Estimating the lipophobic contributions in model membranes - Dubey, Vikas; Prasanna, Xavier; Sengupta, Durba (Journal of Physical Chemistry B, 2017)
The insertion and association of membrane proteins is critical in several cellular processes. These processes were thought to be protein-driven, but increasing evidence points toward an important role of the lipid bilayer. The lipid-mediated contribution has been shown to be important in the association of membrane peptides, but the corresponding ``lipophobic'' component has not been directly estimated. Here, we calculate the free energy of insertion for transmembrane peptides and estimate the lipophobic component from the cost of cavity formation. The free-energy calculations were performed using the coarse-grain Martini force field, which has been successful in predicting membrane protein interactions. As expected, the charged moieties have the least favorable free energy of insertion and the highest cost of cavity formation. A length dependence was observed in polyalanine peptides with the lipid-mediated component increasing nonlinearly with peptide length. Membrane fluidity was tested by varying the temperature, and opposing effects were observed for short and long peptides. The dependence of the lipid-mediated effects on peptide length and temperature was not uniform and gives valuable insight into the anisotropic nature of the membrane. The results are an important step in estimating membrane effects in protein insertion and association.

Examination into the taxonomic position of Bacillus thermotolerans Yang et al., 2013, proposal for its reclassification into a new genus and species Quasibacillus thermotolerans gen. nov., comb. nov. and reclassification of B. encimensis Dastager et al., - Verma, Ashish; Pal, Yash; Khatri, Indu; Ojha, Anup Kumar; Gruber-Vodicka, Harald; Schumann, Peter; Dastager, Syed Gulam; Subramanian, Srikrishna; Mayilraj, Shanmugam; Krishnamurthi, Srinivasan (Systematic and Applied Microbiology, 2017)
Two novel Gram-staining positive, rod-shaped, moderately halotolerant, endospore forming bacterial strains 5.5LF 38TD and 5.5LF 48TD were isolated and taxonomically characterized from a landfill in Chandigarh, India. The analysis of 16S rRNA gene sequences of the strains confirmed their closest identity to Bacillus thermotolerans SgZ-8T with 99.9% sequence similarity. A comparative phylogenetic analysis of strains 5.5LF 38TD, 5.5LF 48TD and B. thermotolerans SgZ-8(T) confirmed their separation into a novel genus with B. badius and genus Domibacillus as the closest phylogenetic relatives. The major fatty acids of the strains are iso-C15:0 and iso-C16:0 and MK-7 is the only quinone. The major polar lipids are diphosphatidylglycerol, phosphatidylglycerol and phosphatidylethanolamine. The digital DNA-DNA hybridization (DDH) and ortho average nucleotide identity (ANI) values calculated through whole genome sequences indicated that the three strains showed low relatedness with their phylogenetic neighbours. Based on evidences from phylogenomic analyses and polyphasic taxonomic characterization we propose reclassification of the species B. thermotolerans into a novel genus named Quasibacillus thermotolerans gen. nov., comb. nov with the type strain SgZ-8(T) (=CCTCC AB2012108(T)=KACC 16706(T)). Further our analyses also revealed that B. encimensis SGD-V-25(T) is a later heterotypic synonym of Bacillus badius DSM 23(T).

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

Facile synthesis and electrochemical evaluation of PANI/CNT/MoS2 ternary composite as an electrode material for high performance supercapacitor - Thakur, A.K.; Deshmukh, A. B.; Choudhary, R. B.; Karbhal, I.; Majumder, M.; Shelke, M.V. (Materials Science and Engineering B: Solid-State Materials for Advanced Technology, 2017)
Synthesis of a novel ternary composite consisting of polyaniline (PANI), functionalized multi-walled carbon nanotubes (CNTs) and molybdenum disulfide (MoS2), via an in-situ polymerization method is reported. Detailed structural and electrochemical characterization shows that incorporation of a small amount of MoS2 in PANI/CNT composite tends to eliminate agglomeration problem of CNT. The PANI/CNT/MoS2 ternary composite reaches a specific capacitance of 350 F/g at the current density 1 A/g corresponding to a 5% MoS2 content. This ternary composite shows good cycling stability even at a higher energy density of 10 A/g. Further, PANI/CNT/MoS2 composite electrode shows higher energy density (7.77 Wh/kg) and power density (2140 W/kg) as compared to PANI/CNT composite without MoS2.
Keywords: MoS2; polyaniline; supercapacitor; Ternary Composite

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

Facile synthesis of 3D anode assembly with Si nanoparticles sealed in highly pure few layer graphene deposited on porous current collector for long life Li‐Ion battery - Shelke, Manjusha V.; Gullapalli, Hemtej; Kalaga, Kaushik; Rodrigues, Marco; Devarapalli, Rami Reddy; Vajtai, Robert; Ajayan, Pulickel M. (Advanced Materials Interfaces, 2017)
With its exceptional theoretical charge capacity, silicon holds great promise as an anode material for realization of high energy density Li-ion batteries. However, extensive volume expansion and poor cycle stability of silicon compromise its actual use. In an effort to tame volume expansion and structural disintegration during cycling, an innovative 3D electrode assembly is fabricated involving continuous layer of graphene coated on porous current collector and Si nanoparticles sealed in as an active material. Graphene deposition and pore formation in metal current collector is achieved in a unique single step synthesis. All the active components like current collector, reacting material, and conducting material are manipulated in a way to produce synergistic architecture in a chemical vapor deposition process. Highly pure graphene deposited in this process enables efficient electron transfer from allover of the surface of silicon nanoparticles and prevents continuous solid electrolyte interphase layer formation. This binder free anode assembly shows extremely stable lithium storage performance for over 1000 cycles with 88% of initial capacity retention and 100% Coulombic efficiency.

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

ffects of cations, anions and H+ concentration of acidic ionic liquids on the valorization of polysaccharides into furfural - Matsagar, Babasaheb M.; Dhepe, Paresh L. (New Journal of Chemistry, 2017)
The valorization of hemicellulose into valuable chemicals, such as C5 sugars and furfural, in a one-pot fashion is crucial. In this work, acidic ionic liquids in the presence of water showed high yields of C5 sugars (>80%) with >99% conversion of hemicelluloses at 160 degrees C. With a water + toluene biphasic solvent system, within 4 h, an 85% furfural yield was obtained directly from hemicellulose in a one-pot fashion using a catalytic amount of 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate. It was seen that Bronsted acidic ionic liquids (BAILs) perform better than solid acid [Faujasite and Mordenite zeolites; ion exchange resin, Amberlyst-15] and mineral catalysts [HCl and H2SO4]. The higher activity of BAILs compared to solid acids and mineral acids was correlated to the Hammett acidity function (Ho) and ion-dipole type of interactions. The catalysts were characterized using NMR (H-1 and C-13), elemental analysis and TGA to confirm that they were stable under reaction conditions and were thus recyclable.

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

Functional stability and structural transitions of kallikrein: spectroscopic and molecular dynamics studies - Dalal, Sayli; Mhashal, Anil; Kadoo, Narendra; Gaikwad, Sushama M. (Journal of Biomolecular Structure & Dynamics, 2017)
Kallikrein, a physiologically vital serine protease, was investigated for its functional and conformational transitions during chemical (organic solvents, Gdn-HCl), thermal, and pH induced denaturation using biochemical and biophysical techniques and molecular dynamics (MD) simulations approach. The enzyme was exceptionally stable in isopropanol and ethanol showing 110% and 75% activity, respectively, after 96h, showed moderate tolerance in acetonitrile (45% activity after 72h) and much lower stability in methanol (40% activity after 24h) (all the solvents [90% v/v]). Far UV CD and fluorescence spectra indicated apparent reduction in compactness of KLKp structure in isopropanol system. MD simulation studies of the enzyme in isopropanol revealed (1) minimal deviation of the structure from native state (2) marginal increase in radius of gyration and solvent accessible surface area (SASA) of the protein and the active site, and (3) loss of density barrier at the active site possibly leading to increased accessibility of substrate to catalytic triad as compared to methanol and acetonitrile. Although kallikrein was structurally stable up to 90 degrees C as indicated by secondary structure monitoring, it was functionally stable only up to 45 degrees C, implicating thermolabile active site geometry. In GdnHCl [1.0M], 75% of the activity of KLKp was retained after incubation for 4h, indicating its denaturant tolerance. A molten globule-like structure of KLKp formed at pH 1.0 was more thermostable and exhibited interesting structural transitions in organic solvents. The above results provide deeper understanding of functional and structural stability of the serine proteases at molecular level.
Keywords: isopropanol tolerance; Kallikrein; MD Simulation; Molten globule; Serine protease; Thermostability

Fungal differentiation: a model phenomenon to screen antifungal drugs - Pathan, E.K.; Tupe, S.G.; Deshpande, M.V. (Developments in Fungal Biology and Applied Mycology, 2017)
Pathogenic fungi change the morphology to a suitable vegetative form such as unicellular yeast or filamentous mycelium for the survival and proliferation in the host as well as to defeat cellular and physiological defences of the host. The microenvironment of the pathogen triggers different biochemical processes finally leading to differentiation. These biochemical processes, which correlate with morphological change from saprophytic/less virulent to pathogenic form, can be targeted for the development of novel antifungal agents. The present chapter deals with the role of differentiation in fungal pathogenesis and discusses different biochemical events as target for the antifungal strategies.

