of the ground and first four excited states of alpha-pyranose, the structure that dominates in the gas phase, were calculated using high-level electronic structure methods. An appearance energy of 9.1(+/- 0.05) eV was recorded, which agrees reasonably well with a theoretical value of 8.8 eV for the adiabatic ionization energy. A clear picture of the dissociative photoionization dynamics of deoxyribose emerges from the fragmentation pattern recorded using mass spectrometry and from ab initio molecular dynamics calculations. The experimental threshold 9.4 (+/- 0.05) eV for neutral water elimination upon ionization is captured well in the calculations, and qualitative insights are provided by molecular orbital analysis and molecular dynamics snapshots along the reaction coordinate.

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

Biocatalysis: fungi mediated novel and selective 12 beta- or 17 beta-hydroxylation on the basic limonoid skeleton - Haldar, Saikat; Kolet, Swati P.; Thulasiram, Hirekodathakallu V. (Green Chemistry, 2013)
Basic limonoids carrying a 4,4,8-trimethyl-17-furanylsteroid skeleton are a class of triterpenoids and well-known for their insecticidal as well as a vast array of pharmacological activities. Rare and synthetically challenging 12 beta- and 17 beta-hydroxylation was achieved on the basic limonoid skeleton to produce a novel series of hydroxylated limonoids using fungi-mediated biocatalysis. The fungal system belonging to the genera of Mucor efficiently converted azadiradione, epoxyazadiradione, gedunin and their derivatives into corresponding 12 beta- and/or 17 beta-hydroxy derivatives. The position and stereochemistry of hydroxylation was determined by rigorous spectroscopic and crystallographic studies. This fungi-mediated stereo- and regio-selective hydroxylation process was highly efficient and mild enough to sustain chemically sensitive functional groups around the basic limonoid skeleton. Modifications of specific functional groups and variation in biocatalyst were shown to bring selectivity among 12 beta- or 17 beta-hydroxylation.

Biocatalyst mediated production of 6 beta,11 alpha-dihydroxy derivatives of 4-ene-3-one steroids - Kolet, Swati P.; Niloferjahan, Siddiqui; Haldar, Saikat; Gonnade, Rajesh G.; Thulasiram, Hirekodathakallu V. (Steroids, 2013)
Biotransformation of steroids with 4-ene-3-one functionality such as progesterone (I), testosterone (II), 17 alpha-methyltestosterone (III), 4-androstene-3,17-dione (IV) and 19-nortestosterone (V) were studied by using a fungal system belonging to the genera of Mucor (M881). The fungal system efficiently and quantitatively converted these steroids in regio- and stereo-selective manner into corresponding 6 beta,11 alpha-dihydroxy compounds. Time course experiments suggested that the transformation was initiated by hydroxylation at 6 beta- or 11 alpha-(10 beta-hydroxy in case of V) to form monohydroxy derivatives which upon prolonged incubation were converted into corresponding 613,11oc-dihydroxy derivatives. The fermentation studies carried out using 5 L table-top fermentor with substrates (I and II) clearly indicates that 6 beta,11 alpha-dihydroxy derivatives of steroids with 4-ene-3-one functionality can be produced in large scale by using M881. (C) 2013 Elsevier Ltd.
Keywords: 4-Ene-3-one steroids; Biotransformation; Mucor sp.

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

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

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

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

Copolymerization of ethylene with unsaturated alcohols and methylmethacrylate using a silylated alpha-diimine nickel catalyst: molecular modeling and photodegradation studies - Matos, Ines; Fernandes, Susete N.; Liu, Hua-Rong; Tevtia, Amit K.; Singh, R. P.; Manda, Lemos; Lemos, Francisco; Marques, Maria M. (Journal of Applied Polymer Science, 2013)
In this article, the experimental results obtained in the copolymerization of ethylene with polar monomers using a silylated -diimine nickel catalyst are described and compared with those obtained with a non-silylate similar one. The results show that the introduction of a siliyl group in the para-position of the imine moiety turns the catalyst less sensitive toward polar functionalities. However, the reactivity observed in copolymerization reactions was found to be reduced both the global polymerization and incorporation rates. Molecular modeling calculation allowed us to understand both the preferred insertion mode and the intermediate product structures for E/MMA copolymerization. Photodegradation studies showed that the presence of polar groups in the copolymers increases their rate of oxidation and turn them more easily degradable. The stabilization performed by Tinuvin 770 showed that for long-exposure times, it is not very effective regardless it is only mixed or grafted to the copolymer. (c) 2012 Wiley Periodicals, Inc.
Keywords: ageing; copolymers; Degradation; grafting

Crystallization kinetics of Sn-MFI molecular sieve formation by dry gel cross mark conversion method - Niphadkar, P. S.; Tangale, N. P.; Joshi, P. N.; Awate, S. V. (Microporous and Mesoporous Materials, 2013)
The conversion of amorphous stannosilicate dry gel into crystalline molecular sieve with MFI structure (Sn-MFI) was achieved by dry gel conversion (DGC) method at 413, 443 and 473 K. For comparison purpose, Sn-MFI molecular sieve with similar SiO2/SnO2 mole ratio was also obtained by hydrothermal crystallization route. Crystallization curves were established by conducting time dependant studies on progressive crystallization processes for both the systems. The values of activation energy of nucleation (E-n), activation energy of crystallization (E-c), and their pre-exponential factors (InA(n), InA(c) respectively) were calculated from Arrhenius plots. Compared to the hydrothermal method, shorter induction period was observed when DGC method was employed. Both the E-n (49.70 kJ/mol) and E-c (52.82 kJ/mol) for DGC method were found to be lower than that of the E-n (55.70 kJ/mop and E-c (60.23 kJ/mol) for hydrothermal method. The kinetics parameters viz. K and q were derived from kinetic expressions and DGC method showed higher value of K and lower value of q compared to hydrothermal crystallization method at identical temperature. Various DGC method parameters such as water content at the bottom of autoclave and SiO2/SnO2 mole ratio have shown the influence on the kinetics of crystallization of Sn-MFI. (C) 2013 Elsevier Inc. All rights reserved.
Keywords: Crystallization; DGC; kinetics; Nucleation; Sn-MFI

Cyanate ester resins containing pentadecyl-substituted cyclohexyl moiety: synthesis, curing and structure-property relationship - Kulkarni, Arun D.; Tawade, Bhausaheb V.; Wadgaonkar, Prakash P. (High Performance Polymers, 2013)
Cyanate ester (CE) monomers containing pentadecyl-substituted cyclohexyl moieties such as 1,1-bis(4-cyanatophenyl) 3-pentadecylcyclohexane and 1,1-bis(4-cyanatophenyl) cyclohexane were synthesized and characterized by Fourier transform infrared, proton-nuclear magnetic resonance (H-1-NMR) and carbon-nuclear magnetic resonance (C-13-NMR) spectroscopies as well as differential scanning calorimetry (DSC). Both 1,1-bis(4-cyanatophenyl) 3-pentadecylcyclohexane and 1,1-bis(4-cyanatophenyl) cyclohexane exhibited better processability coupled with lower melting points, lower cure onset with broad cure exotherm than the commercially available CE monomer, namely, 2,2-bis(4-cyanatophenyl) propane. Glass transition temperatures of cured 2,2-bis(4-cyanatophenyl) propane, 1,1-bis(4-cyanatophenyl) cyclohexane and 1,1-bis(4-cyanatophenyl) 3-pentadecylcyclohexane were observed to be 288 degrees C, 302 degrees C and 160 degrees C, respectively. Cured 1,1-bis(4-cyanatophenyl) cyclohexane displayed higher storage modulus (1.59 x 10(9) Pa) than 1,1-bis(4-cyanatophenyl) 3-pentadecylcyclohexane (1.07 x 10(9) Pa) and 2,2-bis(4-cyanatophenyl) propane (1.39 x 10(9) Pa). The order of thermal stability of cured polycyanurates was found to be 2,2-bis(4-cyanatophenyl) propane > 1,1-bis(4-cyanatophenyl) cyclohexane > 1,1-bis(4-cyanato phenyl) 3-pentadecylcyclohexane. The moisture absorption of cured resins derived from 1,1-bis(4-cyanatophenyl) 3-pentadecyl cyclohexane and 1,1-bis(4-cynatophenyl) cyclohexane was found to be lower than that of 2,2-bis(4-cynatophenyl) propane implying the role of pentadecyl substituent and/or cyclohexyl moiety in imparting hydrophobicity to the polycyanurates.
Keywords: (pentadecyl substituted) cyclohexyl; curing; cyanate ester resin; thermosets

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

Dehydrogenation of cyclohexanol over Cu/Al2O3 catalysts prepared with different precipitating agents - Tangale, Nilesh P.; Niphadkar, Prashant S.; Deshpande, Shilpa S.; Joshi, Praphulla N. (Applied Catalysis A-General, 2013)
Dehydrogenation of cyclohexanol over Cu/Al2O3 catalysts (molar Cu:Al = 1:1) prepared by reduction of mixed oxide precursors synthesized using different precipitating agents viz, potassium carbonate, tetraalkyl ammonium hydroxides (TAAOHs) and urea was investigated. In order to assess the efficacy of TAAOH further, the chain length of tetraalkyl ammonium cations was also varied and the resulted catalysts were evaluated for their catalytic performance. The catalysts were characterized by powder X-ray diffraction, low temperature nitrogen adsorption, temperature programmed desorption of ammonia and UV-visible diffuse reflectance spectroscopy. The dependence of the catalyst performance on the precipitating agent employed during its synthesis has been clearly demonstrated. The use of TAAOH as precipitating agent led to the formation of a catalyst with better catalytic activity than those prepared using potassium carbonate and urea. Further improvement in the catalytic performance was observed when TAAOH with longer alkyl chain ammonium cation was used. The optimum catalyst prepared by reduction of mixed oxide precursor synthesized using tetrapropyl ammonium hydroxide as precipitating agent, showed highest cyclohexanol conversion (81.5%) and cyclohexanone selectivity (79.6%) at 250 degrees C on account of higher Cu+/Cu-0 ratio, well dispersed copper, higher surface area and lower total acidity with higher contribution of sites with moderate strength. (C) 2013 Elsevier B.V. All rights reserved.
Keywords: Characterization; Cu/Al2O3; Cyclohexanol dehydrogenation; Precipitating agent; Tetraalkyl ammonium hydroxide

Design of a high performance thin all-solid-state supercapacitor mimicking the active interface of its liquid-state counterpart - Anothumakkool, Bihag; Torris, Arun A. T.; Bhange, Siddheshwar N.; Unni, SreeKuttan M.; Badiger, Manohar V.; Kurungot, Sreekumar (ACS Applied Materials & Interfaces, 2013)
Here we report an all-solid-state supercapacitor (ASSP) which closely mimics the electrode-electrolyte interface of its liquid-state counterpart by impregnating polyaniline (PANO-coated carbon paper with polyvinyl alcohol-H2SO4 (PVA-H2SO4) gel/plasticized polymer electrolyte. The well penetrated PVA-H2SO4 network along the porous carbon matrix essentially enhanced the electrode-electrolyte interface of the resulting device with a very low equivalent series resistance (ESR) of 1 Omega/cm(2) and established an interfacial structure very similar to a liquid electrolyte. The designed interface of the device was confirmed by cross-sectional elemental mapping and scanning electron microscopy (SEM) images. The PANI in the device displayed a specific capacitance of 647 F/g with an areal capacitance of 1 F/cm(2) at 0.5 A/g and a capacitance retention of 62% at 20 A/g. The above values are the highest among those reported for any solid-state-supercapacitor. The whole device, including the electrolyte, shows a capacitance of 12 F/g with a significantly low leakage current of 16 mu A(2). Apart from this, the device showed excellent stability for 10000 cycles with a coulombic efficiency of 100%. Energy density of the PANI in the device is 14.3 Wh/kg.
Keywords: all-solid-state; cyclic voltametry; impedance analysis; polyaniline; polyvinyl alcohol; supercapacitor

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

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

Effect of organic modification on the intercalation and the properties of poly(phenylene oxide)/polystyrene blend-clay nanocomposites - Tiwari, Rajkiran R.; Natarajan, Upendra (Journal of Thermoplastic Composite Materials, 2013)
Nanocomposites prepared by the dispersion of unmodified and organically modified montmorillonite (MMT) clay into poly(2,6-dimethyl phenylene oxide)/polystyrene miscible blend in the range of 2-10 wt% clay were investigated by wide-angle x-ray diffraction, transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis and tensile mechanical tests. The systems based on unmodified sodium MMT (Na+MMT) as well as Cloisite 20A, Cloisite 30B and Cloisite 10A organically modified clays showed polymer intercalation. The glass transition temperature (T-g) value was not affected by the volume fraction of clay and chemical nature of the organoclay. The thermal degradation stability of nanocomposites is found to be only slightly better than that of the blend matrix. A percolation threshold of around 4 wt% organoclay loading is observed. An improvement of 35% relative to unfilled polymer blend matrix is observed for the modulus, for Cloisite 20A nanocomposite containing 2 wt% organoclay. The observed modulus improvement with significant retention of elongational tensile strength and tensile ductility in case of unmodified Na-MMT and Cloisite 30B nanocomposites appears promising. The modulus prediction using Halpin-Tsai model is found to be closer to the experimental data when MMT volume fraction rather than the organoclay volume fraction is used.
Keywords: filler; interface; interphase; mechanical properties; Nanostructures; Polymer-matrix composites

Expedient preparative isolation, quantification and characterization of limonoids from neem fruits - Haldar, Saikat; Phapale, Prasad B.; Kolet, Swati P.; Thulasiram, Hirekodathakallu V. (Analytical Methods, 2013)
Major basic limonoids from Neem fruits such as azadirone, epoxyazadiradione and azadiradione were isolated in preparative scale using an automated and rapid medium pressure liquid chromatography (MPLC)-based protocol. They were individually quantified using HPLC. An LC-ESI-MS/MS-based rapid identification technique was developed for the high-throughput screening of these limonoids in phytochemical extracts.

Facile strategy for synthesis of ,-heterobifunctionalized poly (epsilon-caprolactones) and poly (methyl methacrylate)s containing ``clickable'' aldehyde and allyloxy functional groups using initiator approach - Sane, Prakash S.; Tawade, Bhausaheb V.; Parmar, Indravadan; Kumari, Savita; Nagane, Samadhan; Wadgaonkar, Prakash P. (Journal of Polymer Science Part A-Polymer Chemistry, 2013)
Two new initiators, namely, 4-(4-(2-(4-(allyloxy) phenyl)-5-hydroxypentane 2-yl) phenoxy)benzaldehyde and 4-(4-(allyloxy) phenyl)-4-(4-(4-formylphenoxy) phenyl) pentyl 2-bromo-2-methyl propanoate containing clickable hetero-functionalities namely aldehyde and allyloxy were synthesized starting from commercially available 4,4-bis(4-hydroxyphenyl) pentanoic acid. These initiators were utilized, respectively, for ring opening polymerization of epsilon-caprolactone and atom transfer radical polymerization of methyl methacrylate. Well-defined -aldehyde, -allyloxy heterobifunctionalized poly(epsilon-caprolactones) (Mn,GPC: 590029,000, PDI: 1.261.43) and poly(methyl methacrylate)s (Mn,GPC: 530028800, PDI: 1.191.25) were synthesized. The kinetic study of methyl methacrylate polymerization demonstrated controlled polymerization behavior. The presence of aldehyde and allyloxy functionality on polymers was confirmed by 1H NMR spectroscopy. Aldehyde-aminooxy and thiol-ene metal-free double click strategy was used to demonstrate reactivity of functional groups on polymers. (c) 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013, 51, 2091-2103
Keywords: atom transfer radical polymerization; Click chemistry; functional polymers; ring opening polymerization

Ferromagnetism in metal oxide systems: interfaces, dopants, and defects - Thakare, Vishal P.; Game, Onkar S.; Ogale, Satishchandra B. (Journal of Materials Chemistry C, 2013)
Ferromagnetism in metal oxide systems has always attracted scientific attention in view of the intriguing and interesting interplay of spin, charge, orbital and lattice degrees of freedom that such systems display. This trend appears to be continuing with enhanced focus on interface systems, multiferroics, diluted magnetic semiconducting oxides (DMSOs) and nanomaterial magnetism. Newer techniques are being applied to bring out materials issues that are critical to the precise understanding of the origin of magnetism in certain cases. Interest is also beginning to grow in exploring application potential of some such systems. In this article we review the developments in this field by late 2011 and 2012.

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

Identification of molecular crystals capable of undergoing an acyl-transfer reaction based on intermolecular interactions in the crystal lattice - Tamboli, Majid I.; Krishnaswamy, Shobhana; Gonnade, Rajesh G.; Shashidhar, Mysore S. (Chemistry-A European Journal, 2013)
Investigation of the intermolecular acyl-transfer reactivity in molecular crystals of myo-inositol orthoester derivatives and its correlation with crystal structures enabled us to identify the essential parameters to support efficient acyl-transfer reactions in crystals: 1)the favorable geometry of the nucleophile (OH) and the electrophile (CO) and 2)the molecular assembly, reinforced by CH interactions, which supports a domino-type reaction in crystals. These parameters were used to identify another reactive crystal through a data-mining study of the Cambridge Structural Database. A 2:1 co-crystal of 2,3-naphthalene diol and its di-p-methylbenzoate was selected as a potentially reactive crystal and its reactivity was tested by heating the co-crystals in the presence of solid sodium carbonate. A facile intermolecular p-toluoyl group transfer was observed as predicted. The successful identification of reactive crystals opens up a new method for the detection of molecular crystals capable of exhibiting acyl-transfer reactivity.
Keywords: Acylation; domino reactions; intermolecular interactions; solid-state reactions; X-ray diffraction

Liquefied petroleum gas sensing performance of cerium doped copper ferrite - Khandekar, M. S.; Tarwal, N. L.; Patil, J. Y.; Shaikh, F. I.; Mulla, Imtiaz S.; Suryavanshi, S. S. (Ceramics International, 2013)
Undoped and cerium (Ce) doped nanocrystalline copper ferrite (CuFe2O4) materials were synthesized via the molten-salt (M-S) method. Effects of Ce doping on the structural, morphological and gas sensing properties of the CuFe2O4 ferrite have been investigated. X-ray diffraction (XRD) analysis revealed the formation of spinel CuFe2O4. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) investigations showed that the synthesized ferrite is made up of very fine spherical nanoparticles. Moreover, the gas sensing properties of sintered samples were studied towards different reducing gases such as liquefied petroleum gas (LPG), acetone, ethanol and ammonia. The sample with 4% cerium doped CuFe2O4 (Ce4) showed the maximum gas sensitivity (86%) towards LPG with fast response time of 5 s and good recovery time of 68 s. (C) 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: Ferrite; Gas sensor; Molten-salt method; TEM

Low-pressure synthesis and characterization of hydrogen-filled ice ic - Kumar, Rajnish; Klug, Dennis D.; Ratcliffe, Christopher I.; Tulk, Christopher A.; Ripmeester, John A. (Angewandte Chemie-International Edition, 2013)
Keywords: Clathrates; cubic ice; hydrates; Hydrogen

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

Necking in extrusion film casting: the role of macromolecular architecture - Pol, Harshawardhan V.; Thete, Sumeet Suresh; Doshi, Pankaj; Lele, Ashish K. (Journal of Rheology, 2013)
Extrusion film casting (EFC) is used on an industrial scale to produce several thousand tons of polymer films and coatings. While significant research has been carried out on necking of films of viscoelastic melts in EFC, the influence of macromolecular chain architecture on the necking behavior is not yet fully understood. In the present research, we have explored experimentally and theoretically the effects of long chain branching and molecular weight distribution on the extent of necking during EFC. Polyethylenes of essentially linear architecture but having narrow and broad molecular weight distributions, and polyethylenes having long chain branching were used for experimental studies. The EFC process was analyzed using the one-dimensional flow model of Silagy et al. [Polym. Eng. Sci. 36(21), 2614-2625 (1996)] in which multimode molecular constitutive equations namely the ``extended pom-pom'' equation (for long chain branched polymer melts) and the ``Rolie-Poly (Rouse linear entangled polymers)'' equation (for linear polymer melts) were incorporated. We show that the model qualitatively captures the salient features of the experimental data thereby elucidating the role of chain architecture on the extent of necking. (C) 2013 The Society of Rheology. [http://dx.doi.org/10.1122/1.4788911]

One-pot fluorescent labeling protocol for complex hydroxylated bioactive natural products - Haldar, Saikat; Kumar, Santosh; Kolet, Swati P.; Patil, Harshal S.; Kumar, Dhiraj; Kundu, Gopal C.; Thulasiram, Hirekodathakallu V. (Journal of Organic Chemistry, 2013)
Tagging of small bioactive molecules with a fluorophore is a highly sensitive method to trace their cellular activities through real-time visual information. Here we disclose a 7-nitrobenzo-2-oxa-1,3-diazole (NBD)-based, high-yielding, one-pot labeling protocol for hydroxylated molecules using Yamaguchi coupling as the key reaction. This methodology was successfully applied on several sensitive and complex hydroxylated bioactive compounds including 7-deacetylazadiradione, simvastatin, camptothecin, andrographolide, cinchonine, beta-dihydroartemisinin, and azadirachtin A. Further, utility of this protocol was illustrated on the cytotoxic activity of azadiradione derivatives against several cancer cell lines through cell imaging of two qualified fluorescent probes.

Photopolymerization of bis-aromatic and alicyclic based solid urethane acrylate macromonomer in the presence of large excess of reactive diluent Kinetics and modeling - Harikrishna, Reghunathan; Ponrathnam, S.; Rajan, C. R.; Tambe, S. S. (Journal of Thermal Analysis and Calorimetry, 2013)
A solid urethane acrylate macromonomer with bis-aromatic as well as alicyclic moieties was synthesized and the kinetics of photopolymerization reactions were studied in the presence of varying concentration of photoinitiator and large excess of reactive diluent using photo DSC. The studies show that the rate of maximum polymerization was found to increase with increase in concentration of photoinitiator while a decrease was observed by an increase in temperature. The final conversion showed a decrease at highest isothermal condition due to vitrification. Estimation of kinetic parameters including applicability of autocatalytic and modified autocatalytic models were investigated by nonlinear regression. It was observed that the modified models gave a better fit with the experimental data and kinetic parameters showed a decrease with increase in temperature and an increase with increase in concentration of photoinitiator.
Keywords: Autocatalytic model; kinetics; Levenberg-Marquardt method; Photopolymerization

Plasticity of protease gene expression in helicoverpa armigera upon exposure to multi-domain capsicum annuum protease inhibitor - Mahajan, Neha S.; Mishra, Manasi; Tamhane, Vaijayanti A.; Gupta, Vidya S.; Giri, Ashok P. (Biochimica et Biophysica Acta (BBA) - General Subjects, 2013)
Background A multi-domain Pin-II type protease inhibitor from Capsicum annuum (CanPI-7) is known to be effective against the insect pest, Helicoverpa armigera. The present study is an attempt to investigate the optimal dose of recombinant CanPI-7 (rCanPI-7) for effective antibiosis to H. armigera and further to characterize the responses of digestive proteases upon rCanPI-7 ingestion. Methods The gut protease activity was assessed biochemically and transcript accumulation pattern for selected trypsin and chymotrypsin genes was analyzed by quantitative Real-Time PCR. Results The growth retardation upon exposure to rCanPI-7 was more prominent in neonates as compared to third instar larvae. Influence of stage and dosage of rCanPI-7 was conspicuous on the expression and regulation of candidate trypsin and chymotrypsin genes in H. armigera. The transcript accumulation pattern correlated with the protease activity in rCanPI-7 exposed larvae. Conclusions We conclude that early exposure and specific dose of protease inhibitor are essential for effective antibiosis despite the large diversity and plasticity in the expression of protease genes in H. armigera. Moreover, it is also evident that the regulation and expression of H. armigera gut proteases are specific to the stage of PI exposure. General significance These results highlight the requirement of optimal PI concentration for effective growth retardation and for inhibiting the major gut proteases of H. armigera.

Poly-L-arginine grafted silica mesoporous nanoparticles for enhanced cellular uptake and their application in DNA delivery and controlled drug release - Kar, Mrityunjoy; Tiwari, Neha; Tiwari, Mitali; Lahiri, Mayurika; Sen Gupta, Sayam (Particle & Particle Systems Characterization, 2013)
Mesoporous silica nanoparticles (MSNs), that are capable of delivering gene and drugs to organisms in an effective and selective way have attracted much attention lately for its potential in the treatment of cancer. However, the successful application of MSNs for delivery of plasmid DNA or drugs requires surface modification of the silica with positively charged functional groups so that it binds to the negatively charged nucleic acids and also helps it penetrate through the cell membrane. We report for the first time the synthesis of a hybrid MSN where the cell penetrating cationic polypeptide poly-L-arginine synthesized by NCA polymerization is grafted onto the external surface of MSN using click chemistry. These poly-L-arginine grafted MSNs show low cytotoxity (85% cell viability at 100 g/mL MSN concentration) and high cellular uptake by both HeLa and A549 (>90%). The poly-L-arginine grafted MSNs were used effectively to deliver mCherry DNA plasmid into cells leading to expression of the protein mCherry inside the cells (transfection efficiency 60%). In contrast, poly-L-arginine grafted non-porous silica nanoparticles were unable to express the protein mCherry inside the cells although their uptake into the cells was as efficient as with poly-L-arginine grafted MSNs. We also show preliminary results to demonstrate that these hybrid MSNs can be used as a delivery vehicle for the anticancer drug Doxorubicin towards cancerous cells HeLa and A549. The biocompatibility of poly-L-arginine and its cell penetrating ability are expected to make these MSN conjugates very useful carriers for the delivery of genes and drugs into cancer cells.

Production, purification and characterization of cholesterol oxidase from a newly isolated streptomyces sp. - Niwas, Ram; Singh, Vineeta; Singh, Rajbir; Tripathi, Divya; Tripathi, C. K. M. (World Journal of Microbiology & Biotechnology, 2013)
Cholesterol oxidase production (COD) by a new isolate characterized as Streptomyces sp. was studied in different production media and fermentation conditions. Individual supplementation of 1 % maltose, lactose, sucrose, peptone, soybean meal and yeast extract enhanced COD production by 80-110 % in comparison to the basal production medium (2.4 U/ml). Supplementation of 0.05 % cholesterol (inducer) enhanced COD production by 150 %. COD was purified 14.3-fold and its molecular weight was found to be 62 kDa. V-max (21.93 mu M/min mg) and substrate affinity K-m (101.3 mu M) suggested high affinity of the COD for cholesterol. In presence of Ba2+ and Hg2+ the enzyme activity was inhibited while Cu2+ enhanced the activity nearly threefold. Relative activity of the enzyme was found maximum in triton X-100 whereas sodium dodecyl sulfate inactivated the enzyme. The enzyme activity was also inhibited by the thiol-reducing reagents like Dithiothreitol and beta-mercaptoethanol. The COD showed moderate stability towards all organic solvents except acetone, benzene and chloroform. The activity increased in presence of isopropanol and ethanol. The enzyme was most active at pH 7 and 37 A degrees C temperature. This organism is not reported to produce COD.
Keywords: Affinity chromatography; Cholesterol oxidase; HPLC; SDS PAGE; Streptomyces sp.

Proteome wide reduction in AGE modification in streptozotocin induced diabetic mice by hydralazine mediated transglycation - Kesavan, Suresh K.; Bhat, Shweta; Golegaonkar, Sandeep B.; Jagadeeshaprasad, Mashanipalya G.; Deshmukh, Arati B.; Patil, Harshal S.; Bhosale, Santosh D.; Shaikh, Mahemud L.; Thulasiram, Hirekodathakallu V.; Boppana, Ramanamurthy; Kulkarni, Mahesh J. (Scientific Reports, 2013)
The non-enzymatic reaction between glucose and protein can be chemically reversed by transglycation. Here we report the transglycation activity of hydralazine using a newly developed MALDI-TOF-MS based assay. Hydralazine mediated transglycation of HbA1c, plasma proteins and kidney proteins was demonstrated in streptozotocin (STZ) induced diabetic mice, as evidenced by decrease in protein glycation, as well as presence of hydralazine-glucose conjugate in urine of diabetic mice treated with hydralazine. Hydralazine down regulated the expression of Receptor for Advanced Glycation End products (RAGE), NADPH oxidase (NOX), and super oxide dismutase (SOD). These findings will provide a new dimension for developing intervention strategies for the treatment of glycation associated diseases such as diabetes complications, atherosclerosis, and aging.

Self-assembly to function: design, synthesis and broad spectrum antimicrobial properties of short hybrid E-vinylogous lipopeptides - Shankar, S. Shiva; Benke, Sushil N.; Nagendra, Narem; Srivastava, Prabhakar Lal; Thulasiram, Hirekodathakallu V.; Gopi, Hosahudya N. (Journal of Medicinal Chemistry, 2013)
Nonribosomal E-vinylogous gamma-amino acids are widely present in many peptide natural products and have been exploited as inhibitors for serine and cysteine proteases. Here, we are reporting the broad spectrum antimicrobial properties and self-assembled nanostructures of various hybrid lipopeptides composed of 1:1 alternating alpha-and E-vinylogous residues. Analysis of the results revealed that self-assembled nanostructures also play a significant role in the antimicrobial and hemolytic activities. In contrast to the alpha-peptide counterparts, vinylogous hybrid peptides displayed excellent antimicrobial properties against various bacterial and fungal strains. Peptides that adopted nanofiber structures displayed less hemolytic activity, while peptides that adopted nanoneedle structures displayed the highest hemolytic activity.

Syntheses and determination of absolute configurations and biological activities of the enantiomers of the longtailed mealybug pheromone - Ramesh, Remya; Swaroop, Pandrangi Siva; Gonnade, Rajesh G.; Thirupath, Choppari; Waterworth, Rebeccah A.; Millar, Jocelyn G.; Reddy, D. Srinivasa (Journal of Organic Chemistry, 2013)
Preparation and assignment of absolute configurations to both enantiomers of the sex pheromone of the longtailed mealybug, an irregular monoterpenoid with extraordinary biological activity, has been completed. Comparison of the biological activities of both enantiomers and the racemate in field trials showed that the (S)-(+)-enantiomer was highly attractive to male mealybugs, strongly suggesting that female longtailed mealybugs produce this enantiomer. The (R)-(-)-enantiomer was benign, being neither attractive nor inhibitory.

Synthesis and characterization of poly(ether ether ketone)s and poly(ether ether ketone ketone) s containing pendant biphenyl and naphthyl groups - Honkhambe, Pandurang N.; Dhamdhere, Neelam A.; Tawade, Bhausaheb V.; Salunkhe, Manikrao M.; Wadgaonkar, Prakash P. (High Performance Polymers, 2013)
New poly(ether ether ketone)s (PEEKs) and poly(ether ether ketone ketone)s (PEEKKs) containing pendant biphenyl and naphthyl groups were synthesized by nucleophilic substitution reaction of each of the four bisphenols viz., 1-(4- biphenylyl)- 1,1- bis(4- hydroxyphenyl) ethane, 1-(4- biphenylyl)- 1,1- bis(3- methyl, 4- hydroxyphenyl) ethane, 4,4'-[1-(2- naphthalenyl) ethylidene] bis-phenol and 4,4'-[1-(2- naphthalenyl) ethylidene] bis-3-methylphenol with 4,4'- difluorobenzophenone and 1,3- bis(4- fluorobenzoyl) benzene in a solvent mixture of N,N-dimethylacetamide and toluene in the presence of anhydrous potassium carbonate. Inherent viscosities and number-average molecular weights of polymers were in the range of 0.42-0.86 dl/g and 2.40-7.55 x 10(4), respectively. PEEKs and PEEKKs were amorphous in nature and were readily soluble in a wide range of organic solvents and could be cast into flexible and tough films from chloroform solution. Glass transition temperature of PEEKs and PEEKKs were in the range of 180 degrees C -200 degrees C. T-10 values of PEEKs and PEEKKs were in the range of 424 degrees C-512 degrees C in nitrogen atmosphere, indicating their good thermal stability.
Keywords: biphenyl; bisphenol; naphthyl; poly(ether ether ketone ketone)s; poly(ether ether ketone)s; Polycondensation; Thermal properties

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

Triazole-linked anthracenyl-appended calix[4]arene conjugate as receptor for Co(II): synthesis, spectroscopy, microscopy, and computational studies - Mummidivarapu, V. V. Sreenivasu; Hinge, Vijaya Kumar; Tabbasum, Khatija; Gonnade, Rajesh G.; Rao, Chebrolu P. (Journal of Organic Chemistry, 2013)
A new triazole-linked anthracenyl-appended calix[4]arene-1,3-diconjugate (L) has been synthesized and characterized, and its single crystal XRD structure has been established. Binding properties of L toward different biologically relevant metal ions have been studied by fluorescence and absorption spectroscopy in ethanol. L exhibits selective recognition of Co2+ and can detect down to a concentration of 55 ppb (0.92 mu M). The roles of the calix[4]arene platform as well as the preorganized binding core in L's selective recognition have been demonstrated by studying appropriate control molecules. The mode of binding of L with Co2+ has been modeled both by DFT and MD computational calculations. L and its Co2+ complex could be differentiated on the basis of the nanostructural features observed in AFM and TEM.

All-solid-state-supercapacitor and a process for the fabrication thereof - Kurungot, Sreekumar; Badiger, Manohar V.; Anothumakkool, Bihag; Torris, Arun (WO2014170912 A1, 2014)
The present invention discloses. all-solid-state supercapacitor (ASSP) with enhanced electrode-electrolyte interface which gives highest very high specific capacitance, areal capacitance and shows very low internal resistance (ESR). The invention particularly discloses the fabrication of all-solid-state supercapacitor by intercalation of solid state polymer electrolyte inside the conducting porous substrate coated with a charge storage electrode material to achieve the desired effect.

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

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

Antimicrobial activity of ZnO nanoparticles against pathogenic bacteria and fungi - Navale, G. R.; Thripuranthaka, M.; Late, Dattatray J.; Shinde, Sandip S. (JSM Nanotechnology and Nanomedicine, 2014)

Arthrobacter enclensis sp. nov., isolated from sediment sample - Dastager, Syed Gulam; Qin, Liu; Tang, Shan-Kun; Krishnamurthi, Srinivasan; Lee, Jae-Chan; Li, Wen-Jun (Archives of Microbiology, 2014)
A novel bacterial strain designated as NIO-1008(T) was isolated from marine sediments sample in Chorao Island India. Cells of the strains were gram positive and non-motile, displayed a rod-coccus life cycle and formed cream to light grey colonies on nutrient agar. Strain NIO-1008(T) had the chemotaxonomic markers that were consistent for classification in the genus Arthrobacter, i.e. MK-9(H-2) (50.3 %), as the major menaquinone, and the minor amount of MK-7 (H-2-27.5 %), MK-8 (H-4-11.6 %) and MK-8 (H-2-10.4 %). anteiso-C-15:0, iso-C-15:0, iso-C-16:0 and C-15:0 were the predominant fatty acids. Galactose, glucose and rhamnose are the cell-wall sugars, and DNA G+C content was 61.3 mol%. Phylogenetic analysis, based on 16S rRNA gene sequencing, showed that the strains were most similar to Arthrobacter equi IMMIB L-1606(T), Arthrobacter chlorophenolicus DSM 12829(T), Arthrobacter defluvii KCTC 19209(T) and Arthrobacter niigatensis CCTCC AB 206012(T) with 98.5, 98.4, 98.0 and 97.8 %, respectively, and formed a separate lineage. Combined phenotypic data and DNA-DNA hybridization data supported the conclusion that strains NIO-1008(T) represent a novel species within the genus Arthrobacter, for which the name Arthrobacter enclensis sp. nov., is proposed. The type strain is NIO-1008(T) = (NCIM 5488(T) = DSM 25279(T)).
Keywords: Arthrobacter; Chorao Island; Marine sediment; Polyphasic

Arthrobacter enclensis sp. nov., isolated from sediment sample (vol 196, pg 775, 2014) - Dastager, Syed Gulam; Liu, Qing; Tang, Shan-Kun; Krishnamurthi, Srinivasan; Lee, Jae-Chan; Li, Wen-Jun (Archives of Microbiology, 2014)

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

Bacillus enclensis sp nov., isolated from sediment sample - Dastager, Syed Gulam; Mawlankar, Rahul R.; Tang, Shan-Kun; Srinivasan, Krishnamurthi; Ramana, V. Venkata; Shouche, Yogesh S. (Antonie Van Leeuwenhoek International Journal of General and Molecular Microbiology, 2014)
A novel bacterial strain, designated SGD-1123(T) was isolated from Chorao Island, in Goa Province, India. The strain was found to be able to grow at 15-42 A degrees C, pH 5-12 and 0-12 % (w/v) NaCl. The whole cell hydrolysates were found to contain meso-diaminopimelic acid, galactose and arabinose. The major fatty acids were identified as iso-C-15:0 and anteiso-C-15:0, MK-7 was identified as the predominant menaquinone and the predominant polar lipids were identified as diphosphatidylglycerol, phosphatidylglycerol, phosphatidylethanolamine and an unidentified aminolipid. The genomic DNA G+C content was determined to be 44.6 mol%. Phylogenetic analysis based on 16S rRNA gene sequences placed the isolate within the genus Bacillus and further revealed that strain SGD-1123(T) had highest sequence similarity with Bacillus aquimaris, and forms a separate clade with its closest relatives i.e. B. aquimaris, Bacillus vietnamensis and Bacillus marisflavi, with which it shares 94.5, 94.1 and 94.1 % similarity respectively. The phylogenetic, chemotaxonomic and phenotypic analyses indicated that strain SGD-1123(T) represents a novel species within the genus Bacillus, for which the name Bacillus enclensis is proposed. The type strain is SGD-1123(T) (NCIM 5450(T)=CCTCC AB 2011125(T)).
Keywords: Bacillus sp; Marine sediment; Polyphasic

Back-to-back MOS–Schottky (Pt–SiO2–Si–C–Pt) nano-heterojunction device as an efficient self-powered photodetector: one step fabrication by pulsed laser deposition - Shaikh, P. A.; Thakare, V. P.; Late, D. J.; Ogale, S. (Nanoscale, 2014)
An efficient self-powered photodetector design involving a C–Si hetero-interface with back-to-back MOS–Schottky (Pt–SiO2–Si–C–Pt) device action is presented. Pulsed laser deposition of a carbon thin film is used which dynamically removes the native surface oxide to form the desired Schottky interface. The combined device action yields two orders of magnitude photoresponse at zero bias.

Biocatalyst mediated functionalization of salannin, an insecticidal limonoid - Haldar, Saikat; Kolet, Swati P.; Dandekar, Devdutta S.; Kale, Balaji S.; Gonnade, Rajesh G.; Thulasiram, Hirekodathakallu V. (RSC Advances, 2014)
Transformation of salannin, an insecticidal C-seco limonoid was investigated using a fungal system, Cunninghamella echinulata. Salannin was efficiently converted into two metabolites, where the C-17 furan moiety was transformed into gamma-hydroxybutenolide (salanninolide) and N-(2-hydroxyethyl)-alpha,beta-unsaturated-gamma-lactam (salanninactam) analogues. Present studies have indicated salanninolide to be a metabolite in the C-seco limonoid biosynthetic pathway.

Biocatalyst mediated regio- and stereo-selective hydroxylation and epoxidation of (Z)-alpha-santalol - Daramwar, Pankaj P.; Srivastava, Prabhakar Lal; Kolet, Swati P.; Thulasiram, Hirekodathakallu V. (Organic & Biomolecular Chemistry, 2014)
Biocatalyst mediated regio- and stereo-selective hydroxylation and epoxidation on (Z)-alpha-santalol were achieved for the first time, using a fungal strain Mucor piriformis. Four novel metabolites were characterized as 10,11-cis-beta-epoxy-alpha-santalol, 5 alpha-hydroxy-(Z)-alpha-santalol, 10,11-dihydroxy-alpha-santalol and 5 alpha-hydroxy-10,11-cis-beta-epoxy-alpha-santalol. Using Amano PS lipase from Burkholderia cepacia, alpha- and beta-isomers of 10,11-cis-epoxy-alpha-santalol were resolved efficiently.

Biodegradable iron chelate for H2S abatement: modeling and optimization using artificial intelligence strategies - Hamid, Aashti; Deshpande, Aniruddha S.; Badhe, Yogesh P.; Barve, Prashant P.; Tambe, Sanjeev S.; Kulkarni, Bhaskar D. (Chemical Engineering Research & Design, 2014)
A batch reactor process for the abatement of a common pollutant, namely, H2S using Fe3+-malic acid chelate (Fe3+-MA) catalyst has been developed. Further, process modeling and optimization was conducted in the three stages with a view to maximize the H2S conversion: (i) sensitivity analysis of process inputs was performed to select the most influential process operating variables and parameters, (ii) an artificial neural network (ANN)-based data-driven process model was developed using the influential process variables and parameters as model inputs, and H2S conversion (%) as the model output, and (iii) the input space of the ANN model was optimized using the artificial immune systems (AIS) formalism. The AIS is a recently proposed stochastic nonlinear search and optimization method based on the human biological immune system and has been introduced in this study for chemical process optimization. The AIS-based optimum process conditions have been compared with those obtained using the genetic algorithms (GA) formalism. The AIS-optimized process conditions leading to high (approximate to 97%) H2S conversion, were tested experimentally and the results obtained thereby show an excellent match with the AIS-maximized H2S conversion. It was also observed that the AIS required lesser number of generations and function evaluations to reach the convergence when compared with the GA. (C) 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Artificial immune systems; Artificial neural networks; Batch reactor; Genetic algorithms; Sensitivity analysis

Capturing a novel metastable polymorph of the anticancer drug gefitinib - Thorat, Shridhar H.; Patwadkar, Manjusha V.; Gonnade, Rajesh G.; Vaidhyanathan, R. (CrystEngComm, 2014)
Gefitinib, a life-extending anticancer drug, exhibits solvent-mediated conformational polymorphism to yield stable (form I) and novel metastable (form II) polymorphs. Crystal structure analysis revealed 3D isostructurality in the molecular organization of the polymorphs, and the metastable polymorph undergoes a crystal-to-crystal thermal phase transition to the stable polymorph.