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

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

Hydrogen production from reforming of biogas: review of technological advances and an Indian perspective - Nahar, G.; Mote, D.; V. Dupont (Renewable and Sustainable Energy Reviews, 2017)
This paper examines the benefits and potential of biogas generation and uses in India, with focus on advances made in hydrogen production by catalytic reforming technologies with steam, O2, and CO2 as the oxidants. Utilization of biomass by means of generating biogas is one of the easiest and cost effective methods of harnessing renewable energy. As India is an agricultural country, a tremendous amount of biomass and livestock waste is generated every year. Likewise the large population of India generates much food and municipal solid waste that is not being utilized for biogas generation. Fuel cells are one of the effective means of utilizing biogas, although the synthesis gas or hydrogen generated from biogas can also be used in internal combustion engines. Higher efficiency of fuel cells (45%) compared to internal combustion engines (30%) and even higher with co-generation systems (70%) make them highly desirable for biogas utilization for power generation. Investigations of hydrogen productionfor fuel cell use are in their infancy stage in India. Apart from a few scattered investigations not much work has been undertaken in the area of research. Large scale hydrogen production is achieved by steam reforming of hydrocarbons, in particular natural gas. Although the process is a proven technology it has come under considerable scrutiny due to its environmental impact and the energy intensive nature of the process. Several technical and scientific challenges have to be overcome for assimilation of the technology for hydrogen production from biogas and wide scale application in India. These challenges include development of less energy intensive features, highly active and poisons-resistant catalyst, and fuel cell development for utilization of biogas generated hydrogen. Hydrogen production from reforming of biogas: Review of technological advances and an Indian perspective. Available from: https://www.researchgate.net/publication/315896154_Hydrogen_production_from_reforming_of_biogas_Review_of_technological_advances_and_an_Indian_perspective [accessed Oct 16 2017].

Identification and synthesis of mycalol analogues with improved potency against anaplastic thyroid carcinonia cell lines - Cutignano, Adele; Seetharamsingh, B.; D'Angelo, Daniela; Nuzzo, Genoveffa; Khairnar, Pankaj V.; Fusco, Alfredo; Reddy, D. Srinivasa; Fontana, Angelo (Journal of Natural Products, 2017)
The marine metabolite mycalol (1) has a specific inhibitory activity on cells of anaplastic thyroid carcinoma (ATC), a very aggressive and rare cancer that does not have effective conventional therapy. In this study, we describe six new related analogues (2-7) that differ in the length of the terminal alkyl residue and the presence of acetate or 3S-hydroxybutyrate (3S)-3HB as a substituent at C-19. Despite the structural' analogies, some of the new members were significantly more-cytotokic than 1 on cell lines,derivecl from human ATC. Structures inclusive of the 2'R,3R,4S,7R,8S,19R absolute configuration were asigned to 2-7 on the basis of detailed spectroscopic analysis, synthesis of different isomers, and application of ECD and Mosher's methods. This work led to the identification of mycal61-578 (3) as the most potent analogue, with an IC50 of 2.3 mu M on FRO cells:

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

Influence of preparation method on activity and stability of Ni catalysts supported on Gd doped ceria in dry reforming of methane - Gurav, Hanmant R.; Dama, Srikanth; Samuel, Violet; Chilukuri, Satyanarayana (Journal of CO2 Utilization, 2017)
Nickel catalysts supported on Gd doped ceria (NGDC), with various Ni content, were prepared through different preparation routes and evaluated for dry reforming of methane (DRM). Their detailed characterization revealed that method of preparation plays an important role in Ni dispersion, with catalysts prepared through co-precipitation showing high Ni dispersion. The co-precipitated 12NGDC-cp catalyst with 12 wt% NiO was found to be superior in terms of high CO2 and CH4 conversions compared to catalysts prepared through citrate gel or impregnation methods Even H-2 and CO yields are high on this catalyst, while it shows excellent durability with stable activity even after 100 h on-stream. Thermogravimetric analysis of spent catalyst showed presence of coke, with transmission electron microscopic studies pointing to the presence of Ni crystallites at the mouth of the carbon whiskers. These Ni crystallites appear to be still active for DRM reaction. Among the spent catalysts, the carbon formation was high on catalysts that have bigger Ni crystallites, with the catalysts prepared through impregnation and citrate gel methods having higher coke. Investigations also reveal that the conversion of active (amorphous) carbon into stable (graphitic) carbon depends on the Ni crystallite size, temperature and duration of the reaction. These studies demonstrate that Gd doped ceria is a good support for Ni, to obtain high DRM activity and very good on-stream stability provided the catalysts are prepared through an appropriate method.

Influence of thermocleavable functionality on organic field-effect transistor performance of small molecules - Mahale, Rajashree Y.; Dharmapurikar, Satej S.; Chini, Mrinmoy Kumar; Venugopalan, Vijay (Chemical Physics Letters, 2017)
Diketopyrrolopyrrole based donor-acceptor-donor conjugated small molecules using ethylene dioxythiophene as a donor was synthesized. Electron deficient diketopyrrolopyrrole unit was substituted with thermocleavable (tert-butyl acetate) side chains. The thermal treatment of the molecules at 160 degrees C eliminated the tert-butyl ester group results in the formation of corresponding acid. Optical and theoretical studies revealed that the molecules adopted a change in molecular arrangement after thermolysis. The conjugated small molecules possessed p-channel charge transport characteristics in organic field effect transistors. The charge carrier mobility was increased after thermolysis of tert-butyl ester group to 5.07 x 10(-5) cm(2)/Vs. (C) 2017 Elsevier B.V. All rights reserved.

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

Investigation into the taxonomy of “ B. aminovorans” and its reclassification to the genus Domibacillus as Domibacillus aminovorans sp. nov. - Verma, Ashish; Ojha, Anup Kumar; Pal, Yash; Kumari, Parveen; Schumann, Peter; Gruber-Vodicka, Harald; Dastager, Syed Gulam; Natarajan, Ramesh Kumar; Mayilraj, Shanmugam; Krishnamurthi, Srinivasan (Systematic and Applied Microbiology, 2017)
The species "Bacillus aminovorans" was categorized as species Incertae Sedis meaning taxa with uncertain taxonomic position because of insufficient description of phenotypic properties and lack of understanding of its phylogenetic relationship (Claus and Berkeley [5]). In this study two strains "B. aminovorans" DSM 1314T and DSM 4337 were phenotypically and phylogenomically analyzed. The strains are Gram-staining-positive, spore forming rods and unable to utilize/ferment most of the sugars tested except glucose. The major fatty acids are anteiso-C15:0 and iso-C15:0. The major polar lipids are diphosphatidylglycerol, phosphatidylglycerol and an aminophosphoglycolipid. The cell wall peptidoglycan is of A1γ type with meso-Dpm as the diamino acid. The menaquinone type present is MK-6. The G+C content of the genomic DNA of the type strain is 40.8mol%. These characteristics were found to be in line with description of the genus Domibacillus. Moreover phylogenetic analysis based on 16S rRNA gene sequence retrieved "B. aminovorans" within the genus Domibacillus with D. antri XD 80T as the closest relative. Additionally genome sequencing of the strains and their comparison with whole genome sequences of other Domibacillus spp. confirmed their distinctiveness and separate species status within the genus based on parameters of genome to genome distance calculator (GGDC) and average nucleotide identity (ANI) values. Therefore a novel species Domibacillus aminovorans sp. nov. (DSM 1314T =LMG 16796T) is proposed.
Keywords: 16S rRNA; Domibacillus aminovorans; MALDI-TOF; ``Bacillus aminovorans''

Isolation and characterization of 9-lipoxygenase and epoxide hydrolase 2 genes: insight into lactone biosynthesis in mango fruit (Mangifera indica L.) - Deshpande, Ashish B.; Chidley, Hemangi G.; Oak, Pranjali S.; Pujari, Keshav H.; Giri, Ashok P.; Gupta, Vidya S. (Phytochemistry, 2017)
Uniqueness and diversity of mango flavour across various cultivars are well known. Among various flavour metabolites lactones form an important class of aroma volatiles in certain mango varieties due to their ripening specific appearance and lower odour detection threshold. In spite of their biological and biochemical importance, lactone biosynthetic pathway in plants remains elusive. Present study encompasses quantitative real-time analysis of 9-lipoxygenase (Mi9LOX), epoxide hydrolase 2 (MiEH2), peroxygenase, hydroperoxide lyase and acyl-CoA-oxidase genes during various developmental and ripening stages in fruit of Alphonso, Paid and Kent cultivars with high, low and no lactone content and explains their variable lactone content. Study also covers isolation, recombinant protein characterization and transient over-expression of Mi9LOX and MiEH2 genes in mango fruits. Recombinant Mi9LOX utilized linoleic and linolenic acids, while MiEH2 utilized aromatic and fatty acid epoxides as their respective substrates depicting their role in fatty acid metabolism. Significant increase in concentration of delta-valerolactone and gamma-decalactone upon Mi9LOX over-expression and that of delta-valerolactone, gamma-hexalactone and delta-hexalactone upon MiEH2 over-expression further suggested probable involvement of these genes in lactone biosynthesis in mango. (C) 2017 Elsevier Ltd. All rights reserved.