Characteristics of HRV patterns for different yoga postures - Pitale, Rahul; Tajane, Kapil; Phadke, Leena; Joshi, Aniruddha; Umale, Jayant (2014 Annual IEEE India Conference (INDICON), 2014)
Human heart rate fluctuates in a complex and non-stationary manner, due to continuous influences from autonomic nervous system and other factors (harmones, temp, etc) on the sinoatrial node (S.A) (Pacemaker of the heart). ANS dysfunction is known to be associated with various cardiovascular and lifestyle diseases. The importance of traditional ancient Indian practice like Yoga has increased significantly due to the observed beneficial effects of it in various lifestyle diseases. Preliminary studies have shown that yoga may have its beneficial effect by influencing autonomic nervous system. Heart rate variability (HRV) is a most promising predictive and prognostic marker of autonomic (ANS) activity. HRV is analyzed by time and frequency domain parameters (Fast Fourier Transform). Being linear parameters these are not able to extract full information regarding the non linear behavior of heart rate fluctuations. In this paper, we propose to analyze HRV by using linear as well as non-linear methods during different yogaasanas. These mathematical models will be useful to understand the underlying physiological mechanisms during different yogasanas.
Keywords: ECG; HRV; Poincare plot; Recurrence plot; Yogasanas

Correlation of the solid-state reactivities of racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate and its 4,4 `-bipyridine cocrystal with their crystal structures - Tamboli, Majid I.; Bahadur, Vir; Gonnade, Rajesh G.; Shashidhar, Mysore S. (Acta Crystallographica Section C-Structural Chemistry, 2014)
Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8, (1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4 `-bipyridine molecules in its cocrystal, C21H18O8 center dot C10H8N2, (1)center dot BP, inhibits the intermolecular benzoyl-group transfer reaction. In (1), molecules are assembled around the crystallographic twofold screw axis (b axis) to form a helical self-assembly through conventional O-H center dot center dot center dot O hydrogen-bonding interactions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hydroxy group (nucleophile, Nu) in proximity, with a preorganized El center dot center dot center dot Nu geometry favourable for the acyl transfer reaction. In the cocrystal (1)center dot BP, the dibenzoate and bipyridine molecules are arranged alternately through OH center dot center dot center dot N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.
Keywords: acyl transfer; cocrystal; crystal structure; design of functional solids; helical assembly; hydrogen bonding; myo-inositol; solid-state reactions

Covalent organic framework-cadmium sulfide hybrid as a prototype photocatalyst for visible-light-driven hydrogen production - Thote, Jayshri; Aiyappa, Harshitha Barike; Deshpande, Aparna; Diaz, David Diaz; Kurungot, Sreekumar; Banerjee, Rahul (Chemistry A-European Journal, 2014)
CdS nanoparticles were deposited on a highly stable, two-dimensional (2D) covalent organic framework (COF) matrix and the hybrid was tested for photocatalytic hydrogen production. The efficiency of CdS-COF hybrid was investigated by varying the COF content. On the introduction of just 1 wt% of COF, a dramatic tenfold increase in the overall photocatalytic activity of the hybrid was observed. Among the various hybrids synthesized, that with 10 wt% COF, named CdS-COF (90: 10), was found to exhibit a steep H2 production amounting to 3678 mmolh(-1) g(-1), which is significantly higher than that of bulk CdS particles (124 mmolh(-1)g(-1)). The presence of a p-conjugated backbone, high surface area, and occurrence of abundant 2D hetero-interface highlight the usage of COF as an effective support for stabilizing the generated photoelectrons, thereby resulting in an efficient and high photocatalytic activity.
Keywords: charge transfer; covalent organic frameworks; hybrid materials; hydrogen production; Photocatalysis

Crystal-to-crystal thermal phase transformation of polymorphs of isomeric 2,3-naphthalene diol ditoluates: mechanism and implications for molecular crystal formation and melting - Tamboli, Majid I.; Krishnaswamy, Shobhana; Gonnade, Rajesh G.; Shashidhar, Mysore S. (Crystal Growth & Design, 2014)
Isomeric para- (1) and meta- (2) ditoluate derivatives of naphthalene 2,3-diol exhibited polymorphism producing three (Forms 1I, 1II, 1III) and two (Forms 2I, 2II) polymorphs each, respectively, depending on the solvent and conditions of crystallization. Crystal forms 1I, 1II, and 2I could be obtained repeatedly, whereas crystal forms 1III and 2II were obtained (separately) in one of the crystallization experiments, each. All the crystal forms were stable at ambient conditions, except for Form 2II, which disintegrated to a powder over 45 days. In contrast, the ortho-ditoluate (3) of naphthalene 2,3-diol did not exhibit polymorphism; it yielded fibrous chiral crystals from different solvents/conditions. Crystal structure analysis of all these polymorphs revealed dominance of energetically similar weak intermolecular interactions such as CH center dot center dot center dot O, CH center dot center dot center dot pi, pi center dot center dot center dot pi, and their interplay in molecular aggregation resulting in polymorphic modifications. Differential scanning calorimetry (DSC), hot stage microscopy, single crystal and powder X-ray diffraction measurements revealed crystal-to-crystal thermal transformation of Forms 1I and 1II crystals to Form 1III crystals and Form 2II crystals to Form 2I crystals. The transformation of Form 1I and Form 1II crystals to Form 1III crystals can be viewed as progressive destabilization of the crystal lattice during heating and converting to metastable phase, whereas the conversion of Form 2II to Form 2I crystals can be considered as reorganization of an unstable crystalline phase to a stable crystalline phase. Hence comparative studies of the structure of stable, metastable, or transient crystals and crystal-to-crystal transformations involving these forms could aid in unraveling the process of crystallization.

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

Diels-alder reaction of tropones with arynes: synthesis of functionalized benzobicyclo[3.2.2]nonatrienones - Thangaraj, Manikandan; Bhojgude, Sachin Suresh; Bisht, Rajesh H.; Gonnade, Rajesh G.; Biju, Akkattu T. (Journal of Organic Chemistry, 2014)
A new procedure for the mild, practical, and scalable Diels–Alder reaction of tropones with arynes is reported. Differently substituted tropones undergo selective [4 + 2] cycloaddition with arynes generated in situ by the fluoride-induced 1,2-elimination of 2-(trimethylsilyl)aryl triflates, allowing the formation of functionalized benzobicyclo[3.2.2]nonatrienone derivatives in moderate to good yields. In addition, the photophysical properties of the cycloadducts are presented.

Discontinuous two step flow synthesis of m-aminoacetophenone - Tibhe, Jagdish; Sharma, Yachita; Joshi, Ramesh A.; Joshi, Rohini R.; Kulkarni, Amol A. (Green Processing and Synthesis, 2014)
The continuous flow nitration of acetophenone followed by reduction of the meta isomer has been demonstrated using simple tubular reactors. Because of ease of separation of the desired isomer from the first step, both steps are made continuous, but separately. The continuous flow nitration was carried out in a safe manner in a shorter reaction time than the conventional approach. The choice of micromixer was seen to affect the performance of the nitration reaction. The effect of different parameters on the yield of the desired product was studied. The reduction step with sodium sulfide was found to be economical and could be carried out efficiently at 70 degrees C using sodium sulfide in ethanol, using a silicone tube. Both steps were demonstrated for several hours, yielding a sufficiently large quantity (similar to 100 g) of m-aminoacetophenone at lab scale in a single day using simple tubular reactors.
Keywords: acetophenone; continuous flow synthesis; microreactor; nitration; reduction

Distinctive PdCl2-mediated transformation of Fe-based metallogels into metal-organic frameworks - Aiyappa, Harshitha Barike; Saha, Subhadeep; Garai, Bikash; Thote, Jayshri; Kurungot, Sreekumar; Banerjee, Rahul (Crystal Growth & Design, 2014)
Simple, efficient conversion of viable Fe3+-based metallogels into Fe-metal-organic frameworks (MOFs) has been achieved by PdCl2-mediated gel degradation. The metallogels and the resulting MOFs have been characterized, and a probable mechanism for the event has been elucidated.

Divergent total synthesis of 1,6,8a-tri-epi-castanospermine and 1-deoxy-6,8a-di-epi-castanospermine from substituted azetidin-2-one (beta-lactam), involving a cascade sequence of reactions as a key step - Tiwari, Dipak Kumar; Bharadwaj, Kishor Chandra; Puranik, Vedavati G.; Tiwari, Dharmendra Kumar (Organic & Biomolecular Chemistry, 2014)
A divergent, short, and novel total synthesis of 1,6,8a-tri-epi-castanospermine (7) and 1-deoxy-6,8a-di-epi-castanospermine (8) has been developed via a common precursor, 15, obtained from D-mannitol derived beta-lactam. The key step involves a one pot cascade sequence of trimethyl sulfoxonium ylide based cyclization of epoxy sulfonamide 14 via epoxide ring opening, one carbon homologation followed by intramolecular cyclization.

Domibacillus enclensis sp nov., isolated from marine sediment, and emended description of the genus domibacillus - Sonalkar, Vidya V.; Mawlankar, Rahul R.; Krishnamurthi, Srinivasan; Tang, Shan-Kun; Dastager, Syed Gulam (International Journal of Systematic and Evolutionary Microbiology, 2014)
A novel red-pigmented bacterial strain, designated NIO-1016(T), was isolated from a sediment sample from Chorao Island, India and was investigated by a polyphasic taxonomic approach. The strain was Gram-reaction-positive, strictly aerobic, motile and catalase-positive and produced spherical to slightly ellipsoidal endospores with subterminal position on swollen sporangia. The genomic DNA G+C content was 46.9 molok. The major fatty acids were anteiso-C-15:0, anteiso-C-17:0, iSO-C-15:0 and C-16:0. The predominant quinones were MK-6 (89.3 %) and MK-7 (8.7 %). The polar lipids consisted of diphosphatidylglycerol, phosphatidylglycerol, and an unidentified phospholipid. meso-Diaminopimelic acid (type My) was present in the cell-wall peptidoglycan and the major whole-cell sugars were glucose and ribose. The closest phylogenetic neighbours were identified as Domibacillus robiginosus DSM 25058(T) (98.0% similarity) and Domibacillus indicus DSM 28032(T) (97.2% similarity), other species of the genus Bacillus displayed below 96% similarity. Phylogenetic, physiological, biochemical and morphological differences between strain NI0-1016(T) and its closest neighbours indicate that this strain represents a novel species in the genus Domibacillus in the family Bacillaceae for which the name Domibacillus enclensis sp. nov. is proposed with the type species N10-1016(T) (=DSM 25145(T)=NCIM 5462(T)=CCTCC AB 2011121(T)).

Efforts towards the synthesis of microsporin B: ready access to both the enantiomers of the key amino acid fragment - Swaroop, Pandrangi Siva; Tripathy, Sibanarayan; Jachak, Gorakhnath R.; Reddy, D. Srinivasa (Tetrahedron Letters, 2014)
Both the isomers methyl-(2S,8R)-2-((tert-butoxycarbonyl)amino)-8-hydroxydecanoate and methyl-(2S,8S)-2-((tert-butoxycarbonyl)amino)-8-hydroxydecanoate of an unusual amino acid residue and the key fragment of microsporin B are prepared. The key steps include cross metathesis and enzymatic kinetic resolution. In addition, a linear tetrapeptide with desired components towards total synthesis is also reported. (C) 2014 Elsevier Ltd. All rights reserved.
Keywords: Cross metathesis; Enzymatic resolution; HDAC inhibitor; Microsporin; Tetrapeptide

Electrodeposited polyethylenedioxythiophene with infiltrated gel electrolyte interface: a close contest of an all-solid-state supercapacitor with its liquid-state counterpart - Anothumakkool, Bihag; Torris, Arun A. T.; Bhange, Siddheshwar N.; Badiger, Manohar V.; Kurungot, Sreekumar (Nanoscale, 2014)
We report the design of an all-solid-state supercapacitor, which has charge storage characteristics closely matching that of its liquid-state counterpart even under extreme temperature and humidity conditions. The prototype is made by electro-depositing polyethylenedioxythiophene (PEDOT) onto the individual carbon fibers of a porous carbon substrate followed by intercalating the matrix with polyvinyl alcohol-sulphuric acid (PVA-H2SO4) gel electrolyte. The electrodeposited layer of PEDOT maintained a flower-like growth pattern along the threads of each carbon fiber. This morphology and the alignment of PEDOT led to an enhanced surface area and electrical conductivity, and the pores in the system enabled effective intercalation of the polymer-gel electrolyte. Thus, the established electrode-electrolyte interface nearly mimics that of its counterpart based on the liquid electrolyte. Consequently, the solid device attained very low internal resistance (1.1 Omega cm(-2)) and a high specific capacitance (181 F g(-1)) for PEDOT at a discharge current density of 0.5 A g(-1). Even with a high areal capacitance of 836 mF cm(-2) and volumetric capacitance of 28 F cm(-3), the solid device retained a mass-specific capacitance of 111 F g(-1) for PEDOT. This is in close agreement with the value displayed by the corresponding liquid-state system (112 F g(-1)), which was fabricated by replacing the gel electrolyte with 0.5 M H2SO4. The device also showed excellent charge-discharge stability for 12 000 cycles at 5 A g(-1). The performance of the device was consistent even under wide-ranging humidity (30-80%) and temperature (-10 to 80 degrees C) conditions. Finally, a device fabricated by increasing the electrode area four times was used to light an LED, which validated the scalability of the process.

Electronically and catalytically functional carbon cloth as a permeable and flexible counter electrode for dye sensitized solar cell - Tathavadekar, Mukta; Biswal, Mandakini; Agarkar, Shruti A.; Giribabu, Lingamallu; Ogale, Satishchandra (Electrochimica Acta, 2014)
In this work we demonstrate that a conducting carbon cloth obtained by one-step pyrolysis of easily available cellulose fabric competes favorably with the commonly employed expensive platinum/FTO system as a counter electrode for dye sensitized solar cell (DSSC). In view of the low carbonization temperature (1000 degrees C) which forbids full graphitization, the nature of carbon in this case is represented by topologically randomly assembled nanoscale graphene units (turbostratic carbon). This morphology has high density of edge states and oxygen containing surface groups rendering multitude of catalytic sites for the reduction of I-3(-). Moreover the cloth is permeable to the dye and/or liquid electrolyte and its absorption properties also help retain the electrolyte. A fairly high efficiency of 5.8% is achieved using such cloth as a counter electrode as against 7% with the conventional Pt/FTO system. Moreover, the permeable property of the cloth eliminates a complete step of drilling hard TCO substrates for final dispensing of electrolyte into the device and the sealing process is also facile. In fact even the dye can be dispensed through the cloth. Finally, the flexibility of the carbon cloth can adapt easily to flexible/wearable DSSC designs. (C) 2014 Elsevier Ltd. All rights reserved.
Keywords: conducting carbon cloth; counter electrode; DSSC; without drilling

Enhanced mineralization of gaseous organic pollutant by photo-oxidation using Au-Doped TiO2/MCM-41 - Tangale, Nilesh P.; Belhekar, Anuja A.; Kale, Kishor B.; Awate, Shobhana V. (Water Air and Soil Pollution, 2014)
The synthesis, characterization, and photocatalytic evaluation of titania-loaded MCM-41 with and without Au doping are reported in the present study. The samples were characterized by powder XRD, TEM, low temperature N-2 adsorption/desorption, UV-Vis, and FTIR. UV-induced vapor-phase photo-oxidation of acetone was used as a probe reaction to study the role of Au in mineralization of volatile organic compounds (VOCs), viz. acetone at different concentrations. The doping of Au in titania-loaded MCM-41 resulted in the decrease of BET surface area, total pore volume, and average pore size. UV-Vis diffuse reflectance spectra of Au-doped titania-loaded MCM-41 showed the red shift in their absorption bands compared to titania-loaded MCM-41. The activity of mineralization of acetone by photocatalysis for 2 % Au-doped titania-loaded MCM-41 was found to be similar to 1.6 times higher than titania-loaded MCM-41. The presence of cocatalytic nanosized gold might be responsible for their enhanced activity on account of the delayed recombination of electron/hole pair. Although, almost complete mineralization of acetone was observed irrespective of the initial concentration of acetone in air (up to 3.72 mol%) by all the catalysts, 2 wt.% Au-doped titania-loaded MCM-41 has shown the most enhanced activity.
Keywords: Acetone; Doping; Gold; Mineralization of VOCs; Photo-oxidation; TiO2/MCM-41

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

Expedient preparative isolation and tandem mass spectrometric characterization of C-seco triterpenoids from neem oil - Haldar, Saikat; Mulani, Fayaj A.; Aarthy, Thiagarayaselvam; Dandekar, Devdutta S.; Thulasiram, Hirekodathakallu V. (Journal of Chromatography A, 2014)
C-seco triterpenoids are widely bioactive class of natural products with high structural complexity and diversity. The preparative isolation of these molecules with high purity is greatly desirable, although restricted due to the complexity of natural extracts. In this article we have demonstrated a Medium Pressure Liquid Chromatography (MPLC) based protocol for the isolation of eight major C-seco triterpenoids of salannin skeleton from Neem (Azadirachta indica) oil. Successive application of normal phase pre-packed silica-gel columns for the fractionation followed by reverse phase in automated MPLC system expedited the process and furnished highly pure metabolites. Furthermore, eight isolated triterpenoids along with five semi-synthesized derivatives were characterized using ultra performance liquid chromatography-electrospray ionization-quadrupole/orbitrap-MS/MS spectrometry as a rapid and sensitive identification technique. The structure-fragment relationships were established on the basis of plausible mechanistic pathway for the generation of daughter ions. The MS/MS spectral information of the triterpenoids was further utilized for the identification of studied molecules in the complex extract of stem and bark tissues from Neem. (C) 2014 Elsevier B.V. All rights reserved.
Keywords: ESI(+)-quadrupole/orbitrap-MS/MS; MPLC; Neem oil; Preparative isolation; Salannin; Triterpenoids

Facile esterification of carboxylic acid using amide functionalized benzimidazolium dicationic ionic liquids - Muskawar, Prashant Narayan; Thenmozhi, K.; Gajbhiye, Jayant M.; Bhagat, Pundlik Rambhau (Applied Catalysis A-General, 2014)
Herein, we report the synthesis of a new series of amide functionalized dicationic benzimidazolium based ionic liquids (DBimILs) and appraised their efficacy towards perceptive esterification of carboxylic acids with alkyl/allyl/aryl halides in presence of triethylamine. The amide groups present in this new series of DBimILs are expected to form hydrogen bonding with the carboxylic acids and this could facilitate the esterification reactions under mild conditions devoid of any added catalyst or organic solvent. The plausible mechanism for the enhanced catalytic activity in presence of this new series of ILs has been proposed. The corresponding alkyl/allyl/aryl esters isolated from this reaction were of high purity after simple extraction, which wipe out the necessity for further purification. This protocol addresses clean methodology and the efficient recyclability as well as reusability of the catalyst. (C) 2014 Elsevier B.V. All rights reserved.
Keywords: Benzimidazolium; Dicationic ionic liquids; Esterification; Homogenous catalysis

Facile gamma radiolytic synthesis of synergistic Co3O4-rGO nanocomposite: direct use in photocatalytic water splitting - Gupta, Bhavana; Melvin, Ambrose A.; Matthews, Tom; Dash, S.; Tyagi, A. K. (Materials Research Express, 2014)
Nanostructured Co3O4 was synthesized through a gamma (gamma)-radiolysis technique using alcoholic (iso-propanol) salt solutions of cobalt ions with and without suspended graphene oxide (GO) nanoparticles, respectively. Formation of Co3O4 accompanied with GO reduction takes place simultaneously (in situ) upon.-ray exposure carried out at a rate of 5.1 KGy h(-1). Reduction of GO and formation of Co3O4 were confirmed by XRD, Raman and UV-vis spectroscopy. XRD and HRTEM results supports the embedding of nano-crystalline Co3O4 in an amorphous matrix. Relatively larger crystallites of cobalt oxide obtained in the presence of rGO proved to be a decisive supporting material for the directional growth of Co3O4. Electrochemical characterization established the fact that rGO is indeed considered as a proficient medium for electrochemical electron transfer process. Photo-assisted H-2 generation studies using Co3O4 and Co3O4-rGO nano-composite yielded 3 and 30 mu mol h(-1) g(-1) of hydrogen (H-2) generation, respectively, supports the action of rGO as an electron trap.
Keywords: nano cobalt oxide; photocatalytic hydrogen production; Reduced graphene oxide

Fictibacillus enclensis sp nov., isolated from marine sediment - Dastager, Syed Gulam; Mawlankar, Rahul R.; Srinivasan, Krishnamurthi; Tang, Shan-Kun; Lee, Jae-Chan; Ramana, V. Venkata; Shouche, Yogesh S. (Antonie Van Leeuwenhoek International Journal of General and Molecular Microbiology, 2014)
A novel Gram-positive strain, designated NIO-1003(T), was isolated from a marine sediment sample collected from the Chorao Island, Goa Provence, India. Strain NIO-1003(T) was found to be strictly aerobic, motile, endospore-forming rods. Phylogenetic analysis based on 16S rRNA gene sequences indicated that strain NIO-1003(T) belongs to the genus Fictibacillus and to be most closely related to Fictibacillus rigui KCTC 13278(T), Fictibacillus solisalsi KCTC 13181(T) and Fictibacillus barbaricus DSM 14730(T) with 98.2, 98.0 and 97.2 % similarity and 25, 28, 39 nucleotide differences respectively. Strain NIO-1003(T) was characterized by having cell-wall peptidoglycan based on meso-diaminopimelic acid and MK-7 as the predominant menaquinone. The polar lipid profile exhibited the major compounds diphosphatidylglycerol, phosphatidylglycerol and phosphatidylethanolamine. In addition, minor amounts of an aminophospholipid were detected. The major fatty acids were identified as ai-C-15:0, iso-C-15:0, ai-C-17:0 and C-16:0, supporting the grouping of strain NIO-1003(T) into the family Bacillaceae. The DNA G+C content of strain NIO-1003(T) was determined to be 42.6 mol%. On the basis of phenotypic properties, phylogeny and DNA-DNA hybridisation analysis, strain NIO-1003(T) is considered to represent a novel species of the genus Fictibacillus for which the name Fictibacillus enclensis sp. nov. is proposed. The type strain is NIO-1003(T) (= NCIM 5458(T) = DSM 25142(T)).
Keywords: Chorao Island; Fictibacillus sp.; Polyphasic taxonomy

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

Functionalization of cardanol: towards biobased polymers and additives - Voirin, Coline; Caillol, Sylvain; Sadavarte, Nilakshi V.; Tawade, Bhausaheb V.; Boutevin, Bernard; Wadgaonkar, Prakash P. (Polymer Chemistry, 2014)
Among the renewable resource materials, cashew nut shell liquid (CNSL) is considered as an important starting material due to its unique structural features, abundant availability and low cost. A large number of chemicals and products have been developed starting from CNSL by taking advantage of the three reactive sites, namely, phenolic hydroxyl, aromatic ring and unsaturation(s) in the alkenyl side chain. This comprehensive review deals with general information on CNSL, its purification and separation methods, reactivity and applications in polymer chemistry.