Kocuria indica sp. nov., isolated from a sediment sample (vol 64, pg 869, 2014) - Dastager, Syed G.; Tang, Shan-Kun; Srinivasan, Krishnamurthi; Lee, Jae-Chan; Li, Wen-Jun (International Journal of Systematic and Evolutionary Microbiology, 2017)

L-Proline functionalized dicationic framework of bifunctional mesoporous organosilica for the simultaneous removal of lead and nitrate ions - Dinker, Manish K.; Ajithkumar, Thalasseril G.; Kulkarni, Prashant S. (ACS Sustainable Chemistry & Engineering, 2017)
A novel bifunctional mesoporous organosilica, PEG-functionalized bis-prolinium chloride bridged mesoporous organosilica (BPBMO) was synthesized by reacting the precursor, PEG-functionalized bis-prolinium chloride bridged organosilane (BPRIL) with tetraethyl orthosilicate (TEOS) in the presence of surfactant. The chemical conformation of BPBMO was investigated by using Fourier transform infrared (FTIR), thermogravimentric analysis (TGA), C-13, and Si-29 cross-polarization/magic angle spinning (CP/MAS) NMR techniques. The characterization represents PEG-linked-prolinium (-N+Cl-) and carboxyl (-COOH) entities, constructing the dicationic framework through siloxane (Si-O-Si) linkages. The pore-wall distribution and the periodicity of BPBMO retained during the synthesis were examined by small-angle X-ray scattering (SAXS), Brunauer-Emmett-TellerBarrett-Joyner-Halenda (BET-BJH), and transmission electron microscopy (TEM) techniques. The results revealed BPBMO as a spherical shaped solid (50-100 nm) having mesopore channels hexagonally arranged with interparticle porosity (S-BET = 487 m(2)/g and D-BJH = 5.1 nm). The material has provided active binding sites for the simultaneous removal of NO3- and Pb2+ ions when introduced in the aqueous solutions of Pb(NO3)(2) (50 mg/L, pH 6). The removal of NO3- by ion-exchange with prolinium (-N+Cl-) entities and the electrostatic interaction of Pb2+ with carboxylate (-COO-) group were characterized by using Raman spectroscopy, ion chromatography, and X-ray photoelectron spectroscopy (XPS) technique. The maximum removal of NO3- and Pia' ions were achieved within 1 h of the adsorption reaction. The adsorption has followed the Langmuir isotherm model with the adsorption capacities (q(m)) of 23.04 and 21.92 mg/g for NO3- and Pb2+ ions, respectively. The efficiency of the adsorbent was also compared with other adsorbents. Further, the BPBMO material has depicted three consecutive adsorption/desorption cycles with negligible loss in the structural conformation.

Magnetic studies of SiO2 coated CoFe2O4 nanoparticles - Limaye, M.V. (Journal of Magnetism and Magnetic Materials, 2017)
Oleic acid capped CoFe2O4 nanoparticles which exhibit a high coercivity of ∼9.47 kOe at room temperature were coated with a robust coating of SiO2. We have used chemical synthesis method to obtain SiO2 coated CoFe2O4 nanoparticles with different weight percentages of CoFe2O4 in SiO2 (1.5, 3.1 and 4.8 wt.%). The morphological investigation of the coated nanoparticles by transmission electron microscopy shows that the particles are spherical with average size ∼160 nm. Infrared spectroscopy reveals that oleic acid capping on the surface of CoFe2O4 nanoparticles is retained after silica coating process. The complete coating of SiO2 on CoFe2O4 nanoparticles is confirmed by X-ray photoelectron spectroscopy as there is no signature of cobalt or iron ions on the surface. Magnetic measurements show that coercivity of SiO2 coated CoFe2O4 particles remains more or less unaffected as in CoFe2O4 nanoparticles at room temperature. In addition, the temperature dependent magnetic measurements show that at 5 K the CoFe2O4 and SiO2 coated 1.5 wt.% CoFe2O4 samples exhibit a very high value of coercivity (∼20 kOe) which is more than twice as compared to room temperature coercivity value (∼9.47 kOe). We conclude that silica coating in our study does not significantly affect the coercivity of CoFe2O4 nanoparticles.
Keywords: Coatings; coercive force; High Resolution Transmission Elctron Microscopy; infrared spectroscopy; Magnetic materials

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

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

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

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

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

Microreactor-based continuous process for controlled synthesis of poly-methyl-methacrylate-methacrylic acid (PMMA) nanoparticles - Dobhal, Anurag; Kulkarni, Amol; Dandekar, Prajakta; Jain, Ratnesh (Journal of Materials Chemistry B, 2017)
We have developed a microreactor-based continuous process for synthesizing PMMA nanoparticles (NPs), based on the principle of nanoprecipitation. Our objective was to identify the critical parameters governing the size of nanoparticles, produced in microreactors, to enable reproducible synthesis of mono-disperse particles. Experiments were carried out in a microreactor, where parameters like flow rates of aqueous and organic phases, residence time and polymer concentrations were varied to examine their influence on particle size and homogeneity. The results from Dynamic Light Scattering confirmed that the particle size decreased with decreasing residence time, whereas when the aqueous to organic phase flow rate ratio was changed sequentially from 9 : 1, 4 : 1, 7 : 3, 3 : 2, to 1 : 1 (v/v), the particle size increased. Particles fabricated using a microreactor demonstrated a narrow and homogenous distribution, thus confirming their monodispersity. TEM, SEM and XRD were also performed for morphology analysis and phase identification of the particles. Further, paclitaxel encapsulated PMMA nanoparticles were prepared using the microreactor, demonstrating an increase in mean size of around 30 nm and a slightly higher polydispersity index compared to the blank nanoparticles. The drug encapsulation efficiency and drug release kinetics of these nanoparticles were comparable to those prepared in batch-experiments, thus establishing the suitability of the technology for preparing drug-loaded nanoparticles. Also, it was observed that at all the residence times (10 min to 10 s), about 80% of the polymer got transformed into nanoparticulate form, thus confirming the efficiency of the microreactor. In recent times, much work has been conducted to synthesize polymeric nanoparticles using different types of microreactors, but they lack detailed investigation of the effect of various parameters on the physiochemical properties of the resulting particles. Our investigation synthesizes PMMA NPs, using microreactor technology, for the very first time, to the best of our knowledge. Furthermore, we have performed a detailed analysis of the influence of various process parameters on the size and uniformity of the resulting nanoparticles. These critical parameters can serve as a useful tool to synthesize a myriad of nanoparticles of alternative polymers, using microreactor technology.

Microvirga indica sp. Nov., an arsenite-oxidizing alphaproteobacterium, isolated from metal industry waste soil - Tapase, S. R. (International Journal of Systematic and Evolutionary Microbiology, 2017)
A novel Gram-stain-negative bacterium, strain S-MI1bT, belonging to the genus Microvirga was isolated from a metal industry waste soil sample in Pirangut village, Pune District, Maharashtra, India. Cells were non-spore-forming, small rod-shapes, motile and strictly aerobic with light-pink colonies. The strain grew in 0-7.0 % (w/v) NaCl and at 25-45 °C, with optimal growth at 40 °C. The predominant fatty acids detected were summed feature 8 (C18 : 1 ω7c and/or C18 : 1 ω6c) and C19 : 0 cyclo ω8c. The predominant isoprenoid quinone was Q-10. The G+C content was 67.2 mol% and DNA-DNA relatedness values between strain S-MI1bTand Microvirga subterranea DSM 14364T and Microvirgaaerophila 5420S-12T were 53.9 and 54.8 %, respectively. Phylogenetic analysis, based on 16S rRNA gene sequences, indicated that strain S-MI1bT is a member of the genus Microvirga, with greatest sequence similarities of 97.7 and 97.4 % with M. subterranea DSM 14364T and M.aerophila 5420S-12T, respectively. Phylogenetic analysis showed that strain S-MI1bT forms a clade with the type strain of M. subterranea DSM 14364T, and was readily distinguishable from it due to various phenotypic characteristics. The combination of genotypic and phenotypic data suggests that the isolate represents a novel species of the genus Microvirga, for which the name Microvirga indica sp. nov. is proposed. The type strain is S-MI1bT (=NCIM-5595T=KACC 18792T=BCRC 80972T)

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

Molecular methods for identification of clostridium tetani by targeting neurotoxin - Dharne, Mahesh S.; Nagoba, Basavraj S.; Gohil, Kushal N. (Methods Molecular Biology, 2017)
Tetanus is a potentially fatal muscle spasm disease. It is an important public health problem, especially in rural/tribal areas of developing countries. Tetanus toxin, a neurotoxin (tetanospasmin ), is the most important virulence factor that plays a key role in the pathogenicity of tetanus . Confirmation of virulence by confirming the production of tetanospasmin by infecting species forms the most important part in the diagnosis of tetanus . Various molecular methods have been devised for confirmation of diagnosis by targeting different genes. The most common molecular methods are tetanospasmin producing (TetX) gene-targeted methods using TetX-specific primers. Here, we describe various molecular methods targeting TetX gene such as polymerase chain reaction, pulsed-field gel electrophoresis, Southern blotting, loop-mediated isothermal amplification assay, etc. to confirm the virulence of Cl. tetani.