Functionally engineered egg albumen gel for quasi-solid dye sensitized solar cells - Kelkar, Sarika A.; Pandey, Komal; Agarkar, Shruti A.; Saikhedkar, Nidhi; Tathavadekar, Mukta; Agrawal, Ishita; Gundloori, Rathna V. N.; Ogale, Satishchandra (ACS Sustainable Chemistry & Engineering, 2014)
In this report, we demonstrated an interesting application of a bioderived material for the dye sensitized solar cells (DSSCs). Egg white, the clear liquid in a hen's egg, which possesses a remarkable gelling/cross-linking ability, was applied in the form of a gel electrolyte in a DSSC architecture to enhance its durability. A hybrid gel composed of poly(acrylic acid), polyaniline and egg albumen was synthesized, and the cell efficiency, stability and durability of the corresponding DSSC device were studied in detail. The dye sensitized solar cell with the egg albumen based electrolyte demonstrated a conversion energy efficiency of 4.6%. Further, a chemically modified egg albumen with ethylenediaminetetraacetic dianhydride showed improved cross-linking, microstructural and conductivity properties of the gel, and yielded a remarkable 5.75% conversion efficiency. Electrochemical impedance spectroscopy data showed favorable characteristics for charge transport through the modified gel and supported the efficiency observations very well.
Keywords: dye sensitized solar cells; Egg albumen; gel electrolyte

Fungi mediated production and practical purification of (R)-(-)-3-quinuclidinol - Kolet, Swati P.; Jadhav, Dipesh D.; Priyadarshini, Balaraman; Swarge, Bhagyashree N.; Thulasiram, Hirekodathakallu V. (Tetrahedron Letters, 2014)
A fungal system belonging to Mucoraceae family (Mucor piriformis) was explored for the asymmetric reduction of a prochiral ketone, 3-quinuclidinone (I) in an efficient manner to produce an important pharmaceutical precursor (R)-(-)-3-quinuclidinol (II) with similar to 96% enantiomeric excess. The efficiency of the process was improved by developing a cation exchange resin (Amberlite IR-120) which assisted the purification of water soluble metabolite II from fermentation media. (C) 2014 Elsevier Ltd. All rights reserved.
Keywords: (R)-(-)-3-Quinuclidinol; Amberlite IR-120; Biotransformation; Ion exchange resin; Mucor pinformis

General approach to N-heterocyclic carbenes with a fused tetracyclic core: ligands for suzuki-miyaura cross-coupling reaction - Sutar, Revannath L.; Kumar, Vinod; Shingare, Rahul D.; Thorat, Shridhar; Gonnade, Rajesh G.; Reddy, D. Srinivasa (European Journal of Organic Chemistry, 2014)
The synthesis of an N-heterocyclic carbene (NHC) based on a tetracyclic scaffold by using simple, general, and scalable chemistry is disclosed. The developed route is suitable for introducing multiple substitutions on the tetracyclic scaffold. The utility of the present NHC as a ligand in the Suzuki-Miyaura cross-coupling reaction is demonstrated with a low catalyst loading.
Keywords: C-C coupling; carbenes; Homogeneous catalysis; N ligands; synthetic methods

Green synthesis of polysaccharide stabilized gold nanoparticles: chemo catalytic and room temperature operable vapor sensing application - Tagad, Chandrakant K.; Rajdeo, Kishor S.; Kulkarni, Atul; More, Pooja; Aiyer, Rohini C.; Sabharwal, Sushma G. (RSC Advances, 2014)
A facile, one pot, completely green, and cheap route for the synthesis of gold nanoparticles (AuNPs) has been developed by using locust bean gum (LBG), both as a reducing and a stabilizing agent. Synthesized AuNPs were characterized by UV-vis spectroscopy, TEM, XRD, dynamic light scattering analysis (DLS) and EDAX. A characteristic surface plasmon peak at 537 nm confirmed the formation of AuNPs. Synthesized AuNPs were found to be an efficient catalyst for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). The reaction follows pseudo-first order kinetics with a rate constant of 14.46 X 10(-2) min(-1). Furthermore, the catalytic efficiency of AuNPs for ethanol vapor sensing was investigated by doping AuNPs in a tin oxide (SnO2) matrix synthesized by a single step thermal decomposition method. The AuNPs doped SnO2 sensor showed a fast response (similar to 5 seconds) and excellent ethanol sensing behavior in the range of 10 to 120 ppm at room temperature. A two fold increase in ethanol vapor sensing response was observed with AuNPs doped SnO2 as compared with the pure SnO2 sensor.

Highly efficient chiral resolution of DL-arginine by cocrystal formation followed by recrystallization under preferential-enrichment conditions - Iwama, Sekai; Kuyama, Kazunori; Mori, Yuko; Manoj, Kochunnoonny; Gonnade, Rajesh G.; Suzuki, Katsuaki; Hughes, Colan E.; Williams, P. Andrew; Harris, Kenneth D. M.; Veesler, Stephane; Takahashi, Hiroki; Tsue, Hirohito; et al. (Chemistry-A European Journal, 2014)
An excellent chiral symmetry-breaking spontaneous enantiomeric resolution phenomenon, denoted preferential enrichment, was observed on recrystallization of the 1:1 cocrystal of dl-arginine and fumaric acid, which is classified as a racemic compound crystal with a high eutectic ee value (>95%), under non-equilibrium crystallization conditions. On the basis of temperature-controlled video microscopy and in situ time-resolved solid-state (CNMR)-C-13 spectroscopic studies on the crystallization process, a new mechanism of phase transition that can induce preferential enrichment is proposed.
Keywords: Amino acids; chiral resolution; cocrystals; Crystal growth; phase transitions

Humidity-sensing studies of cerium oxide nanoparticles synthesizedby non-isothermal precipitation - Khadse, V. R.; Thakur, Sharada; Patil, K. R.; Patil, Pradip (Sensors and Actuators B-Chemical, 2014)
We report the fabrication of a highly sensitive and fast humidity sensor based on cerium oxide (CeO2) nanoparticles, which were prepared at low cost via a simple non-isothermal precipitation method. The asprepared CeO2 nanoparticles were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy( TEM) and the results indicated the formation of face centered cubic phase of CeO2 with average crystallite size of approximately 10-12 nm. Humidity sensors based on CeO2 nanoparticles exhibit high and linear response within the whole relative humidity (RH) range of 11-97% at an operating frequency of 60 Hz. The corresponding impedance changes by approximately three orders of magnitude within the entire humidity range from 11% to 97% RH. The response and recovery times are about 2-3 and 9-10 s, respectively, when RH was switched between 11% and 97%. Furthermore, the sensors also show relatively small hysteresis, excellent reproducibility, long term stability and broad range of operation (11-97% RH). The complex impedance spectra of the sensor at different RHs and the equivalent circuit were analyzed to explore the humidity-sensing mechanism. This study demonstrates that the CeO2 nanoparticles prepared by non-precipitation method can be used as the humidity-sensing material for the fabrication of humidity sensors. (C) 2014 Elsevier B. V. All rights reserved.
Keywords: CeO2 nanoparticles; Complex impedance spectra; humidity sensor; Non-isothermal precipitation; TEM

In situ synthesized BSA capped gold nanoparticles: effective carrier of anticancer drug methotrexate to MCF-7 breast cancer cells - Murawala, Priyanka; Tirmale, Amruta; Shiras, Anjali; Bhagavatula L. V. Prasad (Materials Science & Engineering C-Materials For Biological Applications, 2014)
The proficiency of MTX loaded BSA capped gold nanoparticles (Au-BSA-MTX) in inhibiting the proliferation of breast cancer cells MCF-7 as compared to the free drug Methotrexate (MTX) is demonstrated based on MTT and Ki-67 proliferation assays. In addition, DNA ladder gel electrophoresis studies, flow cytometry and TUNEL assay confirmed the induction of apoptosis by MTX and Au-BSA-MTX in MCF-7 cells. Notably, Au-BSA-MTX: was found to have higher cytotoxicity on MCF-7 cells compared with an equivalent dose of free MTX. The enhanced activity is attributed to the preferential uptake of Au-BSA-MTX particles by MCF-7 cells due to the presence of BSA that acts as a source of nutrient and energy to the rapidly proliferating MCF-7 cells. Moreover, the targeting ability of the drug MTX to the over expressed folate receptors on MCF-7 cells also contributes to the enhanced uptake and activity. Taken together, these results unveil that Au-BSA-MTX could be more effective than free drug for cancer treatment. (C) 2013 Elsevier B.V. All rights reserved.
Keywords: Apoptosis; Bovine serum albumin; Cancer therapy; Cytotoxicity; Dual active agents; gold nanoparticles

Insecticidal potential of defense metabolites from ocimum kilimandscharicum against helicoverpa armigera - Singh, Priyanka; Jayaramaiah, Ramesha H.; Sarate, Priya; Thulasiram, Hirekodathakallu V.; Kulkarni, Mahesh J.; Giri, Ashok P. (Plos One, 2014)
Genus Ocimum contains a reservoir of diverse secondary metabolites, which are known for their defense and medicinal value. However, the defense-related metabolites from this genus have not been studied in depth. To gain deeper insight into inducible defense metabolites, we examined the overall biochemical and metabolic changes in Ocimum kilimandscharicum that occurred in response to the feeding of Helicoverpa armigera larvae. Metabolic analysis revealed that the primary and secondary metabolism of local and systemic tissues in O. kilimandscharicum was severely affected following larval infestation. Moreover, levels of specific secondary metabolites like camphor, limonene and beta-caryophyllene (known to be involved in defense) significantly increased in leaves upon insect attack. Choice assays conducted by exposing H. armigera larvae on O. kilimandscharicum and tomato leaves, demonstrated that O. kilimandscharicum significantly deters larval feeding. Further, when larvae were fed on O. kilimandscharicum leaves, average body weight decreased and mortality the larvae increased. Larvae fed on artificial diet supplemented with O. kilimandscharicum leaf extract, camphor, limonene and beta-caryophyllene showed growth retardation, increased mortality rates and pupal deformities. Digestive enzymes of H. armigera - namely, amylase, protease and lipase- showed variable patterns after feeding on O. kilimandscharicum, which implies striving of the larvae to attain required nutrition for growth, development and metamorphosis. Evidently, selected metabolites from O. kilimandscharicum possess significant insecticidal activity.

Kocuria indica sp nov., isolated from a sediment sample - Dastager, Syed Gulam; Tang, Shan-Kun; Srinivasan, Krishnamurthi; Lee, Jae-Chan; Li, Wen-Jun (International Journal of Systematic and Evolutionary Microbiology, 2014)
An actinobacterial strain was isolated from a sediment sample from Chorao Island, in Goa province, India, and subjected to a taxonomic investigation. The isolate, designated NIO-1021(T), was a Gram-stain positive, aerobic, non-motile and coccoid. Strain NIO-1021(T) was identified as a member of the genus Kocuria by a polyphasic approach. Strain NIO-1021(T) could be differentiated from other members of the genus Kocuria on the basis of physiology and 16S rRNA gene sequence analysis. The 16S rRNA gene sequence similarity of strain NIO-1021(T) to the most closely related species, Kocuria marina KCTC 9943(T), was 98.6% with 19 nt differences). Furthermore, DNA-DNA hybridization analysis revealed that the novel strain had lower relatedness with the type strains of other members of the genus Kocuria. The strain formed a monophyletic clade with K. marina with 100% bootstrap values. The major phospholipids were phosphatidylglycerol, diphosphatidylglycerol and two unidentified lipids. The predominant menaquinone was MK-7(H-2). The major fatty acids were anteiso-C-15:0, iso-C-(16:0) and anteiso-C-17:0. The DNA G+C content of strain NIO-1021(T) was 60.5 mol%. Chemotaxonomic and phylogenetic properties of the strain were consistent with its classification as representing a member of the genus Kocuria. On the basis of phenotypic, chemotypic and molecular characteristics, strain NIO-1021(T) is considered to represent a novel species of the genus Kocuria, for which the name Kocuria indica sp. nov. is proposed, with strain NIO-1021(T) (=NCIM 5455(T)=DSM 25126(T)=CCTCC AA 209050(T)) as the type strain.

Lipase mediated separation of triterpene structural isomers, alpha- and beta-amyrin - Haldar, Saikat; Kale, Balaji S.; Jadhav, Dipesh D.; Thulasiram, Hirekodathakallu V. (Tetrahedron Letters, 2014)
Pentacyclic triterpenoids alpha- and beta-amyrin possess a wide range of biological and pharmacological activities. High structural similarity between these two structural isomers makes their chromatographic separation an ineffective and tedious choice. In this study, Candida rugosa lipase catalyzed separation protocol for the isolation of individual isomers has been developed. In the presence of vinyl acetate as the acyl donor, Candida rugosa lipase carried out acetylation of beta-amyrin more efficiently as compared to alpha-amyrin leading to a kinetic separation. The conditions of transesterification reaction were optimized systematically, which was utilized to separate alpha- and beta-amyrin from a mixture obtained from the latex of Plumeria obtusa. (C) 2014 Elsevier Ltd. All rights reserved.
Keywords: Amyrin; Candida rugosa; Kinetic separation; Lipase; Structural isomer

MicroRNA156: a potential graft-transmissible microrna that modulates plant architecture and tuberization in solanum tuberosum ssp andigena - Bhogale, Sneha; Mahajan, Ameya S.; Natarajan, Bhavani; Rajabhoj, Mohit; Thulasiram, Hirekodathakallu V.; Banerjee, Anjan K. (Plant Physiology, 2014)
MicroRNA156 (miR156) functions in maintaining the juvenile phase in plants. However, the mobility of this microRNA has not been demonstrated. So far, only three microRNAs, miR399, miR395, and miR172, have been shown to be mobile. We demonstrate here that miR156 is a potential graft-transmissible signal that affects plant architecture and tuberization in potato (Solanum tuberosum). Under tuber-noninductive (long-day) conditions, miR156 shows higher abundance in leaves and stems, whereas an increase in abundance of miR156 has been observed in stolons under tuber-inductive (short-day) conditions, indicative of a photoperiodic control. Detection of miR156 in phloem cells of wild-type plants and mobility assays in heterografts suggest that miR156 is a graft-transmissible signal. This movement was correlated with changes in leaf morphology and longer trichomes in leaves. Overexpression of miR156 in potato caused a drastic phenotype resulting in altered plant architecture and reduced tuber yield. miR156 overexpression plants also exhibited altered levels of cytokinin and strigolactone along with increased levels of LONELY GUY1 and StCyclin D3.1 transcripts as compared with wild-type plants. RNA ligase-mediated rapid amplification of complementary DNA ends analysis validated SQUAMOSA PROMOTER BINDING-LIKE3 (StSPL3), StSPL6, StSPL9, StSPL13, and StLIGULELESS1 as targets of miR156. Gel-shift assays indicate the regulation of miR172 by miR156 through StSPL9. miR156-resistant SPL9 overexpression lines exhibited increased miR172 levels under a short-day photoperiod, supporting miR172 regulation via the miR156-SPL9 module. Overall, our results strongly suggest that miR156 is a phloem-mobile signal regulating potato development.

Modification of crystal anisotropy and enhancement of magnetic moment of Co-doped SnO2 thin films annealed under magnetic field - Loya-Mancilla, Sagrario M.; Poddar, Pankaj; Das, Raja; Ponce, Hilda E. Esparza; Templeton-Olivares, Ivan L.; Solis-Canto, Oscar O.; Ornelas-Gutierrez, Carlos E.; Espinosa-Magaa, Francisco; Olive-Mendez, Sion F. (Nanoscale Research Letters, 2014)
Co-doped SnO2 thin films were grown by sputtering technique on SiO2/Si(001) substrates at room temperature, and then, thermal treatments with and without an applied magnetic field (H-TT) were performed in vacuum at 600 degrees C for 20 min. H-TT was applied parallel and perpendicular to the substrate surface. Magnetic M(H) measurements reveal the coexistence of a strong antiferromagnetic (AFM) signal and a ferromagnetic (FM) component. The AFM component has a N,el temperature higher than room temperature, the spin axis lies parallel to the substrate surface, and the highest magnetic moment m =7 mu(B)/Co at. is obtained when H-TT is applied parallel to the substrate surface. Our results show an enhancement of FM moment per Co+2 from 0.06 to 0.42 mu(B)/Co at. for the sample on which H-TT was applied perpendicular to the surface. The FM order is attributed to the coupling of Co+2 ions through electrons trapped at the site of oxygen vacancies, as described by the bound magnetic polaron model. Our results suggest that FM order is aligned along [101] direction of Co-doped SnO2 nanocrystals, which is proposed to be the easy magnetization axis.
Keywords: Antiferromagnetism; Crystal anisotropy; Diluted magnetic oxide; Ferromagnetism; Magnetic anisotropy; Magnetic moment; Spin axis; thin film

MoS2 nanoparticles and h-BN nanosheets from direct exfoliation of bulk powder: one-step synthesis method - Thripuranthaka, M.; Rout, Chandra Sekhar; Late, Dattatray J. (Materials Research Express, 2014)
We report facile synthesis of MoS2 nanoparticles and h-BN nanosheets using ultrasonication method in suitable solvents such as N-Methyl-2-pyrrolidone and ethylene glycol, respectively. The average size of MoS2 nanoparticles observed from TEM analysis were 4-5 nm and about a few hundreds of nm for h-BN nanosheets. Raman spectroscopy carried out on nanoparticle samples confirms the formation of MoS2 nanoparticles and h-BN nanosheets. UV-vis absorption and photoluminescence (PL) measurements carried out on the products show typical absorption and luminescence spectra of MoS2 and h-BN. Further, we attempted to decorate gold nanoparticles on nanosheets of MoS2 and h-BN which show subsequent change in Raman spectra due to charge transfer interaction.
Keywords: h-BN; MoS2; Nanoparticles; nanosheets; Optical properties

Mucor hiemalis mediated 14 alpha-hydroxylation on steroids: In vivo and in vitro investigations of 14 alpha-hydroxylase activity - Kolet, Swati P.; Haldar, Saikat; Niloferjahan, Siddiqui; Thulasiram, Hirekodathakallu V. (Steroids, 2014)
Transformation of testosterone and progesterone into synthetically challenging 14 alpha-hydroxy derivatives was achieved by using fungal strain Mucor hiemalis. Prolonged incubation led to the formation of corresponding 6 beta/7 alpha,14 alpha-dihydroxy metabolites. The position and stereochemistry of newly introduced hydroxyl group was determined by detailed spectroscopic analyses. The time course experiment indicated that fungal strain initiated transformation by hydroxylation at 14 alpha-position followed by at 6 beta- or 7 alpha-positions. Studies using cell-free extracts suggest that the 14 alpha-hydroxylase activity is NADPH dependent and belongs to the cytochrome P450 family. (C) 2014 Elsevier Inc. All rights reserved.
Keywords: 14 alpha-Hydroxylase; Biotransformation; Mucor hiemalis; Progesterone; Testosterone

Nanocrystalline Ce doped CoFe2O4 as an acetone gas sensor - Khandekar, M. S.; Tarwal, N. L.; Mulla, Imtiaz S.; Suryavanshi, S. S. (Ceramics International, 2014)
Nanocrystalline CoFe2-xCexO4 ferrites (x=0, 0.04, 0.08) were synthesized by using the inexpensive, simple and eco-friendly molten-salt (M-S) method. Effects of Ce doping on the structural, morphological and gas sensing properties of the CoFe2O4 ferrite were investigated. X-ray diffraction (XRD) analysis revealed the formation of spinel CoFe2O4. Transmission electron microscopy (TEM) investigations showed that the synthesized ferrite is made up of very fine spherical nanoparticles. Furthermore, the gas response of nanocrystalline ferrite materials was investigated in the temperature range of 200-450 degrees C toward the reducing gases like liquefied petroleum gas (LPG), acetone, ethanol and ammonia. The sensor response was found to be sensitive and selective toward acetone as compared to other reducing gases. It is observed that the addition of Ce (4 wt%) strongly influenced the response and the operating temperature of the sensor material and thus can serve as acetone-sensing sensors. (C) 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: CoFe2O4; Ferrite; Gas sensor; Molten-salt method; TEM

Nickel cobalt sulfide nanoneedle array as an effective alternative to pt as a counter electrode in dye sensitized solar cells - Banerjee, Abhik; Upadhyay, Kush Kumar; Bhatnagar, Sumit; Tathavadekar, Mukta; Bansode, Umesh P.; Agarkar, Shruti A.; Ogale, Satishchandra B. (RSC Advances, 2014)
Self supported nickel cobalt sulfide (NCS) nanoneedles are directly formed on FTO glass substrates by sulphurization of nickel cobalt oxide nanoneedles (grown by a hydrothermal method) in the presence of a hydrogen sulfide and argon gas mixture. These NCS nanoneedles when used as a counter electrode for dye sensitized solar cells (DSSCs) show efficient catalytic activity towards the I-/I-3(-) redox couple, and lead to an impressive efficiency of 6.9%, compared with 7.7% obtained with a Pt electrode in similarly constructed devices.