Multicolour and nearly white light emission in YP0.8V0.2O4:Sm3+ nanorods: controlled energy transfer - Singh, N.S. (Journal of Alloys and Compounds, 2017)
Nanorods of YP0.8V0.2O4:Sm³⁺ have been synthesized under hydrothermal conditions. Substitution of vanadium (V⁵⁺) sites in YVO4 by phosphorus ions (P⁵⁺) has been confirmed by Fourier transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. Careful selection of Sm³⁺ concentration in YP0.8V0.2O4 enables to achieve the controlled energy transfer from the VO4³⁻ absorption to the excited states of Sm³⁺ ions. The controlled energy transfer has been confirmed from the steady state luminescence and decay lifetime studies of VO4³⁻ emission. With the controlled retention of VO4³⁻ emission, tuning of light emission from the singly (Sm³⁺) doped YP0.8V0.2O4 nanorods is realized. At a particular doping concentration of Sm³⁺ (1.25 at.%), a nearly white light emission is observed. The quantum yield of this nearly white light emission is found to be ∼28%. Tunability of the light and white light emission are supported by CIE chromaticity. The energy transfer efficiency from the VO4³⁻ absorption to the excited states of Sm³⁺ ion in YP0.8V0.2O4 reaches upto ∼86% with the doping concentration of 2.25 at.%.
Keywords: Energy Transfer; Luminescence; Multicolor; Nanorod

Multilocus sequence typing of Ochrobactrum spp. isolated from gastric niche - Kulkarni, Girish (Journal of Infection and Public Health, 2017)
The human stomach is colonized by diverse bacterial species. The presence of non-Helicobacter pylori bacteria in urease-positive biopsies of individuals has been reported. Bacteria belonging to the Ochrobactrum genus have been documented in the human gastric niche. The co-occurrence of Ochrobactrum spp. with H. pylori was previously reported in an antral biopsy of a non-ulcer dyspeptic (NUD) subject from Northern India. There is no information on the genetic diversity of Ochrobactrum spp. isolated from the gastric niche in the stomach. We aimed to study the species distribution and diversity of Ochrobactrum spp. with and without H. pylori in urease-positive biopsies across three different geographical regions in India. Sixty-two Ochrobactrum isolates recovered from patients with an upper gastric disorder (n=218) were subjected to molecular identification and multilocus sequence typing. H. pylori DNA was found in the majority of biopsies, which had a variable degree of Ochrobactrum spp present. Interestingly, some of the urease-positive biopsies only had Ochrobactrum without any H. pylori DNA. Based on phylogenetic analysis, the Ochrobactrum isolates were distributed into the O. intermedium, O. anthropi and O. oryzae groups. This indicates there are multiple species in the gastric niche irrespective of the presence or absence of H. pylori. Antibiotyping based on colistin and polymyxin B could differentiate between O. intermedium and O. anthropi without revealing the resistance-driven diversity. Considering the prevalence of multiple Ochrobactrum spp. in the human gastric niche, it is important to evaluate the commensal and/or pathogenic nature of non-H. pylori bacteria with respect to their geographical distribution, lifestyle and nutrition needs.
Keywords: Helicobater Pyroli; MLST; Non-Ulcer Dyspepsia; Ochrobactrum

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

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

Nanocrystalline Fe-Fe2O3 particledeposited N-doped graphene as an activity-modulated Pt-free electrocatalyst for oxygen reduction reaction - Dhavale, Vishal M.; Singh, Santosh K.; Nadeema, Ayasha; Gaikwad, Sachin S.; Kurungot, Sreekumar (Nanoscale, 2017)

Nano-heteroarchitectures of two-dimensional MoS 2 @ one-dimensional brookite TiO 2 nanorods: prominent electron emitters for displays - Devan, Rupesh S.; Thakare, Vishal P.; Antad, Vivek V.; Chikate, Parameshwar R.; Khare, Ruchita T.; More, Mahendra; Dhayal, Rajendra S.; Patil, Shankar I.; Ma, Yuan-Ron; Schmidt-Mende, Lukas (ACS Omega, 2017)
We report comparative field electron emission (FE) studies on a large-area array of two-dimensional MoS2-coated @ one-dimensional (1D) brookite (β) TiO2 nanorods synthesized on Si substrate utilizing hot-filament metal vapor deposition technique and pulsed laser deposition method, independently. The 10 nm wide and 760 nm long 1D β-TiO2 nanorods were coated with MoS2 layers of thickness ∼4 (±2), 20 (±3), and 40 (±3) nm. The turn-on field (Eon) of 2.5 V/μm required to a draw current density of 10 μA/cm² observed for MoS2-coated 1D β-TiO2 nanorods emitters is significantly lower than that of doped/undoped 1D TiO2 nanostructures, pristine MoS2 sheets, MoS2@SnO2, and TiO2@MoS2 heterostructure-based field emitters. The orthodoxy test confirms the viability of the field emission measurements, specifically field enhancement factor (βFE) of the MoS2@TiO2/Si emitters. The enhanced FE behavior of the MoS2@TiO2/Si emitter can be attributed to the modulation of the electronic properties due to heterostructure and interface effects, in addition to the high aspect ratio of the vertically aligned TiO2 nanorods. Furthermore, these MoS2@TiO2/Si emitters exhibit better emission stability. The results obtained herein suggest that the heteroarchitecture of MoS2@β-TiO2 nanorods holds the potential for their applications in FE-based nanoelectronic devices such as displays and electron sources. Moreover, the strategy employed here to enhance the FE behavior via rational design of heteroarchitecture structure can be further extended to improve other functionalities of various nanomaterials.

Nature of selenium hydrogen bonding: gas phase spectroscopy and quantum chemistry calculations - Mishra, Kamal K.; Singh, Santosh K.; Ghosh, Paulami; Ghosh, Debashree; Das, Aloke (Physical chemistry Chemical physics, 2017)
<div class="block-record-info" style="margin: 0px 22px 22px; list-style: none; padding: 0px; line-height: 20px; font-size: 13px; color: rgb(51, 51, 51); font-family: arial, helvetica, sans-serif; background-color: rgb(248, 248, 248);"> Subsequent to the recent re-definition of hydrogen bonding by the IUPAC committee, there has been a growing search for finding the presence of this ever interesting non-covalent interaction between a hydrogen atom in an X-H group and any other atom in the periodic table. In recent gas phase experiments, it has been observed that hydrogen bonding interactions involving S and Se are of similar strength to those with an O atom. However, there is no clear explanation for the unusual strength of this interaction in the case of hydrogen bond acceptors which are not conventional electronegative atoms. In this work, we have explored the nature of Se hydrogen bonding by studying indole...dimethyl selenide (indmse) and phenol...dimethyl selenide (phdmse) complexes using gas phase IR spectroscopy and quantum chemistry calculations. We have found through various energy decomposition analysis (EDA) methods and natural bond orbital (NBO) calculations that, along with electrostatics and polarization, charge transfer interactions are important to understand Se/S hydrogen bonding and there is a delicate balance between the various interactions that plays the crucial role rather than a single component of the interaction energy. An in-depth understanding of this type of non-covalent interaction has immense significance in biology as amino acids containing S and Se are widely present in proteins and hence hydrogen bonding interactions involving S and Se atoms contribute to the folding of proteins.
Keywords: Center-Dot-O; Clusters; Co-Ordination; Complexes; intermolecular interactions; Proteins; Replacement; spectra; Strength; Sulfur

N-doped porous reduced graphene oxide as an efficient electrode material for high performance flexible solid-state supercapacitor - Singh, S. K.; Dhavale, V. M.; Boukherroub, R.; Kurungot, S.; Szunerits, S. (Applied Materials Today, 2017)
Supercapacitors (SCs) are energy storage devices with an immense potential to resolve energy related issues. Being a low cost, durable and multifunctional material, graphene and its derivatives are the most promising candidates for SCs. Here, we report the synthesis of N-doped porous reduced graphene (N-pGr) and its use for the fabrication of all-solid-state supercapacitor (ASSC) device. The N-pGr exhibited a specific capacitance of 230 F g(-1) at 1 A g(-1) current density and good capacitance retention up to 88% even after 10,000 galvanostatic charge-discharge cycles recorded at 5 A g(-1) fabricated in a solid-state supercapacitor. The synergistic effect of the porosity and N-doping is believed to be the underlying principle for the improved charge storage ability when compared to other reports. Significantly, the porous nature of N-pGr contributes in increasing the electroactive surface area for the formation of electrical double layer as well as facilitating the faster movement of electrolyte ions inside the electrode network. N-doping is believed to change the electrical properties of the electrode material and also to participate in the pseudo-capacitance which helped to boost the overall capacitance of the fabricated device. The good capacitance retention provides the room for making robust flexible solid-state supercapacitor (FSSC) with the N-pGr material.

New bithiazolyl hydrazones: novel synthesis, characterization and antitubercular evaluation - Bhalerao, Mahendra B.; Dhumal, Sambhaji T.; Deshmukh, Amarsinh R.; Nawale, Laxman U.; Khedkar, Vijay M.; Sarkar, Dhiman; Mane, Ramrao A. (Bioorganic & Medicinal Chemistry Letters, 2017)
New bithiazolyl hydrazones (6a–l) have been first time synthesized by carrying novel one pot cyclocondensation of 5-acyl thiazoles (1a–b), thiosemicarbazide (2) and substituted phenacyl chlorides (4a–f) in freshly prepared ionic liquid, diisopropyl ethyl ammonium acetate (DIPEAc) at room temperature. The newly synthesized compounds have been evaluated for their antitubercular activity and the compounds 3b, 6a, 6b, 6d, 6e, 6f, 6g, and 6l have displayed noticeable antitubercular activity compared to Rifampicin with tolerable cytotoxicity. All these compounds were also screened for their antibacterial activity and found that, compounds 6j and 6k have exhibited a very good antibacterial activity. Molecular docking study has shown better harmony with the evaluation trend shown by these compounds under in vitro antitubercular screening.

New insights into the use of multi-mode phenomenological constitutive equations to model extrusion film casting process - Thete, Sumeet S.; Doshi, Pankaj; Pol, Harshawardhan V. (Journal of Plastic Film & Sheeting, 2017)
This article is concerned with the effect of the individual viscoelastic relaxation modes of a polymer melt on its behavior in polymer melt extrusion film casting process. We compare the predicted versus experimentally obtained film necking or neck-in profile as a function of draw ratio. The predicted necking profile was obtained using well-established one-dimensional isothermal flow kinematics and consisted of using two different phenomenological constitutive equations, upper convected Maxwell and Phan-Thien-Tanner, with a discrete spectrum of relaxation times. The numerical simulations, containing the two different phenomenological constitutive equations, provided an insight into the effect of the slow and the fast relaxing modes on the stresses, strains, and strain/extensional rates that develop in the molten polymer film as it is stretched from the die exit to the chill-roll. The slow relaxing modes follow trends that are directly proportional to strain (similar to Hookean solids), whereas the fast relaxing modes follow trends that are directly proportional to the stretch rate (in accordance with Newton's law of viscosity). Comparing the numerical predictions with the experiments showed that predictions using the upper convected Maxwell constitutive equation best described the long-chain branched polymers (like low-density polyethylene, which shows extensional strain hardening) in the extrusion film casting process. On the other hand, predictions using the Phan-Thien-Tanner constitutive equation best described the linear polymers (like linear low-density polyethylene, which does not show noticeable extensional strain hardening) in the extrusion film casting process.

N-Heterocyclic carbene-catalyzed aldol-lactonization of ketoacids via dynamic kinetic resolution - Mondal, Santigopal; Mukherjee, Subrata; Das, Tamal Kanti; Gonnade, Rajesh; Biju, Akkattu T. (ACS Catalysis, 2017)
N-Heteroryclic carbene (NHC)-catalyzed enantioselective aldol lactonization of acyclic ketoacids, proceeding via dynamic kinetic resolution, is presented. The carbene generated from the chiral anninoinclanol-derived triazolium salt in the presence of LiCl was the key for the success of this transformation. The reaction allowed the diastereoselective and enantioselective synthesis of cyclopentane-fused beta-lactones having three contiguous stereocenters. The reaction products are shown to undergo substrate-controlled beta-lactone opening in the presence of amines to afford succinimide derivatives with four contiguous stereocenters.
Keywords: aldol lactonization; beta-lactones; DKR strategies; ketoacids; N-heterocyclic carbenes; organocatalysis

NIR light-triggered shrinkable thermoresponsive PNVCL nanoshells for cancer theranostics - Chauhan, Deepak S.; Singaravelu, Indulekha; Gottipalli, Rupesh; Reddy, B. Pradeep K.; Chikate, Tanmayee; Gupta, Ramkrishn; Jahagirdar, Dushyant N.; Prasad, Rajendra; De, Abhijit; Srivastava, Rohit (RSC Advances, 2017)
For the localized treatment of a tumor in a more controlled fashion, several stimuli-responsive nanocarriers and minimally or non-invasive techniques like photothermal therapy (PTT) have emerged. However, PTT is limited to only treatment of small and superficial tumors due to the inability of NIR light to penetrate more and kill the core cells of large and deep-seated tumors. As a preliminary step towards addressing the problem, NIR light-triggered thermoresponsive theranostic nanoshell consisting of chitosan-grafted poly(N-vinyl caprolactam) as core and biocompatible gold as shell (Au PNVCL NS) are synthesized and well characterized by various techniques. PNVCL is polymerized from N-vinyl caprolactam using free radical polymerization method, and chitosan is grafted to raise its lower critical solution temperature (LCST) to hyperthermic temperature (∼43 °C). Surface plasmon resonant gold shell over PNVCL NPs core is assembled by ascorbic acid-driven in situ reduction. Core to shell diameter ratio is controlled to tune the peak in NIR region (750 nm). Therapeutic potential of Au PNVCL NS is determined over breast cancer cells MCF-7, while diagnostic potential is compared with the commercial contrast agent-Omnipaque.

Nitrogen-doped graphene anchored with mixed growth patterns of CuPt alloy nanoparticles as a highly efficient and durable electrocatalyst for the oxygen reduction reaction in an alkaline medium - Illathvalappil, Rajith; Dhavale, Vishal M.; Bhange, Siddheshwar N.; Kurungot, Sreekumar (Nanoscale, 2017)
A highly active and durable CuPt alloy catalyst with trigonal bipyramidal and truncated cube-type mixed morphologies, anchored on the nitrogen-doped graphene (NGr) surface (CuPt-TBTC/NGr), was prepared by a simple and fast method. The obtained CuPt alloy showed improved oxygen reduction reaction (ORR) activity, with a 30 mV positive shift in the half-wave potential value, as compared to the state-of-the-art Pt/C catalyst in a 0.1 M KOH solution. The CuPt alloy with the trigonal bipyramidal morphology possesses porous type inter-connected sides, which help to achieve improved mass transport of oxygen during the ORR. The exposure of the (111) plane of the CuPt alloy further improved the catalytic activity towards the dioxygen reduction in alkaline media. The ORR activity of the NGr-supported CuPt alloy was found to be dependent on the reaction time, and improved activity was obtained on the material derived at a reaction time of 90 min (CuPt-TBTC/NGr-90). The material synthesized at a lower or higher reaction time than 90 min resulted in a partially formed trigonal bipyramidal morphology with more truncated cubes or agglomerated trigonal bipyramidal and truncated cubes with closed type structures, respectively. Along with the high intrinsic ORR activity, CuPt-TBTC/NGr-90 displayed excellent electrochemical stability. Even after repeated 1000 potential cycling in a window ranging from 0.10 to 1.0 V (vs. RHE), the system clearly outperformed the state-of-the-art Pt/C catalyst with 15 and 60 mV positive shifts in the onset and half-wave potentials, respectively. CuPt-TBTC/NGr-90 also exhibited 2.1 times higher mass activity and 2.2 times higher specific activity, compared to Pt/C at 0.90 V (vs. RHE). Finally, a zinc-air battery fabricated with the alloy catalyst as the air electrode displayed a peak power density of 300 mW cm(-2), which is much higher than the peak power density of 253 mW cm(-2) obtained for the state-of-the-art Pt/C catalyst as the air electrode.

NiZn double hydroxide nanosheet-anchored nitrogen-doped graphene enriched with the gamma-NiOOH phase as an activity modulated water oxidation electrocatalyst - Nadeema, Ayasha; Dhavale, Vishal M.; Kurungot, Sreekumar (Nanoscale, 2017)
Herein, we report a facile solvothermal process to synthesize an active electrocatalyst for the oxygen evolution reaction (OER) in an alkaline medium by anchoring nanosheets of a NiZn double hydroxide over nitrogen doped reduced graphene oxide after enriching the system with the γ-NiOOH phase. This catalyst possesses a thin, porous and open layered structure, which makes the system more efficient and accessible for a better electrochemical water oxidation reaction. Moreover, we experimentally demonstrated that incorporation of Zn via a single-step solvothermal method provides an easy approach to obtain plenty of exposed γ-NiOOH phases to make the system more viable for OER with a small overpotential of 290 mV at 10 mA cm−2 and a Tafel slope of 44 mV per decade. In addition to this, the oxophilic nature of Zn in the (Zn)Ni-LDH/N-rGO catalyst helps to improve the long-term stability of the whole system. The obtained results open up possibilities for the design of future robust OER electrocatalysts by the use of very cheap and abundant materials like Ni and Zn in place of expensive Ir and Ru in the present commercial electrocatalysts.
Keywords: catalysis; Efficient Electrocatalyst; kinetics; Metal; Nickel-Hydroxide; oxide; Oxygen Evolution Reaction; performance; XPS Spectra; zinc

One-step synthesis of a MoS2-CuS composite with high electrochemical activity as an effective counter electrode for CdS/CdSe sensitized solar cells - Kamaja, Chaitanya Krishna; Devarapalli, Rami Reddy; Shelke, Manjusha V. (Chemelectrochem, 2017)
Inorganic nanostructured composite materials involving metal sulfides are increasingly important in electrochemical applications like solar cells. In this research, we have developed a one-step in situ solvothermal method to synthesize a MoS2-CuS composite. MoS2 sheets increase electron-transfer ability, assisting the improvement in catalytic activity of the MoS2-CuS counter electrode. The charge-transfer resistance derived from impedance spectroscopy for the MoS2-CuS composite counter electrode at the electrode/electrolyte interface is very low, as compared to MoS2, mostly owing to the increased number of active catalytic sites for the reduction of polysulfide electrolyte. The Tafel polarization plot shows excellent electrocatalytic activity of the MoS2-CuS composite towards polysulfide electrolyte. Finally, the CdS/CdSe sensitized solar cell achieves a power conversion efficiency of about 5% upon optimization of the MoS2-CuS composition.