Nonisothermal analysis of extrusion film casting process using molecular constitutive equations - Pol, Harshawardhan; Banik, Sourya; Azad, Lal Busher; Thete, Sumeet Suresh; Doshi, Pankaj; Lele, Ashish K. (Rheologica Acta, 2014)
Extrusion film casting (EFC) is a commercially important process that is used to produce several thousand tons of polymer films and coatings. In a recent work, we demonstrated the influence of polymer chain architecture on the extent of necking in an isothermal film casting operation (Pol et al., J Rheol 57:559-583, 2013). In the present research, we have explored experimentally and theoretically the effects of long-chain branching on the extent of necking during nonisothermal film casting conditions. Polyethylenes of linear and long-chain branched architectures were used for experimental studies. The EFC process was analyzed using the 1-D flow model of Silagy et al. (Polym Eng Sci 36:2614-2625, 1996) in which the energy equation was introduced to model nonisothermal effects, and two multimode constitutive equations, namely the ``extended pom-pom'' (XPP, for long-chain branched polymer melts) equation and the ``Rolie-Poly stretch version'' (RP-S, for linear polymer melts) equation, were incorporated to account for the effects of polymer chain architecture. We show that the model does a better job of capturing the qualitative features of the experimental data, thereby elucidating the role of chain architecture and nonisothermal conditions on the extent of necking.
Keywords: Branched; Extrusion; Film; Linear; Necking; Nonisothermal; Polyethylene

Novel fluorescence probe for estimation of cysteine/histidine in human blood plasma and recognition of endogenous cysteine in live Hct116 cells - Reddy, Upendar G.; Agarwalla, Hridesh; Taye, Nandaraj; Ghorai, Suvankar; Chattopadhyay, Samit; Das, Amitava (Chemical Communications, 2014)
A new Cu(II)-complex is used as a ``Turn-On'' luminescence probe for specific detection of endogenous Cys in live Hct116 cells and Cys present in human blood plasma without any interference from other amino acids, especially GSH and Hcy. Difference in the mechanistic pathway for Cys and His recognition is discussed.

Novel synthesis and characterization of CuO nanomaterials: biological applications - Devi, Ayekpam Bimolini; Moirangthem, Dinesh Singh; Talukdar, Narayan Chandra; Devi, M. Damayanti; Singh, N. Rajen; Luwang, Meitram Niraj (Chinese Chemical Letters, 2014)
CuO nanoparticles were synthesized at a relatively low temperature (80 degrees C) for 2 h using polyethylene glycol-glycerol mixture which acts as a capping agent. A detailed characterization of the synthesized nanomaterials were performed utilizing X-ray diffraction (XRD), infra-red spectroscopy (IR), thermogravimetric analysis (TGA-DTA), transmission electron microscopy (TEM), photoluminescence (PL) by studying its crystalline phase, vibrational mode, thermal analysis, morphology and photoluminescence properties. The effect of annealing on the as-prepared nanoparticles were studied and compared with their corresponding bulk counterpart. The synthesized nanoparticles have been screened for in vitro cytotoxicity (IC50) studies against the human cervical adenocarcinoma cell line (HeLa) using MTT assay methods. The as-prepared nanoparticle inhibits the proliferation of this HeLa cell. The standard disc diffusion method has been used to study the antibacterial activity of the samples against the human pathogenic bacteria Escherichia coli (MTCC 729), Proteus mirabilis (MTCC 425) and Klebsiella pneumoniae subsp. pneumoniae (MTCC 432). The results have been compared with the positive control antibiotic gentamycin. The synthesized nanoparticles would provide a potential alternative to antibiotics for controlling some of the microorganisms causing urolithiasis. (C) 2014 Meitram Niraj Luwang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Keywords: Annealing; Antibacterials; CuO nanoparticles; Cytotoxicity; HeLa cell lines

One-pot synthesis of 5-hydroxymethylfurfural by cellulose hydrolysis over highly active bimodal micro/mesoporous H-ZSM-5 catalyst - Nandiwale, Kakasaheb Y.; Galande, Nitish D.; Thakur, Pratika; Sawant, Sanjay D.; Zambre, Vishal P.; Bokade, Vijay V. (ACS Sustainable Chemistry & Engineering, 2014)
Direct synthesis of 5-hydroxymethylfurfural (5-HMF), a useful renewable biofuel and biochemical, was systematically studied by hydrolysis of microcrystalline cellulose over Bimodal-HZ-5 zeolite. Bimodal-HZ-5 zeolite obtained by post-synthesis modification of H-ZSM-5 with desilication was found to be a potential heterogeneous catalyst with 67% cellulose conversion and 46% yield of 5-HMF. Bimodal-HZ-5 was observed to be reusable for four cycles, without any loss in activity. The detailed optimization of process parameters and catalyst reusability are also presented. The present study opens a new avenue for the renewable one-pot synthesis of 5-HMF, a valuable product.
Keywords: 5-Hydroxymethylfurfural; Biomodal-HZ-5; glucose; Hydrolysis; Microcrystalline cellulose

Optimization of the anti-cancer activity of the phosphatidylinositol-3 kinase pathway inhibitor PITENIN-1: switching thiourea with 1,2,3-triazole - Kommagalla, Yadagiri; Cornea, Sinziana; Riehle, Robert; Torchilin, Vladimir; Degterev, Alexei; Ramana, Chepuri V. (Medchemcomm, 2014)
We previously reported encouraging in vitro and in vivo anti-cancer activity of N-((3-chloro-2-hydroxy-5-nitrophenyl)carbamothioyl) benzamide (termed PITENIN-1). In the current work, we describe the structure-activity relationship study of the PIT-1 series, based on the replacement of a central thiourea unit with 1,2,3-triazole, which leads to increased liver microsomal stability, drug likeness and toxicity towards cancer cells.

Permeation of lipidated protein in bilayer using unbiased simulations reveals signature motif for protein-membrane binding - Thukral, Lipi; Sengupta, Durba; Gokhale, Rajesh S. (Biophysical Journal, 2014)

Pharmacokinetic modeling of caco-2 cell permeability using genetic programming (GP) method - Vyas, Renu; Goel, Purva; Karthikeyan, Muthukumarasamy; Tambe, S. S.; Kulkarni, B. D. (Letters in Drug Design & Discovery, 2014)
An accurate prediction of the pharmacokinetic properties of orally administered drugs is of paramount importance in pharmaceutical industry. Caco-2 cell permeability is a well established parameter for assessing the drug absorption profiles of lead molecules. Due to the restrictions on animal testing, prohibitive in situ models and ethical issues, the development of predictive models is essential. Genetic programming (GP) is an artificial intelligence (AI)-based exclusively data driven modeling paradigm. Given an example input-output data, it searches and optimizes, both the structure and parameters of a well fitting linear/non-linear input-output model. Despite this novelty, GP has not been widely exploited in drug design. Accordingly, in this study we propose a GP based approach for the in silico prediction of Caco-2 cell permeability using a diverse set of molecules. The predictions yielded a high magnitude for the training and test set correlation coefficient with low RMSE, indicating accurate Caco-2 permeability prediction and generalization performance by the GP model. The predictions were better or comparable to artificial neural networks (ANN) and support vector regression (SVR) methods. The GP based modeling approach illustrated will find diverse applications in (QSAR, QSPR and QSTR) modeling for the virtual screening of large libraries.
Keywords: ADME modeling; Caco-2 cell permeability; genetic programming; MLP; SVR

Photocatalytic metal-organic framework from cds quantum dot incubated luminescent metallohydrogel - Saha, Subhadeep; Das, Gobinda; Thote, Jayshri; Banerjee, Rahul (Journal of the American Chemical Society, 2014)
Cadmium sulfide (CdS) quantum dots (<10 nm in size) have been successfully synthesized in situ without any capping agent in a Zn(II)-based low-molecular-weight metallohydrogel (ZAVA). Pristine ZAVA hydrogel shows blue luminescence, but the emission can be tuned upon encapsulation of the CdS quantum dots. Time-dependent tunable emission (white to yellow to orange) of the CdS incubated gel (CdS@ZAVA gel) can be attributed to sluggish growth of the quantum dots inside the gel matrix. Once CdS quantum dots are entrapped, their augmentation can be stopped by converting the gel into xerogel, wherein the quantum dots remains embedded in the solid xerogel matrix. Similar size stabilization of CdS quantum dots can be achieved by means of a unique room-temperature conversion of the CdS incubated ZAVA gel to CdS incubated MOF (CdS@ZAVCl) crystals. This in turn arrests the tunability in emission owing to the restriction in the growth of CdS quantum dots inside xerogel and MOF. These CdS embedded MOFs have been utilized as a catalyst for water splitting under visible light.

Photo-enhanced field emission studies of tapered CdS nanobelts - Chavan, Padmakar G.; More, Mahendra A.; Joag, Dilip S.; Badadhe, Satish S.; Mulla, Imtiaz S. (2014 27th International Vacuum Nanoelectronics Conference (IVNC), 2014)
Field emission and photo-enhanced field emission characteristics of single crystalline tapered CdS nanobelts have been investigated. The turn-on field for the emission current density of similar to 0.1 mu A/cm(2) is found to be similar to 2.1 V/mu m, which is much lower than reported values for various CdS nanostructures. The photo-enhanced field emission current shows a reproducible photo-switching behavior with rise in current level nearly four times that of its initial preset value (similar to 1 mu A) which is found to be very remarkable. Possible mechanism of photo-enhanced field emission is discussed.
Keywords: Current stability; field emission; Nanobelts; Photoswitching

Photosensitive field emission study of SnS2 nanosheets (27th International Vacuum Nanoelectronics Conference ) - Joshi, Padmashree D.; Joag, Dilip S.; Rout, Chandra Shekhar; Late, Dattatray J. (2014 27TH International Vacuum Nanoelectronics Conference (IVNC), 2014)
SnS2 nanosheets (SnS(2)NSs), synthesized by one-step hydrothermal reaction, are subjected to Field Emission (FE) studies. For synthesis, specific concentrations of Na2SnO3 and thioamide solution are used. The FE study is carried out in all metal Ultra High Vacuum (UHV) chamber in planar diode configuration at a base pressure of similar to 10(-8) torr. A maximum current density of 110 mu A/cm(2) was attainable. The turn on field required to draw a current density of 1 mu A/cm(2) is found to be 2.6 V/mu m. A separate study was carried out to investigate the photosensitivity of the emitter by illuminating the specimen under visible light. In dark, the FN plot is non-linear, indicative of semiconductor nature of the emitter. However, on illumination, the FN plot is observed to be linear. This remarkable change can be explained by the photoconductivity imparted on illumination. The field at the tip is high in presence of light, than in dark, due to enhanced conductivity. It is also observed that on switching ON the light, the FE current increases almost instantaneously. Repetitive switching is observed at a fixed applied voltage, generating current pulses. The visible light soaking of the sample is carried out by illuminating the lamp for more than 100 minutes, where the current seems to saturate. On switching off the lamp the emission current decayed almost to its initial value exponentially. The photosensitivity has been studied for different wavelengths in the visible spectra. The maximum photosensitive field emission is observed for green filter. With this photoresponse, it is envisaged that SnS2 nanosheets are a potential candidate for optoelectronic applications of field emitters.
Keywords: field emission; photosensitivity; Photoswitching

Plasmonic light harvesting of dye sensitized solar cells by Au-nanoparticle loaded TiO2 nanofibers - Naphade, Rounak A.; Tathavadekar, Mukta; Jog, Jyoti P.; Agarkar, Shruti; Ogale, Satishchandra (Journal of Materials Chemistry A, 2014)
We report a significant enhancement in the performance of dye sensitized solar cells by using in situ Au nanoparticle (Au NP) loaded TiO2 nanofibers (Au: TiO2 NFs) as the light harvesting (LH) layer as compared to the use of only TiO2 nanofibers (NFs) as the LH layer. The Au NP: TiO2 nanofibers are prepared by electro-spinning of a precursor mixture whereby nanostructured porous TiO2 nanofibers are formed and get in situ loaded with only 4-5 nm AuNPs. The as-synthesized nanofibers are characterized by X-ray diffraction, Raman, photoluminescence (PL) and Mott-Schottky analyses. The presence of gold nanoparticles shows considerable improvements in light harvesting and the electrochemical properties of TiO2 nanofibers. A remarkable enhancement in the efficiency by 25% is achieved with the AuNF LH layer as compared to 12% with the NF layer, over the value without any light harvesting layer. The IPCE and impedance analyses reveal commensurate improvements. The impedance study shows a decrease in the transport resistance (R-TiO2) and an increment in the chemical capacitance and life time of the solar cell. Systematic analyses of the optical properties suggest that the enhanced light harvesting by Au NP loaded TiO2 nanofibers is caused by the role of plasmon-polariton modes at the distributed nanoscale Schottky junctions in the Au: TiO2 nanofibers.

Poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (3,4-ethylenedioxythiophene)-few walled carbon nanotube (PEDOT-FWCNT) nanocomposite based thin films for Schottky diode application - Gupta, Bhavana; Mehta, Minisha; Melvin, Ambrose A.; Kamalakannan, R.; Dash, Sitaram; Kamruddin, M.; Tyagi, A. K. (Materials Chemistry and Physics, 2014)
Transparent, conductive films of poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (3,4-ethylenedioxythiophene)-few walled carbon nanotube (PEDOT-FWCNT) nanocomposite were synthesized by in-situ oxidative polymerization and investigated for their Schottky diode property. The prepared films were characterized by UV-Vis spectroscopy, thermal gravimetric analysis (TGA), surface resistivity, cyclic voltametery, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). SEM reveals the formation of homogeneous and adhesive polymer films while HRTEM confirms the uniform wrapping of polymer chains around the nanotube walls for PEDOT-FWCNT film. Improved thermal stability, conductivity and charge storage property of PEDOT in the presence of FWCNT is observed. Among different compositions, 5 wt. % of FWCNT is found to be optimum with sheet resistance and transmittance of 500 Omega sq(-1) and 77%, respectively. Moreover, the electronic and junction properties of polymer films were studied and compared by fabricating sandwich type devices with a configuration of Al/PEDOT or PEDOT-FWCNT nanocomposite/indium tin oxide (ITO) coated glass. The measured current density-voltage characteristics show typical rectifying behavior for both configurations. However, enhanced rectification ratio and higher forward current density is observed in case of PEDOT-FWCNT based Schottky diode. Furthermore, reliability test depicts smaller hysteresis effect and better performance of PEDOT-FWCNT based diodes. (C) 2014 Elsevier B.V. All rights reserved.
Keywords: Composite materials; Electrical properties; Polymer; Thin films

Polyketide synthesis in tobacco plants transformed with a plumbago zeylanica type III hexaketide synthase - Jadhav, Supriya; Phapale, Prasad; Thulasiram, Hirekodathakallu V.; Bhargava, Sujata (Phytochemistry, 2014)
A type III polyketide synthase from Plumbago zeylanica (PzPKS) was cloned and expressed in tobacco plants to study whether the transgenic tobacco plants expressing PzPKS synthesize the pharmacologically important polyketide, plumbagin. High resolution mass spectrometry based metabolite profiling of two transgenic events and wild type tobacco plants was carried out to investigate changes in polyketides, including plumbagin. Ten polyketides, which included six pyrones and four naphthalene derivatives, were identified in PzPKS transgenic plants. While one pyrone, styry1-2-pyranone, was detected in both, wild type and transgenic tobacco plants, three pyrones were expressed only in the leaves of transgenic tobacco plants. The transgenic tobacco plants did not accumulate plumbagin, but showed accumulation of isoshinanolone in the roots, which is postulated to be the reduction product of plumbagin. In addition, leaves of transgenic tobacco plants accumulated 3-methyl-1,8-naphthalenediol, a postulated precursor of plumbagin. The results indicated the requirement of additional Plumbago-specific components in the biosynthetic pathway of this polyketide. (C) 2013 Elsevier Ltd. All rights reserved.
Keywords: HR-MS; Metabolite profiling; Napthalene derivatives; Plumbago zeylanica L.; Polyketide synthase; Pyrones; Tobacco transgenics

Practical synthesis of phthalimides and benzamides by a multicomponent reaction involving arynes, isocyanides, and CO2/H2O - Kaicharla, Trinadh; Thangaraj, Manikandan; Biju, Akkattu T. (Organic Letters, 2014)
Transition-metal-free multicomponent reactions involving arynes and isocyanides with either CO2 or H2O have been reported. With CO2 as the third component, the reactions resulted in the formation of N-substituted phthalimides. The utility of water as the third component furnished benzamide derivatives in moderate to good yields. These reactions took place under mild conditions with broad scope.

Prediction of higher heating value of solid biomass fuels using artificial intelligence formalisms - Ghugare, Suhas B.; Tiwary, S.; Elangovan, V.; Tambe, S. S. (Bioenergy Research, 2014)
The higher heating value (HHV) is an important property defining the energy content of biomass fuels. A number of proximate and/or ultimate analysis based predominantly linear correlations have been proposed for predicting the HHV of biomass fuels. A scrutiny of the relationships between the constituents of the proximate and ultimate analyses and the corresponding HHVs suggests that all relationships are not linear and thus nonlinear models may be more appropriate. Accordingly, a novel artificial intelligence (AI) formalism, namely genetic programming (GP) has been employed for the first time for developing two biomass HHV prediction models, respectively using the constituents of the proximate and ultimate analyses as the model inputs. The prediction and generalization performance of these models was compared rigorously with the corresponding multilayer perceptron (MLP) neural network based as also currently available high-performing linear and nonlinear HHV models. This comparison reveals that the HHV prediction performance of the GP and MLP models is consistently better than that of their existing linear and/or nonlinear counterparts. Specifically, the GP- and MLP-based models exhibit an excellent overall prediction accuracy and generalization performance with high (> 0.95) magnitudes of the coefficient of correlation and low (< 4.5 %) magnitudes of mean absolute percentage error in respect of the experimental and model-predicted HHVs. It is also found that the proximate analysis-based GP model has outperformed all the existing high-performing linear biomass HHV prediction models. In the case of ultimate analysis-based HHV models, the MLP model has exhibited best prediction accuracy and generalization performance when compared with the existing linear and nonlinear models. The AI-based models introduced in this paper due to their excellent performance have the potential to replace the existing biomass HHV prediction models.
Keywords: Artificial intelligence; Artificial neural networks; Biomass fuels; genetic programming; Higher heating value; Multilayer perceptron

Processable aromatic polyesters based on bisphenol derived from cashew nut shell liquid: synthesis and characterization - Tawade, Bhausaheb V.; Salunke, Jagadish K.; Sane, Prakash S.; Wadgaonkar, Prakash P. (Journal of Polymer Research, 2014)
A new bisphenol viz., 4-(4-hydroxyphenoxy)-3-pentadecylphenol (HPPDP) was synthesized starting from cashew nut shell liquid (CNSL). Aromatic (co)polyesters containing ether linkages in the main chain and pendent pentadecyl chains were synthesized by the interfacial polycondensation of HPPDP with terephthalic acid chloride (TPC), isophthalic acid chloride (IPC) and a mixture of TPC and IPC (50: 50 mol %) and by polycondenation of varying composition of HPPDP and bisphenol-A (BPA) with TPC. The resultant (co) polyesters exhibited inherent viscosities in the range 0.70-1.21 dL g(-1) and number-average molecular weights in the range 16,000-48,200 (GPC, polystyrene standard). Polyesters were soluble in common organic solvents such as chloroform and dichloromethane and could be cast into films from chloroform solution. Polyesters exhibited T-10 values in the range 430-455 degrees C and Tg values were in the range 29-202 degrees C. Dynamic mechanical storage modulus and maximum on transition of tan delta curve decreased with increased content of HPPDP in copolyesters. Importantly, the large difference between Tg and T-10 values offers the possibility to process these polyesters in the melt.
Keywords: Aromatic polyesters; Cashew nut shell liquid; pentadecyl; Polycondensation; processability; Thermal properties

Proteomics of arsenic stress in the gram-positive organism Exiguobacterium sp PS NCIM 5463 - Sacheti, Poonam; Patil, Rajendra; Dube, Ankita; Bhonsle, Hemangi S.; Thombre, Dipalee; Marathe, Sayali; Vidhate, Ravindra; Wagh, Priyanka; Kulkarni, Mahesh J.; Rapole, Srikanth; Gade, Wasudeo N. (Applied Microbiology and Biotechnology, 2014)
The general responses of microorganisms to environmental onslaughts are modulated by altering the gene expression pattern to reduce damage in the cell and produce compensating stress responses. The present study attempts to unravel the response of the Gram-positive Exiguobacterium sp. PS NCIM 5463 in the presence of [As(III)] and arsenate [As(V)] using comparative proteomics via two-dimension gel electrophoresis (2-DE) coupled with identification of proteins using matrix-assisted laser desorption/ionisation (MALDI-TOF/MALDI-TOF/TOF). Out of 926 Coomassie-stained proteins, 45 were differentially expressed (p < 0.05). Considering the resolution and abundance level, 24 spots (peptides) were subjected to MALDI analysis, identified and categorised into several functional categories, viz., nitrogen metabolism, energy and stress regulators, carbohydrate metabolism, protein synthesis components and others. A functional role of each protein is discussed in Exiguobacterium sp. PS 5463 under arsenic stress and validated at their transcript level using a quantitative real-time polymerase chain reaction. Unlike previous reports that unravel the responses toward arsenic stress in Gram-negative organisms, the present study identified new proteins under arsenic stress in a Gram-positive organism, Exiguobacterium sp. PS NCIM 5463, which could elucidate the physiology of organisms under arsenic stress.
Keywords: Arsenic; Exiguobacterium; proteomics; Stress; Transcriptomics