Optimization for the production of mycelial biomass from Benjaminiella poitrasii to isolate highly deacetylated chitosan - Mane, S. R.; Pathan, Ejaj K.; Kale, D.; Ghormade, Vandana; Gadre, Ramchandra V.; Rajamohanan, Pattuparambil Ramanpillai; Badiger, Manohar V.; Deshpande, Mukund V. (Journal of Polymer Materials, 2017)
Benjaminiella poitrasii, a dimorphic zygomycetous fungus contains more chitosan in the mycelial cell wall than the cell wall of its yeast form. The optimized medium containing yeast extract, peptone, MgSO4, KH2PO4, trace metals (Fe2+, Mn2+ Zn2+ and Co2+ ) solution and 1% starch produced 10-12 g/L(dry wt.) of mycelial biomass in 48 h in a 2L fermenter. Using 1N NaOH treatment from 1 g of dried biomass 51.00 ± 0.52 mg of chitosan of 42.82 KDa molecular weight and 94.24 % degree of deacetylation was extracted. With Metarhizium anisopliae chitin deacetylase (CDA), chitosan yield was 59.00 ± 0.84 mg while treatment with CDA of B. poitrasii it was 78.05 ± 0.58 mg/g of dry wt. of biomass. The chitosan dissolved in 2% acetic acid showed higher antifungal activity against Candida albicans (MIC90 0.025 mg/mL) and Candida glabrata (MIC90 0.2 mg/mL) than chitosan extracted from marine source (MIC90 >1.6 mg/mL) suggesting use of fungal chitosan in healthcare.

Oral feeding with polyunsaturated fatty acids fosters hematopoiesis and thrombopoiesis in healthy and bone marrow-transplanted mice - Limbkar, Kedar; Dhenge, Ankita; Jadhav, Dipesh D.; Thulasiram, Hirekodathakallu V.; Kale, Vaijayanti; Limaye, Lalita (Journal of Nutritional Biochemistry, 2017)
Hematopoietic stem cells play the vital role of maintaining appropriate levels of cells in blood. Therefore, regulation of their fate is essential for their effective therapeutic use. Here we report the role of polyunsaturated fatty acids (PUFAs) in regulating hematopoiesis which has not been explored well so far. Mice were fed daily for 10 days with n-6/n-3 PUFAs, viz. linoleic acid (LA), arachidonic acid (AA), alpha-linolenic acid and docosahexanoic acid (DHA) in four separate test groups with phosphate-buffered saline fed mice as control set. The bone marrow cells of PUFA-fed mice showed a significantly higher hematopoiesis as assessed using side population, Lin-Sca-1(+)ckit+, colony-forming unit (CFU), long-term culture, CFU-spleen assay and engraftment potential as compared to the control set. Thrombopoiesis was also stimulated in PUFA-fed mice. A combination of DHA and AA was found to be more effective than when either was fed individually. Higher incorporation of PUFAs as well as products of their metabolism was observed in the bone marrow cells of PUFA-fed mice. A stimulation of the Wnt, CXCR4 and Notch1 pathways was observed in PUFA-fed mice. The clinical relevance of this study was evident when bone marrow-transplanted recipient mice, which were fed with PUFAs, showed higher engraftment of donor cells, suggesting that the bone marrow microenvironment may also be stimulated by feeding with PUFAs. These data indicate that oral administration of PUFAs in mice stimulates hematopoiesis and thrombopoiesis and could serve as a valuable supplemental therapy in situations of hematopoietic failure. (C) 2017 Elsevier Inc. All rights reserved.
Keywords: Bone Marrow Transplantation (Bmt); Cord Blood; Down-regulation; Ex-vivo Expansion; Hematopoiesis; Hematopoietic Stem Cells (Hscs); Lipid rafts; Myocardial-infarction; Polyunsaturated Fatty Acids; Progenitor Cells; Prostaglandin-e2; Self-renewal; Spleen Colonies; Stem-cell Proliferation; Thrombopoiesis

Overcoming the lack of oral availability of cyclic hexapeptides: design of a selective and orally available ligand for the integrin alpha v beta 3 - Weinmueller, Michael; Rechenmacher, Florian; Marelli, Udaya Kiran; Reichart, Florian; Kapp, Tobias G.; Raeder, Andreas F. B.; Di Leva, Francesco Saverio; Marinelli, Luciana; Novellino, Ettore; Munoz-Felix, Jose M.; Hodivala-Dilke, Kairbaan; Schumacher, Adi; et al. (Angewandte Chemie-International Edition, 2017)
Ahighly systematic approach for the development of both orally bioavailable and bioactive cyclic N-methylated hexapeptides as high affinity ligands for the integrin alpha v beta 3 is based on two concepts: a) screening of systematically designed libraries with spatial diversity and b) masking of the peptide charge with a lipophilic protecting group. The key steps of the method are 1) initial design of a combinatorial library of Nmethylated analogues of the stem peptide cyclo(d-Ala-Ala(5)); 2) selection of cyclic peptides with the highest intestinal permeability; 3) design of sublibraries with the bioactive RGD sequence in all possible positions; 4) selection of the best ligands for RGD-recognizing integrin subtypes; 5) finetuning of the affinity and selectivity by additional Ala to Xaa substitutions; 6) protection of the charged functional groups according to the prodrug concept to regain intestinal and oral permeability; 7) proof of biological effects in mice after oral administration.

Oxidant mediated one-step complete conversion of multi-walled carbon nanotubes to graphene quantum dots and their bioactivity against mammalian and bacterial cells - Biswas, Anupam; Khandelwal, Puneet; Das, Raja; Salunke, Gayatri; Alam, Aftab; Ghorai, Suvankar; Chattopadhyay, Samit; Poddar, Pankaj (Journal of Materials Chemistry B, 2017)
It is essential for any antibacterial agent (for clinical applications) that it should have high and selective toxicity towards bacterial cells only, and should not affect the human cells at the concentration used. Graphene quantum dots (GQDs) have emerged as a potential candidate for biomedical applications. However, a simple, low cost, safe, easy to execute, one-step synthesis of uniform and monodispersed GQDs with selective toxicity towards bacterial cells rather than mammalian cells is difficult to achieve. Herein, we have reported a one-step, low-cost, aqueous-phase, simple approach for the complete conversion of multi-walled carbon nanotubes into water-dispersible GQDs with an average size of similar to 3 nm using sodium bismuthate (NaBiO3) as a strong oxidant. The cyclic voltammetry and X-ray photoelectron spectroscopy results indicated that the as-synthesized GQDs suspension possess almost negligible amounts of metallic impurities. The cytotoxicity studies of GQDs against mammalian NIH 3T3 (mouse embryo fibroblast cells) and HEK 293T (human embryonic kidney cells) cells showed that the as-synthesized GQDs were non-cytotoxic up to the concentration of similar to 200 mu g mL(-1). The antimicrobial study shows that the synthesized GQDs have high and selective toxicity towards bacterial cells with a minimum inhibitory concentration of similar to 256 mu g mL(-1) for E. coli and B. subtilis and similar to 512 mu g mL(-1) for P. aeruginosa and S. aureus. The scanning electron microscopy and atomic force microscopy images show extensive cell damage via the perturbation of bacterial cell walls, which was consistent with the enhancement of reactive oxygen species production by almost two times in the bacterial cells upon incubation with similar to 256 mu g mL(-1) GQDs. Our study suggested that the as-synthesized GQDs can be used as a potential candidate for clinical applications as they possess high toxicity to bacterial cells and low toxicity to mammalian cells.

Palladium supported on fluorinated magnesium hydroxide: an efficient catalyst for hydrogenation under ambient conditions - Kokane, Reshma S.; Acham, Vaibhav R.; Kulal, Atul B.; Kemnitz, Erhard; Dongare, Mohan K.; Umbarkar, Shubhangi B. (Chemistryselect, 2017)
In this study palladium supported on fluorinated magnesium hydroxide (Pd-MgF2-x(OH)(x)) was synthesized by fluorination of magnesium hydroxide using aqueous HF as fluorinating agent. The Mg(OH)(2) dissolves in HF and precipitates as magnesium hydroxide fluoride. The Pd precursor was added in the same pot during precipitation of MgF2-x(OH)(x). The final catalyst after drying at 250 degrees C has shown very high efficiency for hydrogenation of styrene and range of nitro aromatics at room temperature and atmospheric pressure. Hydrogenation of styrene has led to 37% conversion with 100% selectivity for hydrogenation of double bond after 3 h. The catalyst was successfully recycled for styrene hydrogenation without appreciable loss in the activity. Further hydrogenation of nitro-aromatics was achieved with 99% conversion and 100% aniline selectivity at room temperature and atmospheric pressure. The turnover number of similar to 21774 was obtained for nitrobenzene hydrogenation. The catalyst has shown mesoporous nature (pore volume 0.25 cc/g, pore diameter 4.8 nm) with very high surface area of 106 m(2)/g. The palladium particle size was found to be in the range of 10-11 nm. Acidity measurements by FTIR of adsorbed pyridine revealed presence of Lewis acidic sites with moderate acidity. Mechanistic studies using in-situ FTIR analysis for nitrobenzene hydrogenation revealed activation of nitrobenzene on the Lewis acid sites of the support whereas activation of hydrogen by heterolytic cleavage on Pd center.

Performance of colloidal CdS sensitized solar cells with ZnO nanorods/nanoparticles - Roy, Anurag; Das, Partha Pratim; Tathavadekar, Mukta; Das, Sumita; Devi, Parukuttyamma Sujatha (Beilstein Journal of Nanotechnology, 2017)
As an alternative photosensitizer in dye-sensitized solar cells, bovine serum albumin (BSA) (a nonhazardous protein) was used in the synthesis of colloidal CdS nanoparticles (NPs). This system has been employed to replace the commonly used N719 dye molecule. Various nanostructured forms of ZnO, namely, nanorod and nanoparticle-based photoanodes, have been sensitized with colloidal CdS NPs to evaluate their effective performance towards quantum dot sensitized solar cells (QDSSCs). A polysulphide (S-x(2-))-based electrolyte and CuxS counter electrode were used for cell fabrication and testing. An interesting improvement in the performance of the device by imposing nanorods as a scattering layer on a particle layer has been observed. As a consequence, a maximum conversion efficiency of 1.06% with an open-circuit voltage (V-OC) of 0.67 V was achieved for the ZnO nanorod/nanoparticle assembled structure. The introduction of ZnO nanorods over the nanoparticle led to a significant enhancement of the overall efficiency compared to the corresponding bare nanoparticles.

Phenol oxidative dearomatization of modified nucleoside templates: a simple access to the c7-spiroannulated octosyl acid framework - Mullapudi, Venkannababu; Bhogade, Ravindra B.; Deshpande, Mukund V.; Ramana, Chepuri V. (Synthesis-Stuttgart, 2017)
Phenol oxidative dearomatization and cyclization has been executed successfully on nucleoside templates to synthesize C7-spiroannulated perhydrofuropyran nucleosides and C6-spiroannulated perhydrofurofuran nucleosides as novel analogues of octosyl acid and related peptidyl nucleosides.
Keywords: Analogs; antibiotics; Biosynthesis; Chitin synthase; Derivatives; Ezomycins; Glucose Diacetonide Natural-products; Griseofulvin; Malayamycin; Modified nucleosides; Moiety; Peptidyl Glycosides; Phenol Oxidative Dearomatization; Vorbruggen Glycosylation

Photocatalytic degradation of herbicide by using aeroxide®P-90 TiO2 photocatalyst and photo-fenton process in the presence of artificial and solar radiation - Telang, T.,; Deosarkar, M.P.; Shetty, R.; Kamble, S.P. (Novel water treatment and separation methods: simulation of chemical processes, 2017)
The presence of herbicide residues in the aquatic environment is an emerging issue due to their uncontrolled release through water and accumulation in the environment that may affect living organisms, environment, and public health. Consequently, the efforts are being made to develop the viable methods to eliminate the herbicides from the environment. The degradation of herbicide particularly amitrole has been investigated in aqueous solutions by using artificial and solar radiation. The effect of Aeroxide TiO2 P-90 photocatalyst loading (1-4 g L-1) on photocatalytic degradation of amitrole (50 mg L-1) was investigated. The degradation of amitrole (initial concentration ranging from 20 to 100 mg L-1) also studied by using photo-Fenton process (FeSO4 (10-30 mg L-1) and H2O2 (100-300 mg L-1)). The effect of pH (3-11), effect of co-existing salts (ammonium sulfate, sodium chloride, and sodium carbonate) as well as effect of type of radiation (artificial or solar radiation) on the degradation of amitrole was evaluated and optimized. The degradation of amitrole was accompanied by formation of intermediates which were detected by LC-MS. According to the results presented in this study, the photo-Fenton process using solar radiation is an efficient technique for degradation of amitrole.

Photo-induced cytotoxicity and anti-metastatic activity of ruthenium(II)-polypyridyl complexes functionalized with tyrosine or tryptophan - Ramu, Vadde; Aute, Sunil; Taye, Nandaraj; Guha, Rweetuparna; Walker, Michael G.; Mogare, Devaraj; Parulekar, Apoorva; Thomas, Jim A.; Chattopadhyay, Samit; Das, Amitava (Dalton Transactions, 2017)
The synergistic effect of oxygen, light, and photosensitizer (PS) has found applications in medicine for the treatment of cancer through photodynamic therapy (PDT). Induction of apoptosis to cancerous cells will prevent tumor metastasis that spreads cancer cells to the neighboring organs/tissues. Herein, we report the two apoptotic Ru(II)-polypyridyl complexes that are functionalized with pendant amino acid moieties tyrosine (1) and tryptophan (2), respectively. These two water soluble complexes were found to interact strongly (K-a(1) = (1.18 +/- 0.28) x 10(5) M-1 and K-a(2) = (1.57 +/- 0.77) x 10(5) M-1) with CT-DNA. Isothermal titration calorimetry (ITC) studies revealed that these complexes bind to CT-DNA through an entropically driven process. Both the complexes showed photo-induced cytotoxicity and exhibit apoptotic activity under photo-irradiation conditions. The comet assay indicated that these complexes can damage cellular DNA, which is attributed to the significant build-up of O-1(2) level even on irradiation with low intensity light (10 J cm(-2), lambda(Range) 450-480 nm). This photoinduced DNA damage and apoptosis in A549 cells was induced by reactive oxygen species (ROS) and occurred through up-regulation of apoptotic marker caspase-3. Control experiments under dark conditions revealed an insignificant cytotoxicity towards these cells for two photosensitive molecules.

Photovoltaic and photocatalytic performance of electrospun Zn2SnO4 hollow fibers - Das, P. P.; Roy, A .; Tathavadekar, M.; Devi, P. S. (Applied Catalysis B, 2017)
The phase pure hollow Zn2SnO4 and green emitting ZnO-SnO2-Zn2SnO4 composite fiber have been prepared by post calcining the as formed fiber by electrospin technique. Depending upon the calcination temperature, the as prepared fiber exhibited a striking variation in composition, microstructure, optical and photo-electrochemical properties. The composition dependent dissimilarity in photovoltaic performance and photocatalytic activity has been established in this work. A relatively enhanced open circuit voltage (Voc) of 0.76 V, fill factor (FF) of 59.78%, short circuit current Qsc) of 4.2 mA/cm(2) and an overall conversion efficiency (n) of 1.93% have been achieved for the phase pure Zn2SnO4 porous fiber obtained at the elevated calcination temperature of 1000 degrees C. On the contrary, a relatively reduced Voc, FF, J(sc) and n of 0.70 V, 42.54%, 3.8 mA/cm(2) and 1.17%, respectively, have been achieved for the 800 degrees C calcined dense fiber consisting of a mixture of three distinct phases ZnO, SnO2 and Zn2SnO4. Unlike photovoltaic behaviour the trend in photocatalytic performance interestingly got reversed for the ZnO-nO(2)-Zn2SnO4 composite fiber owing to its superior photo-induced charge separation ability followed by generation of larger amount of active hydroxyl radicals (OFF). Our results establish the composite fiber as a preferred photocatalyst in comparison to phase pure Zn2SnO4 towards the textile dyes Methylene blue and Congo red and non absorbing organic pollutants such as Phenol and Bisphenol A under UV illumination.

Phytase production by aspergillus niger NCIM 563 for a novel application to degrade organophosphorus pesticides - Shah, Parin C.; Kumar, V. Ravi; Dastager, Syed G.; Khire, Jayant M. (AMB Express, 2017)
The production of phytase using Aspergillus niger NCIM 563 under submerged fermentation conditions was studied using protein rich chickpea flour as substrate. Employing a hybrid statistical media optimization strategy of Plackett-Burman and Box-Behnken experimental designs in shake-flasks gave an increased phytase activity from an initial 66 IU/mL in 216 h to 160 IU/mL in a reduced time of 132 h. Productivity, thus increased by 3.97 times from 7.3 to 29 IU/mL/day. Using the optimized media, the production was successfully scaled-up further and improved up to 164 IU/mL in 96 h by studies carried out employing 2 and 10-L fermenters. The enzyme supernatant was recovered using centrifugal separation of biomass and the stability of the produced phytase was tested for animal feed applications under gastric conditions. In vitro degradation studies of water soluble monocrotophos, methyl parathion and water insoluble chlorpyrifos, pesticides used extensively in agriculture was carried out. It was observed by HPLC analysis that phytase could degrade 72% of chlorpyrifos at pH 7.0, 35 degrees C. Comparable results were obtained with monocrotophos and methyl parathion. With chlorpyrifos at higher temperature 50 degrees C as much as 91% degradation could be obtained. The degradation of chlorpyrifos was further validated by spraying phytase on harvested green chilli ( Capsicum annuum L) under normal conditions of pH 7.0, 35 degrees C and the degradation products obtained analyzed by LCMS. Thus, the present study brings out a potentially novel application of phytase for biodegradation of organophosphorus pesticides.