Reaction kinetics and modeling of photoinitiated cationic polymerization of an alicyclic based diglycidyl ether - Harikrishna, Reghunathan; Ponrathnam, S.; Tambe, S. S. (Nuclear Instruments & Methods in Physics Research Section B-Beam Interactions with Materials and Atoms, 2014)
Photoinitiated cationic polymerization of cycloaliphatic diepoxides had received tremendous attention, while studies with lesser polymerizable diglycidyl ethers are comparatively less reported. The present work deals with the photoinitiated cationic polymerization of cyclohexane dimethanol diglycidyl ether followed by estimation of kinetic parameters. The effects of concentration of photoinitiator and temperature on curing performance were studied using photo differential scanning calorimeter or photo DSC with polychromatic radiation. It was observed that the rate of polymerization as well as ultimate conversion increased with increasing concentration of photoinitiator and temperature. The influences of gelation as well as diffusional restrictions have remarkable effect on cure performance. The kinetic parameters as per autocatalytic kinetic model were studied by Levenberg-Marquardt nonlinear regression method instead of conventional linear method for obtaining more accurate values of apparent rate constant. It was observed that the model fits with data from initial stages to almost towards the end of the reaction. The activation energy was found to be higher than the values reported for more reactive cycloaliphatic diepoxides. The value of pre-exponential factor increased with increase in activation energy showing influence of gelation at early stages of reaction. (C) 2013 Elsevier B.V. All rights reserved.
Keywords: Autocatalytic model; kinetics; Levenberg-Marquardt method; Photopolymerization

Remarkable efficiency of a pin-II proteinase inhibitor sans two conserved disulfide bonds is due to enhanced flexibility and hydrogen bond density in the reactive site loop - Joshi, Rakesh S.; Mishra, Manasi; Tamhane, Vaijayanti A.; Ghosh, Anirban; Sonavane, Uddhavesh; Suresh, C. G.; Joshi, Rajendra; Gupta, Vidya S.; Giri, Ashok P. (Journal of Biomolecular Structure & Dynamics, 2014)
Capsicum annuum (L.) expresses diverse potato type II family proteinase inhibitors comprising of inhibitory repeat domain (IRD) as basic functional unit. Most IRDs contain eight conserved cysteines forming four disulfide bonds, which are indispensible for their stability and activity. We investigated the functional significance of evolutionary variations in IRDs and their role in mediating interaction between the inhibitor and cognate proteinase. Among the 18 IRDs encoded by C. annuum, IRD-7, -9, and -12 were selected for further characterization on the basis of variation in their reactive site loop, number of conserved cysteine residues, and higher theoretical G(bind) for interaction with Helicoverpa armigera trypsin. Moreover, inhibition kinetics showed that IRD-9, despite loss of some of the disulfide bonds, was a more potent proteinase inhibitor among the three selected IRDs. Molecular dynamic simulations revealed that serine residues in the place of cysteines at seventh and eighth positions of IRD-9 resulted in an increase in the density of intramolecular hydrogen bonds and reactive site loop flexibility. Results of the serine residues chemical modification also supported this observation and provided a possible explanation for the remarkable inhibitory potential of IRD-9. Furthermore, this natural variant among IRDs showed special attributes like stability to proteolysis and synergistic inhibitory effect on other IRDs. It is likely that IRDs have coevolved selective specialization of their structure and function as a response towards specific insect proteases they encountered. Understanding the molecular mechanism of pest protease-plant proteinaceous inhibitor interaction will help in developing effective pest control strategies.An animated interactive 3D complement (I3DC) is available in Proteopedia at http://proteopedia.org/w/Journal:JBSD:39
Keywords: Capsicum annuum; Helicoverpa armigera; Proteases; Proteinase inhibitor

Resistance through inhibition: ectopic expression of serine protease inhibitor offers stress tolerance via delayed senescence in yeast cell - Joshi, Rakesh S.; Tanpure, Rahul S.; Singh, Rajan Kumar; Gupta, Vidya S.; Giri, Ashok P. (Biochemical and Biophysical Research Communications, 2014)
Protease inhibitors have been known to confer multiple stress tolerance in transgenic plants. We have assessed growth of yeast (Pichia pastoris GS115) strains expressing inhibitory repeat domains (PpIRD(+)) of previously characterized Capsicum annuum protease inhibitors under high salt, heavy metal and oxidative stress. PpIRD(+) strains exhibited multiple stress tolerance and showed differential molecular responses at transcriptional and translational level on exposure to stress inducing agents like heavy metal, high salt and H2O2. PpIRD(+) strains display significant reduction in metacaspase (Yca1) activity, the key enzyme in apoptosis, indicates the possibility of cross reactivity of IRDs (serine protease inhibitor) with cysteine proteases. PpIRD(+) and Saccharomyces cerevisiae knockout with Yca1 (Delta Yca1) strain showed similar growth characteristics under stress, which indicated the delayed senescence due to cellular metacaspase inhibition. Molecular docking study showed a close proximity of IRDs reactive site and the active site of metacaspase in the complex that signified their strong interactions. Maintenance of GAPDH activity, primary target of metacaspase, in PpIRD(+) strain evidenced the inhibition of metacaspase activity and survival of these cells under stress. This report demonstrates a potential molecular mechanism of protease inhibitor-based multiple stress tolerance in yeast strains. (C) 2014 Elsevier Inc. All rights reserved.
Keywords: Metacaspase; Multiple stress tolerance; protease inhibitor; Yeast

Rhodococcus enclensis sp nov., a novel member of the genus rhodococcus - Dastager, Syed Gulam; Mawlankar, Rahul R.; Tang, Shan-Kun; Krishnamurthi, Srinivasan; Ramana, V. Venkata; Joseph, Neeta; Shouche, Yogesh S. (International Journal of Systematic and Evolutionary Microbiology, 2014)
A novel actinobacterial strain, designated, NIO-1009(T), was isolated from a marine sediment sample collected from Chorao Island, Goa, India. Phylogenetic analysis comparisons based on 16S rRNA gene sequences between strain MO-1009(T) and other members of the genus Rhodococcus revealed that strain NI0-1009(T) had the closest sequence similarity to Rhodococcus kroppenstedtii DSM 44908(T) and Rhodococcus corynebacterioides DSM 20151(T) with 99.2 and 99.1%, respectively. Furthermore, DNA-DNA hybridization results showed that R. kroppenstedtii DSM 44908(T) and R. corynebacterioides DSM 20151(T) were 39.5 (3.0%) and 41.7 (2.0%) with strain NIO-1009(T), respectively, which were well below the 70% limit for any novel species proposal. Phylogenetically strain NIO-1009(T) forms a stable clade with and R. kroppenstedtii DSM 44908(T) and R. corynebacterioides DSM 201511 with 100% bootstrap values. Strain NI-1009(T) contained meso-diaminopimelic acid as the diagnostic diamino acid and galactose and arabinose as the cell wall sugars. The major fatty acids were C-16:0, C-18:1 omega 9c, C-16:1(omega 6C and/or omega 7c) and 10-methyl C-18:0. The only menaquinone detected was MK-8(H-2), while the major polar lipids were diphosphatidylglycerol, phosphatidylethanolamine, phosphatidylglycerol, phosphatidylinositol, phosphatidylinositol mannoside and one unknown phospholipid. The G + C content of the genomic DNA was 66.9 molok. The phenotypic and genotypic data showed that strain NIO-1009(T) warrants recognition as a novel species of the genus Rhodococcus for which the name Rhodococcus enclensis sp. nov., is proposed; the type strain is NIO-1009(T) (=NCIM 5452(T)=DSM 45688(T)).

Scaling behavior of resistive switching in epitaxial bismuth ferrite heterostructures - Rana, Abhimanyu; Lu, Haidong; Bogle, Kashinath A.; Zhang, Qi; Vasudevan, Rama; Thakare, Vishal; Gruverman, Alexei; Ogale, Satishchandra; Valanoor, Nagarajan (Advanced Functional Materials, 2014)
Resistive switching (RS) of (001) epitaxial multiferroic BiFeO3/La0.67Sr0.33MnO3/SrTiO3 heterostructures is investigated for varying lengths scales in both the thickness and lateral directions. Macroscale current-voltage analyses in conjunction with local conduction atomic force microscopy (CAFM) reveal that whilst both the local and global resistive states are strongly driven by polarization direction, the type of conduction mechanism is different for each distinct thickness regime. Electrode-area dependent studies confirm the RS is dominated by an interface mechanism and not by filamentary formation. Furthermore, CAFM maps allow deconvolution of the roles played by domains and domain walls during the RS process. It is shown that the net polarization direction, and not domain walls, controls the conduction process. An interface mechanism based on barrier height and width alteration due to polarization reversal is proposed, and the role of electronic reconstruction at the interface is further investigated.

Soft colloidal scaffolds capable of elastic recovery after large compressive strains - Rajamanickam, Raja; Kumar, Sushma; Kumar, Deepak; Ghosh, Shankar; Kim, Jong Chul; Tae, Giyoong; Sen Gupta, Sayam; Kumaraswamy, Guruswamy (Chemistry of Materials, 2014)
Assemblies of inorganic or glassy particles are typically brittle and cannot sustain even moderate deformations. This restricts the use of such materials to applications where they do not experience significant loading or deformation. Here, we demonstrate a general strategy to create centimeter-size macroporous monoliths, composed primarily (>90 wt %) of colloidal particles, that recover elastically after compression to about one-tenth their original size. We employ ice templating of an aqueous dispersion of particles, polymer, and cross-linker such that cross-linking happens in the frozen state. This method yields elastic composite scaffolds for starting materials ranging from nanoparticles to micron-sized dispersions of inorganics or glassy lattices. The mechanical response of the monoliths is also qualitatively independent of polymer type, molecular weight, and even cross-linking chemistry. Our results suggest that the monolith mechanical properties arise from the formation of a unique hybrid microstructure, generated by cross-linking the polymer during ice templating. Particles that comprise the scaffold walls are connected by a cross-linked polymeric mesh. This microstructure results in soft monoliths, with moduli similar to O (10(4) Pa), despite the very high particle content in their walls. A remarkable consequence of this microstructure is that the monolith mechanical response is entropic in origin: the modulus of these scaffolds increases with temperature over a range of 140 K. We show that interparticle connections formed by cross-linking during ice templating determine the monolith modulus and also allow relative motion between connected particles, resulting in entropic elasticity.

Soft-sensor development for biochemical systems using genetic programming - Sharma, Suraj; Tambe, Sanjeev S. (Biochemical Engineering Journal, 2014)
Soft-sensors are software based process monitoring systems/models. In real-time they estimate those process variables, which are difficult to measure online or whose measurement by analytical procedures is tedious and time-consuming. In this study, the genetic programming (GP), an artificial intelligence based data-driven modeling formalism, has been introduced for the development of soft-sensors for biochemical processes. The novelty of the GP is that given example input-output data, it searches and optimizes both the form (structure) and parameters of an appropriate linear/nonlinear data-fitting model. In this study, GP-based soft-sensors have been developed for two bioprocesses, namely extracellular production of lipase enzyme and bacterial production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer. While in case study-I, the soft-sensor predicts the time-dependent lipase activity (U/ml), in case study-II it predicts the amount of accumulated polyhydroxyalkanoates (% dcw). The prediction and generalization performance of the GP-based soft-sensors was compared with the corresponding multi-layer perceptron (MLP) neural network and support vector regression (SVR) based soft-sensors. This comparison indicates that in the first case study the GP-based soft-sensor with the training and test set correlation coefficient (root-mean-squared-error) magnitudes of >0.96 (approximate to 0.962 U/ml) has clearly outperformed the two other soft-sensors. In case study-II involving bacterial copolymer production, the GP and SVR based soft-sensors have performed equally well (correlation coefficient approximate to 0.98) while the MLP based soft-sensor's performance was relatively inferior (correlation coefficient approximate to 0.94). (C) 2014 Elsevier B.V. All rights reserved.
Keywords: Artificial intelligence; Batch processing; Bioprocess monitoring; Lipase; Modeling; sensors

Solid base supported metal catalysts for the oxidation and hydrogenation of sugars - Tathod, Anup; Kane, Tanushree; Sanil, E. S.; Dhepe, Paresh Laxmikant (Journal of Molecular Catalysis A-Chemical, 2014)
Pt impregnated on gamma-Al2O3 (acidic support) and hydrotalcite (basic support) catalysts were synthesized, characterized and used in the oxidation and hydrogenation reactions of C5 and C6 sugars. In the absence of homogeneous base, 83% yield for gluconic acid; an oxidation product of glucose can be achieved over Pt/hydrotalcite (HT) catalyst at 50 degrees C under atmospheric oxygen pressure. Similarly, 57% yield for xylonic acid, an oxidation product of xylose is also possible over Pt/HT catalyst. Hydrogenation of glucose conducted using Pt/gamma-Al2O3 + HT catalytic system showed 68% sugar alcohols (sorbitol + mannitol) formation. The 82% yield for C5 sugar alcohols (xylitol + arabitol) was obtained by subjecting xylose to hydrogenation over Pt/gamma-Al2O3 + HT at 60 degrees C. UV analysis helped to establish the fact that under alkaline conditions sugars prefer to remain in open chain form in the solution and thus exposes -CHO group which further undergoes oxidation and hydrogenation reactions to yield acids and alcohols. (c) 2013 Elsevier B.V. All rights reserved.
Keywords: Hydrogenation; Oxidation; Solid base; Sugars; Supported metal catalysts

Solid-state NMR investigations of a MgCl2 center dot 4(CH3)(2)CHCH2OH molecular adduct: a peculiar case of reversible equilibrium between two phases - Thushara, K. S.; Ajithkumar, Thalasseril G.; Rajamohanan, P. R.; Gopinath, Chinnakonda S. (Journal of Physical Chemistry A, 2014)
MgCl2 center dot xROH molecular adducts are extensively employed as a support material for Ziegler-Natta polyolefin catalysis. However, their structural properties are not well understood. Recently, we reported on the preparation of an isobutanol adduct, MgCl2 center dot 4(CH3)(2)CHCH2OH (MgiBuOH) (Dalton Trans. 2012, 41, 11311), which is very sensitive to the preparation conditions, such as the temperature and refluxing time. For the present study, the structural properties of MgiBuOH adducts prepared under different conditions have been investigated thoroughly by solid-state NMR and nonambient XRD. Formation of two phases has been confirmed, and in situ variable temperature solid-state NMR measurements confirm the coexistence of two phases as well as the oscillation from one to another phase. It is expected that such molecular adducts could have a significant role in organic transformation reactions due to an oscillating structural component. An understanding of phase oscillation with the Mg2+ ion as the central metal ion might shed some light toward understanding various biological and structural functions.

Specific probe for Hg2+ to delineate even H+ in pure aqueous buffer/Hct116 colon cancer cells: Hg(II)-eta(2)-arene pi-interaction and a TBET-based fluorescence response - Reddy, Upendar G.; Ramu, Vadde; Roy, Sovan; Taye, Nandaraj; Chattopadhyay, Samit; Das, Amitava (Chemical Communications, 2014)
A new molecular probe that demonstrates a distinct TBET process, induced by the Hg(II)-eta(2)-arene pi-interaction, in pure aqueous medium with a large pseudo-Stokes shift of 200 nm.

Stress inducible proteomic changes in capsicum annuum leaves - Mahajan, Neha S.; Mishra, Manasi; Tamhane, Vaijayanti A.; Gupta, Vidya S.; Giri, Ashok P. (Plant Physiology and Biochemistry, 2014)
Herbivore attack induces defense responses in plants, activating several signaling cascades. As a result, molecules deterrent to the herbivores are produced and accumulated in plants. Expression of defense mechanism/traits requires reorganization of the plant metabolism, redirecting the resources otherwise meant for growth. In the present work, protein profile of Capsicum annuum leaves was examined after herbivore attack/induction. Majority of proteins identified as differentially accumulated, were having roles in redox metabolism and photosynthesis. For example, superoxide dismutase and NADP oxidoreductase were upregulated by 10- and 6-fold while carbonic anhydrase and fructose-1,6-bisphosphatase were downregulated by 9- and 4-fold, respectively. Also, superoxide dismutase, NADPH quinone oxidoreductase and NADP dependent isocitrate dehydrogenase transcripts showed a higher accumulation in induced leaf tissues at early time points. In general, proteins having role in defense and damage repair were upregulated while those involved in photosynthesis appeared downregulated. Thus metabolic reconfiguration to balance defense and tolerance was evident in the stress-induced leaves. (C) 2013 Elsevier Masson SAS. All rights reserved.
Keywords: Capsicum annuum; Oxidative stress; Wounding

Structural basis of Iridoid synthase mediated cyclization of 10-oxogeranial - Sandholu, Anandsukeerthi; H. V. Thulasiram; Sengupta, Jayati; Kulkarni, Kiran (Acta Crystallographica A‐Foundation and Advances, 2014)
Keywords: Cryo-EM; iridoid synthase; Single Particle reconstruction

Structural investigations of porous MgCl2-2-butanol molecular adduct as support for olefin polymerization - Thushara, K. S.; Ajithkumar, Thalasseril G.; Rajamohanan, P. R.; Gopinath, Chinnakonda S. (Applied Catalysis A-General, 2014)
A new heterogeneous Ziegler-Natta (Z-N) catalyst support material, MgCl2 center dot 4(CH3CH(OH)CH2CH3) (Mg2BuOH) has been synthesized. 2-Butanol, a linear, secondary alcohol was chosen for the generation of an active MgCl2 support which results in a Z-N catalyst with TiCl4. Significant feature of this work is the formation of rod shaped molecular adduct with highly porous character. Adduct material is characterized by XRD, TG-DTA, Raman spectroscopy, solid-state NMR and SEM. Activity of the Z-N catalyst supported on Mg2BuOH for ethylene polymerization is comparable with that of commercially available heterogeneous Z-N catalyst. However, there is scope to improve the activity by optimizing textural properties. (C) 2013 Elsevier B.V. All rights reserved.
Keywords: heterogeneous catalysis; MgCl2; Molecular adduct; NMR; Polyolefin; Ziegler-Natta catalyst

Supramolecular synthon hierarchy in bumetanide cocrystals - Allu, Suryanarayana; Bolla, Geetha; Tothadi, Srinu; Nangia, Ashwini (Acta Crystallographica A‐Foundation and Advances, 2014)
Keywords: Novel cocrystals of sulfonamide drug Bumetanide with carboxamides are developed based on supramolecular synthons approach

Synthesis and characterization of 3-[N,N `-bis-3-(salicylidenamino)ethyltriamine] Mo(VI)O-2@SBA-15: a highly stable and reusable catalyst for epoxidation and sulfoxidation reactions - Lazar, Anish; Thiel, Werner R.; Singh, A. P. (RSC Advances, 2014)
The efficient and reusable oxidation catalyst 3-[N,N'-bis-3-(salicylidenamino)ethyltriamine] Mo(VI)O-2@SBA-15 has been synthesized by the anchoring of the 3-[N,N-bis-3-(salicylidenamino)ethyltriamine] ligand (L or Salpr) on the inner surfaces of organofunctionalized SBA-15 and subsequent complexation with Mo(VI) O-2(acac)(2). The physico-chemical properties of the functionalized catalysts were analyzed by elemental analysis, ICP-OES, XRD, N-2-sorption measurements, TG & DTA, solid state C-13, Si-29 NMR spectroscopy, FT-IR, Raman spectroscopy, XPS, DRS UV-Vis spectroscopy, SEM and TEM. XRD and N-2 sorption analyses helped to find out the morphological and textural properties of the synthesized catalysts and confirm that an ordered mesoporous channel structure was retained even after the multistep synthetic procedures. The (100), (110) and (200) reflections in SBA-15 provide hints of a good structural stability, the existence of long range ordering and a high pore wall thickness. TG and DTA results reveal that the thermal stability of (L)Mo(VI)O-2@SBA-15 was maintained up to 300 degrees C. The organic moieties anchored over the surface of the SBA-15 support were determined by solid state C-13 NMR and FT-IR spectroscopy. Further, solid state Si-29 NMR spectroscopy provides the information about the degree of functionalization of the surface silanol groups with the organic moiety. The electronic environment and the oxidation state of the molybdenum site in (L)Mo(VI)O-2@SBA-15 were monitored by Raman spectroscopy, XPS and DRS UV-Vis techniques. Moreover, the morphology and topographic information of the synthesized catalysts were confirmed by SEM and TEM imaging. The synthesized catalysts were evaluated in epoxidation and sulfoxidation reactions, and the results show that (L)Mo(VI)O-2@SBA-15 exhibits high conversion and selectivity towards epoxidation and sulfoxidation reactions in combination with high stability. The anchored solid catalysts can be recycled effectively and reused several times without major loss in activity. In addition, Sheldon's hot filtration test was also carried out.

Synthesis of alpha,beta-unsaturated delta-lactones by vinyl acetate mediated asymmetric cross-aldol reaction of acetaldehyde: mechanistic insights - Kumar, Manjeet; Kumar, Arvind; Rizvi, Masood; Mane, Manoj; Vanka, Kumar; Taneja, Subhash C.; Shah, Bhahwal Ali (European Journal of Organic Chemistry, 2014)
A tandem asymmetric cross-aldol reaction involving the in situ generation of acetaldehyde from vinyl acetate has been developed that may resolve the challenges associated with the handling of acetaldehyde. The simple protocol, mild reaction conditions and unique harmony of an organocatalyst with a biocatalyst make this method a valuable tool for the synthesis of asymmetric beta-hydroxy aldehydes. By using this methodology we have accessed alpha,beta-unstaurated delta-lactones as well as isochromenones with high enantioselectivities from both asymmetric beta-hydroxy aldehydes and ketones. Systemic density functional theory (DFT) studies were also performed to gain mechanistic insights into the role of hydrogen bonding in the asymmetric cross-aldol reaction of acetaldehyde and in the key cis/trans isomerisation step in the synthesis of d-lactones.
Keywords: Aldol reactions; asymmetric catalysis; lactones; reaction mechanisms

Tandem [4 + 2]/[2 + 2] cycloaddition reactions involving indene or benzofurans and arynes - Bhojgude, Sachin Suresh; Thangaraj, Manikandan; Suresh, Eringathodi; Biju, Akkattu T. (Organic Letters, 2014)
The reaction of arynes with indene/benzofurans has been developed. The arynes were generated from 2-(trimethylsilyl)aryl triflates by the fluoride-induced 1,2-elimination react with indene or various benzofurans proceeding via a cascade reaction involving the Diels–Alder reaction and a [2 + 2] cycloaddition reaction. The tandem process afforded functionalized dihydrobenzocyclobutaphenanthrenes in moderate to good yields. Moreover, the method has been utilized for the one-pot synthesis of benzo[b]fluoranthene.

Temperature Dependent Phonon Shifts in Single-Layer WS2 - Thripuranthaka, M.; Late, Dattatray J. (Acs Applied Materials & Interfaces, 2014)
Atomically thin two-dimensional tungsten disulfide (WS2) sheets have attracted much attention due to their potential for future nanoelectronic device applications. We report first experimental investigation on temperature dependent Raman spectra of single-layer WS2 prepared using micromechanical exfoliation. Our temperature dependent Raman spectroscopy results shows that the E-2g(1) and A(1g) modes of single-layer WS2 soften as temperature increases from 77 to 623 K. The calculated temperature coefficients of the frequencies of 2LA(M), E-2g(1), A(1g), and A(1g)(M) + LA(M) modes of single-layer WS2 were observed to be -0.008, -0.006, -0.006, and -0.01 cm(-1) K-1, respectively. The results were explained in terms of a double resonance process which is active in atomically thin nanosheet. This process can also be largely applicable in other emerging single-layer materials.
Keywords: layered materials; phonon vibrations; Raman spectroscopy; thermal effect; WS2

Temperature dependent Raman spectroscopy of chemically derived few layer MoS2 and WS2 nanosheets - Thripuranthaka, M.; Kashid, Ranjit V.; Rout, Chandra Sekhar; Late, Dattatray J. (Applied Physics Letters, 2014)
We have systematically investigated the temperature dependent Raman spectroscopy behavior of a few layered MoS2 and WS2 nanosheets synthesized using simple hydrothermal method. Our result reveals A(1g) and E-2g(1) modes soften as temperature increases from 77 K to 623 K. This behavior can be explained in terms of a double resonance process which is active in single-and few layer thick nanosheets. The frequency shifts and peak broadening can provide unambiguous, nondestructive, and accurate information of a few layered MoS2 and WS2. This mechanism can also be applicable in characterizing the structural, optical, electronic, and vibrational properties of other emerging layered materials. (c) 2014 AIP Publishing LLC.

Temperature dependent Raman spectroscopy of chemically derived few layer MoS2 and WS2 nanosheets (vol 104, 081911, 2014) - Thripuranthaka, M.; Kashid, Ranjit V.; Rout, Chandra Sekhar; Late, Dattatray J. (Applied Physics Letters, 2014)

To study non linear features in circadian heart rate variability amongst healthy subjects - Tajane, Kapil; Pitale, Rahul; Phadke, Leena; Joshi, Aniruddha; Umale, Jayant (2014 International Conference on Advances in Computing, Communications and Informatics (ICACCI), 2014)
ECG signal is used for diagnosis of ailments of heart. HRV is used as a predictive and prognostic marker of autonomic dis-functioning. ANS is known to influence heart and any dis-functioning of this system leads to cardiac disorders. ANS has endogenous circadian rhythm. Circadian rhythms are responsible for physical, mental and behavioral changes that follow a roughly 24-hour cycle. Previous studies have shown large inter and intra individual differences in HRV which has lead to difficulties in establishing standard norms. Therefore the aim of our study is to establish a brief protocol for HRV analysis where we will be able to extract features in shorter duration of recording, representative of 24 hour fluctuations in HRV. In this paper we have studied different linear as well as non-linear techniques to analyze circadian HRV. 24 hour ECG recording of 15 subjects using Minimum Activity Protocol subjected for HRV analysis.
Keywords: Circadian Rhythm; Correlation Dimensions; DFA; ECG; HRV

Towards efficient synthesis of sugar alcohols from mono- and poly-saccharides: role of metals, supports & promoters - Tathod, Anup P.; Dhepe, Paresh Laxmikant (Green Chemistry, 2014)
{Biomass derived sugar alcohols (xylitol, arabitol) find numerous uses in the food, oral hygiene and pharmaceutical industries. Their direct synthesis from poly-saccharides, however, still remains an immense challenge. In this study, we demonstrate in detail the effects of metals, supports and promoters in enhancing the yields of sugar alcohols from mono- and poly-saccharides. We undertook synthesis of bimetallic catalysts, M-M'/S (M

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

Way toward ``dietary pesticides'': molecular investigation of insecticidal action of caffeic acid against helicoverpa armigera - Joshi, Rakesh S.; Wagh, T. P.; Sharma, N.; Mulani, Fayaj A.; Sonavane, U.; Thulasiram, H. V.; Joshi, Rakesh S.; Gupta, Vidya S.; Giri, Ashok P. (Journal of Agricultural and Food Chemistry, 2014)
Bioprospecting of natural molecules is essential to overcome serious environmental issues and pesticide resistance in insects. Here we are reporting insights into insecticidal activity of a plant natural phenol. In silico and in vitro screening of multiple molecules supported by in vivo validations suggested that caffeic acid (CA) is a potent inhibitor of Helicoverpa armigera gut proteases. Protease activity and gene expression were altered in CA-fed larvae. The structure-activity relationship of CA highlighted that all the functional groups are crucial for inhibition of protease activity. Biophysical studies and molecular dynamic simulations revealed that sequential binding of multiple CA molecules induces conformational changes in the protease(s) and thus lead to a significant decline in their activity. CA treatment significantly inhibits the insect's detoxification enzymes, thus intensifying the insecticidal effect. Our findings suggest that CA can be implicated as a potent insecticidal molecule and explored for the development of effective dietary pesticides.
Keywords: Caffeic acid; Helicoverpa armigera; insecticidal activity; protease inhibitor

Ammonium persulfate activated DMSO as a one-carbon synthon for the synthesis of methylenebisamides and other applications - Mahajan, Pankaj S.; Tanpure, Subhash D.; More, Namita A.; Gajbhiye, Jayant M.; Mhaske, Santosh B. (RSC Advances, 2015)
Activation of DMSO to work as an economical and environmentally benign one-carbon synthon has been achieved by using a bench-top reagent ammonium persulfate for general and efficient access to symmetrical methylenebisamides from primary amides. This methodology was used to achieve a three-component Mannich reaction using acetophenone, saccharin and DMSO to furnish a beta-amino ketone. It also provided a metal-free synthesis of thiadiazole and bis(phenyl)methane. Effectively, this method uses DMSO as a safer surrogate to formaldehyde. A mechanism for methylenebisamide formation involving radical intermediates has been proposed based on mechanistic studies.

Assessing the effect of different shapes of glyco-gold nanoparticles on bacterial adhesion and infections - Chaudhary, Preeti Madhukar; Sangabathuni, Sivakoti; Murthy, Raghavendra Vasudeva; Paul, Ajay; Thulasiram, Hirekodathakallu V.; Kikkeri, Raghavendra (Chemical Communications, 2015)
Achieving selective and sensitive carbohydrate-protein interactions (CPIs) using nanotechnology is an intriguing area of research. Here we demonstrate that the different shapes of gold nanoparticles (AuNPs) functionalized with monosaccharides tune the bacterial aggregations. The mechanism of aggregation revealed that the large number of surface interactions of rod shaped mannose-AuNPs with E. coli ORN 178 compared with spherical and star-shaped AuNPs exhibited higher avidity and sensitivity. Moreover, such sensitive binding can be used for effective inhibition of bacterial infection of cells.

Association between serum albumin and glycated hemoglobin in Asian Indian subjects - Tiwari, Shalbha; Botahle, Manish; Hasan, Imtiaz; Kulkarni, Mahesh J.; Sayyad, Mehmood G.; Basu, Rita; Basu, Ananda; Unnikrishnan A. G. (Indian Journal of Endocrinology and Metabolism, 2015)
Protein glycation plays a significant role in diabetic complications. Glycated hemoglobin (HbA1c) is a known predictor of diabetes and its complications. Albumin, found to be profoundly glycated in diabetes, and its level could regulate plasma protein as well as hemoglobin glycation. We aimed to evaluate the association between variations in albumin level with HbA1c in the Asian Indian population. We screened data of 929 subjects who have had a simultaneous measurement of fasting plasma glucose (FPG), HbA1c and albumin levels via the same blood collection. Data were analyzed by SPSS for 610 subjects who met the study criteria. There was a significant negative correlation between HbA1c and albumin concentration (r = -0.284; P < 0.001). Univariate analysis showed the statistically significant decrease of average HbA1c but not for fasting plasma glucose (FPG) across increasing tertiles of albumin. Stepwise multiple regression model showed a significant correlation between HbA1c and serum albumin (P < 0.05), FPG (P < 0.001), hemoglobin (Hb) (P < 0.001) and serum globulin (P < 0.05). FPG was the strongest predictor (63.4%) of variation of HbA1c. The albumin concentration (r = -0.114) accounted for 0.3% (P < 0.05) of the total variance in HbA1c independent of age, body mass index, FPG, Hb, creatinine, total protein and globulin. It was also observed that HbA1c decreases with increasing albumin concentration in those having FPG between 100 to <126 mg/dl. Serum albumin negatively correlates with HbA1c in Asian Indians independent of other variables. This study suggests that predicting diabetes and its complication based on the HbA1c needs to be further investigated in Indian subjects.

Biomass derived beta-cyclodextrin-SO3H as a solid acid catalyst for esterification of carboxylic acids with alcohols - Thombal, Raju S.; Jadhav, Amol R.; Jadhav, Vrushali H. (RSC Advances, 2015)
A novel beta-cyclodextrin-SO3H carbon based solid acid catalyst was prepared in a convenient and ecofriendly manner and was characterized using FTIR, PXRD, EDAX and NH3TPD to illustrate that the carbon material has been functionalized with -SO3H, -COOH and -OH groups. The catalyst was studied for esterification of various carboxylic acids and alcohols under solvent free conditions and showed excellent catalytic performance and gave good yields of esters in the range 78-99% at 70 degrees C. No solvent was used either for catalyst preparation nor for esterification reaction. The catalyst can be easily recovered by simple filtration and reused for subsequent three runs without any significant impact on yields of products. The main advantage of this methodology is easy and ecofriendly catalyst preparation, easy catalyst separation, practical simplicity, safe reaction conditions, recyclable catalyst and high product yields.

c Squalene synthase gene from medicinal herb bacopa monniera: molecular characterization, differential expression, comparative modeling, and docking studies - Vishwakarma, Rishi K.; Patel, Krunal; Sonawane, Prashant; Kumari, Uma; Singh, Somesh; Ruby; Shakeel Abbassi; Agrawal, Dinesh C.; Tsay, Hsin-Sheng; Khan, Bashir Mohammad (Plant Molecular Biology Reporter, 2015)
The widespread pharmaceutically important triterpenoid saponins are synthesized via isoprenoid pathway. The formation of squalene is the key regulatory point in triterpene biosynthesis, catalyzed by squalene synthase (SQS). The present study deals with the detailed characterization of SQS by molecular, biochemical, and computational means from Bacopa monniera, an immensely important medicinal plant rich in triterpenoid saponin, bacosides. A full-length SQS gene was isolated from B. monniera, characterized as B. monniera squalene synthase (BmSQS) (1242 bp) encoding 414 amino acids. Deduced amino acid sequence of BmSQS showed highly conserved consensus aspartate-rich motifs (DXXXD) and catalytic site residues. Phylogenetic analysis showed that BmSQS belongs to dicot group having closest relationship with Salvia miltiorrhiza. Semiquantitative and real-time PCR studies showed that the BmSQS messenger RNA (mRNA) expression level was higher in vegetative parts (roots) as compared to floral parts. Methyl jasmonate induces the BmSQS mRNA expression in all tissues tested, while salicylic acid, cold, and salt induce much higher expression in roots. Homology modeling and docking simulations of BmSQS showed the pivotal roles of Asp77, Asp81, Asp213, Asp217, and Tyr168 in catalysis.
Keywords: Abiotic stress; Bacopa monniera; Comparative modeling and docking; Differential expression; Isoprenoid pathway; Squalene synthase

Calcium phosphate nanocapsule crowned multiwalled carbon nanotubes for pH triggered intracellular anticancer drug release - Banerjee, Shashwat S.; Todkar, Kiran J.; Khutale, Ganesh V.; Chate, Govind P.; Biradar, Ankush V.; Gawande, Manoj B.; Zboril, Radek; Khandare, Jayant J. (Journal of Materials Chemistry B, 2015)
We report calcium phosphate (CaP) nanocapsule crowned multi-walled carbon nanotubes (CNT-GSH-G4-CaP) as a novel platform for intracellular delivery of an anticancer drug. As a proof-of-concept, CNT-GSH-G4-CaP demonstrates release of anticancer drug doxorubicin hydrochloride (DOX) within intracellular lysosomes from the interior cavity of CNT upon pH triggered CaP dissolution. Importantly, we found that the CNT with a CaP nanolid can efficiently prevent untimely drug release at physiological pH but promotes DOX release at increased acidic milieu as observed in subcellular compartments such as lysosomes (similar to 5.0). This ``zero premature release'' characteristic is of clinical significance in delivering cytotoxic drugs, by reducing systemic toxicity and thus beneficial for the effective anticancer treatment. We envision that this pH triggered CaP crowned CNT nanosystem would lead to a new generation of self-regulated platforms for intracellular delivery of a variety of anticancer drugs.

Catalyst-dependent selectivity in the relay catalytic branching cascade - Bansode, Avinash H.; Shaikh, Aslam C.; Kavthe, Rahul D.; Thorat, Shridhar; Gonnade, Rajesh G.; Patil, Nitin T. (Chemistry-A European Journal, 2015)
The synthesis of small organic molecules as probes for discovering new therapeutic agents has been an important aspect of chemical biology. One of the best ways to access collections of small molecules is to use various techniques in diversity-oriented synthesis (DOS). Recently, a new form of DOS, namely relay catalytic branching cascades (RCBCs), has been introduced, wherein a common type of starting material reacts with several scaffold-building agents (SBAs) to obtain structurally diverse molecular scaffolds under the influence of catalysts. Herein, the RCBC reaction of a common type of substrate with SBAs is reported to give two different types of molecular scaffolds and their formation is essentially dependent on the type of catalyst used.
Keywords: alkynols; cascade synthesis; chemoselectivity; diversity-oriented synthesis; Homogeneous catalysis

Characterization of 10-hydroxygeraniol dehydrogenase from catharanthus roseus reveals cascaded enzymatic activity in iridoid biosynthesis - Krithika, Ramakrishnan; Srivastava, Prabhakar Lal; Rani, Bajaj; Kolet, Swati P.; Chopade, Manojkumar; Soniya, Mantri; Thulasiram, Hirekodathakallu V. (Scientific Reports, 2015)
Catharanthus roseus [L.] is a major source of the monoterpene indole alkaloids (MIAs), which are of significant interest due to their therapeutic value. These molecules are formed through an intermediate, cis-trans-nepetalactol, a cyclized product of 10-oxogeranial. One of the key enzymes involved in the biosynthesis of MIAs is an NAD(P)(+) dependent oxidoreductase system, 10-hydroxygeraniol dehydrogenase (Cr10HGO), which catalyses the formation of 10-oxogeranial from 10-hydroxygeraniol via 10-oxogeraniol or 10-hydroxygeranial. This work describes the cloning and functional characterization of Cr10HGO from C. roseus and its role in the iridoid biosynthesis. Substrate specificity studies indicated that, Cr10HGO has good activity on substrates such as 10-hydroxygeraniol, 10-oxogeraniol or 10-hydroxygeranial over monohydroxy linear terpene derivatives. Further it was observed that incubation of 10-hydroxygeraniol with Cr10HGO and iridoid synthase (CrIDS) in the presence of NADP(+) yielded a major metabolite, which was characterized as (1R, 4aS, 7S, 7aR)-nepetalactol by comparing its retention time, mass fragmentation pattern, and co-injection studies with that of the synthesized compound. These results indicate that there is concerted activity of Cr10HGO with iridoid synthase in the formation of (1R, 4aS, 7S, 7aR)-nepetalactol, an important intermediate in iridoid biosynthesis.

Chemically chargeable photo battery - Thimmappa, Ravikumar; Paswan, Bhuneshwar; Gaikwad, Pramod; Devendrachari, Mruthyunjayachari Chattanahalli; Kotresh, Harish Makri Nimbegondi; Mohan, Ramsundar Rani; Alias, Joy Pattayil; Thotiyl, Musthafa Ottakam (Journal of Physical Chemistry C, 2015)
Here we show a surrogate strategy for power production, wherein light is used to actuate a discharge Chemistry in the cathode of an aqueous rechargeable battery (ARB). The proposed photo battery consists of a titaninm nitride photoanode, promising. cathode:material iron(III) hexacyanoferrate(II) as the battery active species, and Na2S2O8 as the chemical charging agent The photo battery delivered negligible capacity in the dark and the capacity shot up to 77.8 mAh/g when artificially shined light, confirming that the battery chemistry is light driven. In the ambient light, the device retained 72% of its artificial light discharge capacity with a stable cycling for more than 100 cycles. Further, an unprecedented means for charging the battery rapidly is presented using Na2S2O8 and it revitalized the battery in 30 s without any external bias. This methodology of expending a photoanode extends to a battery that is free from dissolution of active materials, irreversible structural changes, spontaneous deinsertion reactions, and safety concerns commonly encountered in the state of the art anode materials in ARBs. Apart from bringing out a sustainable way for power production, this device opens up avenues for charging the battery in the likely events of electrical input unavailability, while solving the critcial issues of longer charging time and higher charging voltage.

Chemically grafted graphite nanosheets dispersed in poly(ethylene-glycol) by gamma-radiolysis for enhanced lubrication - Gupta, Bhavana; Panda, Kalpataru; Kumar, Niranjan; Melvin, Ambrose A.; Dash, Sitaram; Tyagi, Ashok Kumar (RSC Advances, 2015)
Graphite nanosheets (Gr-NS) dispersed in poly(ethylene-glycol) (PEG200) medium were subjected to various doses of gamma-irradiation. Hydroxyl functional groups present in PEG are chemically grafted through hydrogen bonding with hydroxyl, carbonyl and carboxylic groups of Gr-NS. The grafting process is driven by the generation of active radicals from solvent radiolysis. Chemical grafting was investigated using X-ray photoelectron spectroscopy (XPS) and Fourier transform infra-red (FTIR) spectroscopy. The results of spectroscopic studies revealed reduction in oxygen functionality of PEG-Gr-NS at higher doses of gamma-irradiation. The gamma-irradiation not only bridges the functionalities between PEG and PEG-Gr-NS but edge and basal plane defects in Gr-NS are further reduced as is evident from Raman analysis. The inter-planar sheet distance in Gr-NS is increased due to intercalated chemical grafting with PEG molecules. The chemical grafting between PEG and Gr-NS and reduction in defects enhance the tribological properties with a decrease of 26% and 32% for the friction coefficient and wear, respectively as compared to PEG alone. The lubrication mechanism is mediated through inter-planar weak forces when PEG is chemically grafted with Gr-NS. The electrostatic interaction of PEG with Gr-NS acts as a molecular bridge thus enhancing the sustainability of tribo-stress. Additionally, in the presence of functionalized PEG-Gr-NS tribo-contact conditions, evidence of deposited graphitic tribo-film was observed from micro-Raman spectroscopy inside the steel wear track. This film further enhanced lubrication mediated through low shear strength interlayer graphite sheets and therefore, antiwear properties were synergistically improved.

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

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

Cocrystallization of 2,3-dihydroxynaphthalene with its para-, meta-, and ortho-ditoluates: insight into cocrystal formation and clues for the construction of supramolecular assemblies capable of intermolecular acyl group transfer reactivity - Tamboli, Majid I.; Bahadur, Vir; Gonnade, Rajesh G.; Shashidhar, Mysore S. (Crystal Growth & Design, 2015)
2,3-Dihydroxynaphthalene forms 2:1 cocrystals with its p-ditoluate and 1:1 cocrystals with its m-ditoluate but not with the o-ditoluate. In 2:1 cocrystals of the p-ditoluate, naphthalene diol molecules form a dimeric motif through OH...O hydrogen bonding interactions. The adjacent dimers sandwich the molecules of p-ditoluate through C-H...pi interactions. In 1:1 cocrystals of the m-ditoluate, naphthalene diol molecules generate a zigzag pattern through O-H...O hydrogen bonding interaction involving -OH of the diol and the C=O of the m-ditoluate. Intermolecular toluoyl group transfer reaction was more facile in cocrystals of the p-ditoluate as compared to cocrystals of the m-ditoluate. This difference in reactivity is consistent with the relative geometry of the electrophile (El, C-O) and the nucleophile (Nu, OH) in these cocrystals. A comparison of the cocrystallization behavior and structure of the two cocrystals with their constituents suggests that the position of the methyl group is crucial for cocrystal formation. A survey of the CSD revealed that the incidence of polymorphism and cocrystals formation decreases (number of hits) in the order para- > ortho- > meta- for disubstituted benzene derivatives. This suggests that compounds prone to exhibit polymorphism have more propensities to form cocrystals as compared to those that resist polymorphism. This information could be useful while selecting cocrystal formers and construction of supramolecular functional assemblies with desired properties.

Crystal structures of the pyrazinamide-p-aminobenzoic acid (1/1) cocrystal and the transamidation reaction product 4-(pyrazine-2-carboxamido)-benzoic acid in the molten state - Thorat, Shridhar H.; Sahu, Sanjay Kumar; Gonnade, Rajesh G. (Acta Crystallographica Section C-Structural Chemistry, 2015)
The synthesis of pharmaceutical cocrystals is a strategy to enhance the performance of active pharmaceutical ingredients (APIs) without affecting their therapeutic efficiency. The 1: 1 pharmaceutical cocrystal of the antituberculosis drug pyrazinamide (PZA) and the cocrystal former p-aminobenzoic acid (p-ABA), C7H7NO2- C5H5N3O, (1), was synthesized successfully and characterized by relevant solid-state characterization methods. The cocrystal crystallizes in the monoclinic space group P21/n containing one molecule of each component. Both molecules associate via intermolecular O-H center dot center dot center dot O and NH center dot center dot center dot O hydrogen bonds [O center dot center dot center dot O = 2.6102 (15)angstrom and O-H center dot center dot center dot O = 168.3 (19)degrees; N center dot center dot center dot O = 2.9259 (18) angstrom and N-H center dot center dot center dot O = 167.7 (16)degrees] to generate a dimeric acidamide synthon. Neighbouring dimers are linked centrosymmetrically through N-H center dot center dot center dot O interactions [N center dot center dot center dot O = 3.1201 (18) angstrom and N-H center dot center dot center dot O = 136.9 (14)degrees] to form a tetrameric assembly supplemented by C-H center dot center dot center dot N interactions [C center dot center dot center dot N = 3.5277 (19) angstrom and C-H center dot center dot center dot N = 147 degrees]. Linking of these tetrameric assemblies through N-H center dot center dot center dot O [N center dot center dot center dot O = 3.3026 (19) angstrom and N-H center dot center dot center dot O = 143.1 (17)degrees], NH center dot center dot center dot N [N center dot center dot center dot N = 3.221 (2) angstrom and N-H center dot center dot center dot N = 177.9 (17)degrees] and C-H center dot center dot center dot O [C center dot center dot center dot O = 3.5354 (18) angstrom and C-H center dot center dot center dot O = 152 degrees] interactions creates the twodimensional packing. Recrystallization of the cocrystals from the molten state revealed the formation of 4-(pyrazine-2-carboxamido) benzoic acid, C12H9N3O3, (2), through a transamidation reaction between PZA and p-ABA. Carboxamide (2) crystallizes in the triclinic space group P1 with one molecule in the asymmetric unit. Molecules of (2) form a centrosymmetric dimeric homosynthon through an acid-acid O-H center dot center dot center dot O hydrogen bond [O center dot center dot center dot O = 2.666 (3) angstrom and O-H center dot center dot center dot O = 178 (4) degrees]. Neighbouring assemblies are connected centrosymmetrically via a C-H center dot center dot center dot N interaction [C center dot center dot center dot N = 3.365 (3) angstrom and C-H center dot center dot center dot N = 142 degrees] engaging the pyrazine groups to generate a linear chain. Adjacent chains are connected loosely via C-H center dot center dot center dot O interactions [C center dot center dot center dot O = 3.212 (3) angstrom and CH center dot center dot center dot O = 149 degrees] to generate a two-dimensional sheet structure. Closely associated two-dimensional sheets in both compounds are stacked via aromatic pi-stacking interactions engaging the pyrazine and benzene rings to create a threedimensional multi-stack structure.
Keywords: acid-amide hetero-synthon; active pharmaceutical ingredient (API); cocrystal; crystal structure; hydrogen bonding; molten-state reaction; powder diffraction; transamidation reaction

Cytostatic ruthenium(II)-platinum(II) bis(terpyridyl) anticancer complex that blocks entry into sphase by up-regulating p27(KIP1) - Ramu, Vadde; Gill, Martin R.; Jarman, Paul J.; Turton, David; Thomas, Jim A.; Das, Amitava; Smythe, Carl (Chemistry-A European Journal, 2015)
Cytostatic agents that interfere with specific cellular components to prevent cancer cell growth offer an attractive alternative, or complement, to traditional cytotoxic chemotherapy. Here, we describe the synthesis and characterization of a new binuclear Ru-II-Pt-II complex [Ru(tpy)(tpypma)Pt(Cl)(DMSO)](3+) (tpy=2,2:6,2-terpyridine and tpypma=4-([2,2:6,2-terpyridine]-4-yl)-N-(pyridin-2-ylmethyl)aniline), VR54, which employs the extended terpyridine tpypma ligand to link the two metal centres. In cell-free conditions, VR54 binds DNA by non-intercalative reversible mechanisms (K-b=1.3x10(5)M(-1)) and does not irreversibly bind guanosine. Cellular studies reveal that VR54 suppresses proliferation of A2780 ovarian cancer cells with no cross-resistance in the A2780CIS cisplatin-resistant cell line. Through the preparation of mononuclear Ru-II and Pt-II structural derivatives it was determined that both metal centres are required for this anti-proliferative activity. In stark contrast to cisplatin, VR54 neither activates the DNA-damage response network nor induces significant levels of cell death. Instead, VR54 is cytostatic and inhibits cell proliferation by up-regulating the cyclin-dependent kinase inhibitor p27(KIP1) and inhibiting retinoblastoma protein phosphorylation, which blocks entry into Sphase and results in G1 cell cycle arrest. Thus, VR54 inhibits cancer cell growth by a gain of function at the G1 restriction point. This is the first metal-coordination compound to demonstrate such activity.
Keywords: antitumor agents; cytostatic; p27KIP1; platinum drugs; ruthenium terpyridine

Deinococcus enclensis sp nov., isolated from a marine sediment sample - Thorat, Meghana N.; Mawlankar, Rahul R.; Sonalkar, Vidya V.; Ramana, V. Venkata; Joseph, Neeta; Shouche, Yogesh S.; Dastager, Syed Gulam (Antonie Van Leeuwenhoek International Journal of General and Molecular Microbiology, 2015)
A novel pale-pink coloured strain, designated NIO-1023(T), was isolated from a marine sediment sample from Chorao Island, Goa, India. The taxonomic position of strain NIO-1023(T) was investigated by using a polyphasic approach. The cells were observed to be Gram-stain positive, coccal shaped and non-spore forming. Phylogenetic analyses using the 16S rRNA gene sequence of the isolate indicated that the organism belongs to the genus Deinococcus. The strain NIO-1023(T) showed highest 16S rRNA gene sequence similarities with Deinococcus ficus (97.8 %), whereas other Deinococcus species showed less than 95 % sequence similarity. The DNA-DNA relatedness with respect to D. ficus CC-FR2-10(T) was 23.9 %. Chemotaxonomic data revealed that strain NIO-1023(T) contains only menaquinone MK-8 as the respiratory quinone and a complex polar lipid profile consisting of different unidentified glycolipids and polar lipids, two unknown phospholipids and three unknown phosphoglycolipids. As in other deinococci, one of these phosphoglycolipids was predominant in the profile. The predominant fatty acids were identified as C-17:1 w8c, C-16:1 w6c/w7c, C-15:1 w6c and C-17:1 w9c. The genomic DNA G + C content of strain NIO-1023(T) was determined to be 67.2 mol%. The biochemical and chemotaxonomic properties demonstrate that strain NIO-1023(T) represents a novel species, for which the name Deinococcus enclensis sp. nov. is proposed. The type strain is NIO-1023(T) (=DSM 25127(T) = NCIM 5456(T)).
Keywords: 16S rRNA; Deinococcus; Marine sediments; Polyphasic

Dinuclear salen cobalt complex incorporating Y(OTf)(3): enhanced enantioselectivity in the hydrolytic kinetic resolution of epoxides - Patel, Deepak; Kurrey, Ganesh Ram; Shinde, Sandip S.; Kumar, Pradeep; Kim, Geon-Joong; Thakur, Santosh Singh (RSC Advances, 2015)
The activation of inactive Jacobsen's chiral salen Co(II) (salen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine) compound is attained by dinuclear chiral salen Co(III)-OTf complex formation with yttrium triflate. The yttrium metal not only displays a promoting effect on electron transfer, but also assists in forming two stereocentres of a Lewis acid complex with Co(III)-OTf. We found that the binuclear Co-complex significantly enhanced reactivity and enantioselectivity in the hydrolytic kinetic resolution of terminal epoxides compared to its analogous monomer and kinetic data are also consistent with these results.

Dripping dynamics of newtonian liquids from a tilted nozzle - Taur, Amaraja; Doshi, Pankaj; Yeoh, Hak Koon (European Journal of Mechanics B-Fluids, 2015)
The dripping dynamics of Newtonian liquids emanating from an inclined nozzle is studied. The fluid viscosity mu flow rate Q, nozzle radius R, and inclination angle theta have been varied independently. The drop breakup times and the different modes of dripping have been identified using high speed imaging. A phase diagram showing the transition between the dripping modes for different theta is constructed in the (We, Ka) space, where We (Weber number) measures the relative importance of inertia to surface tension force and Ka (Kapitza number) measures the relative importance of viscous to surface tension forces. At low values of We and Ka, the system shows a transition from period-1 to limit cycle before chaos. The limit cycle region narrows down with increase in inclination. Further increase in the values of We and Ka gives a direct transition from period-1 to chaos. The new experiments reveal that in the period-1 region, increasing the nozzle inclination angle theta results in lowering of the drop breakup time t(b), suggesting that the surface tension forces cannot hold the drops longer despite the weakened effective gravitational pull. This counter-intuitive finding is further corroborated by pendant drop experiments and computations. More curiously, throughout the period-1 regime, the drop volume is independent of the flow rate. This resulted in a relatively simple correlation for the dimensionless drop volume V = 1.3G(-1)Ka(0.02)(cos theta)(0.37) accurate to within 10% over wide ranges of the independent variables. (C) 2014 Elsevier Masson SAS. All rights reserved.
Keywords: Asymmetric dripping; Breakup time; Drop volume; Inclined nozzle; Phase diagram

Drug-drug molecular salt hydrate of an anticancer drug gefitinib and a loop diuretic drug furosemide: an alternative for multidrug treatment - Thorat, Shridhar H.; Sahu, Sanjay Kumar; Patwadkar, Manjusha V.; Badiger, Manohar V.; Gonnade, Rajesh G. (Journal of Pharmaceutical Sciences, 2015)
A 1:1 monohydrate salt containing gefitinib, an orally administrated chemotherapy treatment for lung and breast cancers and furosemide, a loop diuretic drug, commonly used in the treatment of hypertension and edema, has been prepared. The molecular salt crystallized in triclinic P-1 space group. The CO bond lengths (similar to 1.26 angstrom) in the COOH group show that proton transfer has occurred from furosemide to morpholine moiety of the gefitinib suggesting cocrystal to be ionic. The morpholine moiety of the gefitinib showed significant conformational change because of its involvement in conformation dictating the strong N-H center dot center dot center dot O hydrogen bonding interaction. The strong hydrogen bonding interaction between gefitinib and furosemide places their benzene rings in stacking mode to facilitate the generation of pi-stack dimers. The neighboring dimers are bridged to each other via water molecule through N-H center dot center dot center dot O, C-H center dot center dot center dot O, O-H center dot center dot center dot N, and O-H center dot center dot center dot O interactions. The remarkable stability of the salt hydrate could be attributed to the strong hydrogen bonding interactions in the crystal structure. Interestingly, release of water from the lattice at 140 degrees C produced new anhydrous salt that has better solubility and dissolution rate than salt hydrate. The drug-drug molecular salt may have some bearing on the treatment of patient suffering from anticancer and hypertension. (C) 2015 Wiley Periodicals, Inc. and the American Pharmacists Association
Keywords: cancer chemotherapy; cocrystals; crystal engineering; crystal structure; dissolution rate; hydrate; phase transition; solubility; stability; thermal analysis

Efficient access to enantiopure 1,3-disubstituted isoindolines from selective catalytic fragmentation of an original desymmetrized rigid overbred template - Pandey, Ganesh; Varkhedkar, Rajesh; Tiwari, Divya (Organic & Biomolecular Chemistry, 2015)
An efficient and scalable synthesis of various enantiopure 1,3-disubstituted isoindolines is reported. The base catalyzed nucleophilic fragmentation of a rigid overbred template is established with various substrates to afford the corresponding 1,3-disubstituted isoindoline ester, amide, thioate, 1,3-amino alcohol and isoindolylcarboxylic acid. The crucial rigid overbred template is synthesized in an optically pure form in multigram scale by asymmetric desymmetrization of the corresponding meso compound.

Efficient method for the conversion of agricultural waste into sugar alcohols over supported bimetallic catalysts - Tathod, Anup P.; Dhepe, Paresh Laxmikant (Bioresource Technology, 2015)
Promoter effect of Sn in the PtSn/gamma-Al2O3 (AL) and PtSn/C bimetallic catalysts is studied for the conversion of variety of substrates such as, C5 sugars (xylose, arabinose), C6 sugars (glucose, fructose, galactose), hemicelluloses (xylan, arabinogalactan), inulin and agricultural wastes (bagasse, rice husk, wheat straw) into sugar alcohols (sorbitol, mannitol, xylitol, arabitol, galactitol). In all the reactions, PtSn/AL showed enhanced yields of sugar alcohols by 1.5-3 times than Pt/AL. Compared to C, AL supported bimetallic catalysts showed prominent enhancement in the yields of sugar alcohols. Bimetallic catalysts characterized by X-ray diffraction study revealed the stability of catalyst and absence of alloy formation thereby indicating that Pt and Sn are present as individual particles in PtSn/AL. The TEM analysis also confirmed stability of the catalysts and XPS study disclosed formation of electron deficient Sn species which helps in polarizing carbonyl bond to achieve enhanced hydrogenation activity. (C) 2014 Elsevier Ltd. All rights reserved.
Keywords: Agricultural waste; Bimetallic catalyst; Hydrogenation; Monosaccharides; Polysaccharides

Efficient robust fluorite CeZrO4-delta oxide catalyst for the eco-benign synthesis of styrene - Periyasamy, Kaliyappan; Aswathy, Venugopalan T.; Kumar, Venugopal Ashok; Manikandan, Marimuthu; Shukla, Rakesh; Tyagi, Avesh K.; Raja, Thirumalaiswamy (RSC Advances, 2015)
In this work, we have reported CeO2, ZrO2, physically mixed (PH)-CeO2/ZrO2 and fluorite CeZrO4-delta oxides and their catalytic activities for the oxidative dehydrogenation (ODH) of ethyl benzene (EB) to styrene (ST) using molecular oxygen, air and carbon dioxide as oxidants. The catalysts were prepared by a gel-combustion method followed by calcination at 600 degrees C for 6 h and subjected to catalytic activity measurements. All the catalysts were characterized and studied by various physicochemical methods. The reaction parameters were varied systematically such as different catalysts, oxidants, temperatures, EB flow and oxidant flow. CeZrO4-delta accounted for a 47% styrene yield for 72 h without any significant deactivation under optimized reaction conditions. A thorough analysis of the spent catalysts demonstrated the robustness of the catalyst for this reaction under different oxidants and reaction conditions. Pristine CeO2 deactivated easily and the activity decreased with time on stream of the reaction.

Enantiospecific synthesis of both enantiomers of the longtailed mealybug pheromone and their evaluation in a new zealand vineyard - Ramesh, Remya; Bell, Vaughn; Twidle, Andrew M.; Gonnade, Rajesh G.; Reddy, D. Srinivasa (Journal of Organic Chemistry, 2015)
The irregular monoterpenoid sex pheromone of Pseudococcus longispinus and its enantiomer were prepared from the corresponding bornyl acetates. The use of readily accessible chiral starting materials and lactone lactone rearrangement are the highlights of the present synthesis. The biological activities of the two enantiomers and racemic mixture were tested in a New Zealand vineyard. The (S)-(+)-enantiomer was significantly more attractive to P. longispinus males than the racemic mixture or the (R)-(-)-enantiomer.

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

Enhancing efficiency of perovskite solar cell via surface microstructuring: superior grain growth and light harvesting effect - Tathavadekar, Mukta C.; Agarkar, Shruti A.; Game, Onkar S.; Bansode, Umesh P.; Kulkarni, Sneha A.; Mhaisalkar, Subodh G.; Ogale, Satishchandra B. (Solar Energy, 2015)
We have introduced a novel approach to enhance the perovskite solar cell efficiency by controlling the grain growth and light harvesting properties of perovskite crystallites. Instead of using a mesoporous TiO2 layer, we have modified the surface microstructuring of the TiO2 film by dispensing nano assembled TiO2 submicron structures (nanobeads, NBs) on TiO2 compact layer. With this new approach solar cell efficiency was improved significantly through an increase in both J(sc) and V-oc. This high efficiency is attributed to crystallite size of the perovskite phase. These also act as light scattering centers giving higher current density and reduced recombination effects giving higher open circuit voltage. (C) 2014 Elsevier Ltd. All rights reserved.
Keywords: Grain growth; Light harvesting; Perovskite solar cells; TiO2 nanobeads

Exiguobacterium enclense sp nov., isolated from sediment - Dastager, Syed Gulam; Mawlankar, Rahul R.; Sonalkar, Vidya V.; Thorat, Meghana N.; Mual, Poonam; Verma, Ashish; Krishnamurthi, Srinivasan; Tang, Shan-Kun; Li, Wen-Jun (International Journal of Systematic and Evolutionary Microbiology, 2015)
A Gram-stain-positive bacterium, designated strain NIO-1109(T), was isolated from a marine sediment sample from Chorao Island, Goa, India. Phenotypic and chemotaxonomic characteristics and data from phylogenetic analysis based on 16S rRNA gene sequences indicated that strain NIO-1109(T) was related to the genus Exiguobacterium. Strain NIO-1109(T) exhibited >98.0% 16S rRNA gene sequence similarity with respect to Exiguobacterium indicum HHS 31(T) (99.5%) and Exiguobacterium acetylicum NCIMB 9889(T) (99.1 %); the type strains of other species showed <98% similarity. Levels of DNA DNA relatedness between strain NIO-1109(T) and E. acetylicum DSM 20416(T) and E indicum LMG 23471(T) were less than 70% (33.0 +/- 2.0 and 37 +/- 32%, respectively). Strain NIO-1109(T) also differed from these two closely related species in a number of phenotypic traits. Based on phenotypic, chemotaxonomic and phylogenetic data, strain NIO-1109(T) is considered to represent a novel species of the genus Exiguobacterium, for which the name Exiguobacterium enclense sp. nov. is proposed. The type strain is NIO-1109(T) (=NCIM 5457(T)= DSM 25128(T)=CCTCC AB 2011124(T)).

Facile gamma radiolytic methodology for TiO2-rGO synthesis: effect on photo-catalytic H-2 evolution - Gupta, Bhavana; Melvin, Ambrose A.; Matthews, Tom; Dhara, S.; Dash, Sitaram; Tyagi, A. K. (International Journal of Hydrogen Energy, 2015)
TiO2 (P25) decorated reduced graphene oxide (rGO) is synthesized by gamma-radiolytic technique using water-ethanol solvent medium. Visible light absorpdon was confirmed by UV-Visible spectroscopy. Photoluminescence (PL) study revealed a decline in electron-hole recombination rate signalled by a sharp fall in luminescence of TiO2. Under such scenario, electron transfer from TiO2 conduction band to the conjugated sheet becomes a preferred pathway in the presence of rGO, which is further confirmed by photocurrent measurement. TiO2 -rGO composite with 1 wt. % rGO was found to be the best composition in terms of visible light absorption, while retaining TiO2 crystallinity. Transmission electron microscopy and Raman spectroscopic studies confirmed the coating of rGO sheet with TiO2 nanoparticles. TiO2 -rGO was found to show about 150 times higher photocatalytic H-2 generation under 250 W UV-Visible light irradiation than pristine TiO2. In addition to this, TiO2 -rGO composite shows hydrogen production yield of 35 mu mol/h.g under visible light (lambda = 400 nm) irradiation. Thus gamma-radiolysis can be considered to be a viable technique, which helps in synthesizing photocatalytically active nanocomposite with high H-2 evolution rate. In the light of these interesting aspects, a detail investigation is carried out to study the effect of rGO concentration and illumination time on photocatalytic yield. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
Keywords: gamma-radiolysis; H-2 production; Photocatalysis; Reduced graphene oxide; TiO2

Facile synthesis of Ag nanowire-rGO composites and their promising field emission performance - Samantara, Aneeya K.; Mishra, Dillip Kumar; Suryawanshi, Sachin R.; More, Mahendra A.; Thapa, Ranjit; Late, Dattatray J.; Jena, Bikash Kumar; Rout, Chandra Sekhar (RSC Advances, 2015)
Crystalline, ultra long silver nanowires (Ag NWs), few-layered rGO (reduced graphene oxide) and their rGO-Ag NW nanocomposite have been synthesized using a polyol reflux technique under optimized experimental conditions. The field emission performance of the rGO-Ag NW nanocomposite, rGO and Ag NW emitters was investigated. The turn on field required to draw an emission current density of similar to 1 mA cm(-2) was found to be similar to 5.00, 3.92 and 2.40 V mu m(-1) for the Ag NW, rGO and rGO-Ag NW nanocomposite emitters, respectively. The combined contribution of the sharp edges of the thin graphene sheets and high aspect ratio of the Ag nanowires, and their synergetic effect in the rGO-Ag NW nanocomposite, are responsible for the enhanced field emission behavior. First-principles density functional calculations show that the enhanced field emission may also be due to the overlapping of the electronic structures of the Ag NWs and rGO nanosheets.

Field emission properties of spinel ZnCo2O4 microflowers - Ratha, Satyajit; Khare, Ruchita T.; More, Mahendra A.; Thapa, Ranjit; Late, Dattatray J.; Rout, Chandra Sekhar (RSC Advances, 2015)
ZnCo2O4 microflowers were synthesized by a simple low temperature hydrothermal route. A single three-dimensional microflower consists of hundreds of self-assembled petals, with a thickness of several nanometers. These microflowers have exceptionally thin edges with a few petal layers. The ZnCo2O4 microflowers appeared to be stable and good field emitters.