Polylactic acid (PLA) biocomposites filled with waste leather buff (WLB) - Ambone, Tushar; Joseph, Seena; Deenadayalan, E.; Mishra, Satyendra; Jaisankar, S.; Saravanan, P. (Journal of Polymers and the Environment, 2017)
A large amount of leather waste is generated from tanning industries and most of which are disposed of landfill or discharged into the natural water bodies without any treatment, causing environmental problems. The aim of this study is to develop eco-biocomposites using waste leather buff (WLB) as filler in Polylactic acid (PLA) matrix to reduce the environmental issues and provide sustainable solution. WLB/PLA composites were prepared by twins-screw micro extruder varying the WLB content from 2% to 30 wt%. These composite were extensively characterise by several techniques. Tensile properties of the composites showed addition of WLB resulted in improvement of tensile property of composite and reduction in percentage crystallinity of PLA matrix observed with increase in WLB content. The effect of WLB on properties of interfacial adhesion and dispersion in WLB/PLA composites were studied by SEM. Wettability of composites was tested by contact angle and water absorption studies. WLB/PLA composite showed increase in water absorption with WLB loading. These WLB/PLA composite could be used to develop low cost eco-friendly product material.

Polymerization-incompetent uromodulin in the pregnant stroke-prone spontaneously hypertensive rat - Mary, Sheon; Small, Heather Yvonne; Siwy, Justyna; Mullen, William; Giri, Ashok; Delles, Christian (Hypertension, 2017)
The kidney is centrally involved in blood pressure regulation and undergoes extensive changes during pregnancy. Hypertension during pregnancy may result in an altered urinary peptidome that could be used to indicate new targets of therapeutic or diagnostic interest. The stroke-prone spontaneously hypertensive rat (SHRSP) is a model of maternal chronic hypertension. Capillary electrophoresis-mass spectrometry was conducted to interrogate the urinary peptidome in SHRSP and the control Wistar-Kyoto strain at three time points: prepregnancy and gestational days 12 and 18. The comparison within and between the Wistar-Kyoto and SHRSP peptidome at all time points detected 123 differentially expressed peptides (fold change >1.5; P<0.05). Sequencing of these peptides identified fragments of collagen a-chains, albumin, prothrombin, actin, serpin A3K, proepidermal growth factor, and uromodulin. Uromodulin peptides showed a pregnancy-specific alteration in SHRSP with a 7.8-fold (P<0.01) and 8.8-fold (P<0.05) increase at gestational days 12 and 18, respectively, relative to the Wistar-Kyoto. Further investigation revealed that these peptides belonged to the polymerization-inhibitory region of uromodulin. Two forms of uromodulin (polymerization competent and polymerization incompetent) were found in urine from both Wistar-Kyoto and SHRSP, where the polymerizationincompetent form was increased in a pregnancy-specific manner in SHRSP. Nifedipine-treated pregnant SHRSP showed only polymerization-competent uromodulin, indicating that calcium may be mechanistically involved in uromodulin polymerization. This study highlights, for the first time, a potential role of uromodulin and its polymerization in hypertensive pregnancy.
Keywords: Hypertension; Kidney; Nifedipine; pregnancy; uromodulin

Polyphenylene sulfide- expanded graphite nanocomposites: processing route dependent electrical percolation - Ramanujam, B. T. S.; Radhakrishnan, S.; Deshpande, S. D. (Journal of Thermoplastic Composite Materials, 2017)
Polyphenylene sulfide (PPS)-expanded graphite (ExGr) conducting nanocomposites have been prepared by powder mixing and in situ polymerization routes after sonicating ExGr particles in acetone. Synthesized PPS has been used to make powder mixed composites. The powder mixed composites exhibit a percolation threshold of 3 wt% due to the formation of graphite nanosheets. When PPS-ExGr composites are prepared by in situ polymerization route, very low electrical percolation threshold less than 0.5 wt% ExGr is obtained. The low percolation threshold obtained is attributed to better dispersion of ExGr nanosheets in the polymer matrix when compared to powder mixed composites. The synthesized PPS has been characterized by X-ray diffraction, differential scanning calorimetry, and infrared spectroscopy. The formation of graphite nanosheets has been confirmed by transmission and scanning electron microcopy analysis.

Polypropylene-based conducting nanocomposites: effect of aspect ratio of second conducting filler on the electrical percolation - Ramanujam, B. T. S.; Radhakrishnan, S.; Deshpande, S. D. (Journal of Thermoplastic Composite Materials, 2017)
Powder-mixed polypropylene (PP)-graphite binary composites exhibit an electrical percolation threshold at 10 wt% graphite signifying insulator-semiconductor transition. Three conducting fillers such as carbon black (CB), sonicated expanded graphite (s-ExGr), and carbon nanofiber (CNF) are mixed with PP-7 wt% graphite binary composites. The electrical percolation threshold has been found to have inverse relation to the aspect ratio of second conducting fillers in hybrid composites. The aspect ratio of second conducting fillers varies in the order CB < ExGr < CNF. The electrical percolation threshold is found to vary for the hybrid composites as 2.2 wt% for CB addition, 0.75 wt% for ExGr addition, and 0.2 wt% for CNF addition in the PP-7 wt% graphite binary composites. When the aspect ratio of second conducting fillers increases, they reduce the barrier for the charge transport. The second conducting fillers occupy the interspace of graphite and alternating current studies show that the effective dielectric constant increases with the concentration of second conducting filler in the hybrid composites. The composites are characterized by transmission electron microscopy and scanning electron microscopy. Melt-crystallized PP-7 wt% graphite-CNF composites exhibit higher percolation threshold due to decrease in the polymer viscosity which increases the interparticulate distance.
Keywords: carbon nanofiber; Conducting polymer composites; Electrical properties; graphite nanosheets; hybrid composites; percolation; scanning; transmission electron microscopy

Porous reduced graphene oxide modified electrodes for the analysis of protein aggregation. part 1: lysozyme aggregation at pH 2 and 7.4 - Vasilescu, Alina; Boulahneche, Samia; Chekin, Fereshteh; Gaspar, Szilveszter; Medjram, Mohamed Salah; Diagne, Abdou Aziz; Singh, Santosh K.; Kurungot, Sreekumar; Boukherroub, Rabah; Szunerits, Sabine (Electrochimica Acta, 2017)
Protein instability due to misfolding and aggregation is of big concern for protein based therapeutics because it impacts the bioavailability and immunogenicity of such drugs. The development of simple and cost-effective methods for the analysis of pharmaceutical formulations, indicating the presence or absence of protein aggregates, is consequently of high importance. This work proposes a novel electrochemical interface based on porous reduced graphene oxide coated glassy carbon electrode (GC/prGO) allowing for the early and sensitive identification of protein aggregation by following the change in the oxidative current of the proteins. The novelty of this work lies in the exploration of the ability of GC/prGO interfaces to capture different aggregation behaviors. Lysozyme is used as a model to follow by electrochemistry its aggregation at two pH values, pH 2 and pH 7.4, leading to the formation of amyloid and amorphous aggregates, respectively. Comparing the oxidation peak of lysozyme by differential pulse voltammetry (DPV) for different electrode architectures allowed validating the higher sensitivity of the GC/prGO interface versus bare glassy electrodes or electrodes coated with non-porous reduced graphene oxide. Parallel experiments were performed by fluorescence with thioflavin T, size exclusion chromatography and Atomic Force Microscopy (AFM) imaging. These tests further highlighted the usefulness of GC/prGO electrode to visualize in a fast and reliable manner the changes in the protein structure and the differences between the processes occurring at pH 2 and pH 7.4. In particular, the ability to emphasize changes related to the first steps in aggregation that could be indicative of the aggregation course, recommend the GC/prGO electrode in combination with DPV as a new analytical tool for aggregation studies of biopharmaceuticals. Part 2 of this work will demonstrate later the utility of this approach for the analysis of a fast acting injectable human insulin formulation, Humulin R, used for diabetes treatment as well as for calcitonin. (C) 2017 Elsevier Ltd. All rights reserved.

Processing and characterization of waste leather based polycaprolactone biocomposites - Joseph, Seena; Ambone, Tushar S.; Salvekar, Abhijit V.; Jaisankar, S. N.; Saravanan, P.; Deenadayalan, E. (Polymer Composites, 2017)
Waste leather buff (WLB) filled polycaprolactone (PCL) composites were prepared by twin-screw extrusion varying the WLB content from 2% to 40%. These composites were extensively characterized by several techniques in order to establish micro and macroscopic properties. Addition of WLB resulted in improvement of tensile modulus of neat PCL and reduction in percentage crystallinity of PCL matrix was observed with increase in WLB content. Interfacial adhesion and dispersion of WLB on PCL matrix was investigated using Scanning Electron Microscope. Percentage of water uptake increased with increase in concentration of WLB in the composite. These biodegradable composites could be used to develop low cost materials suitable for applications in footwear industry, for making bags, suitcases, etc., eliminating the environmental issues arising from WLB generated from tanneries in leather industry. POLYM. COMPOS., 38:2889-2897, 2017. (c) 2015 Society of Plastics Engineers

Promotional effect of WOx in Pt-WOx/AlPO4-5 catalyzed deoxygenation of fatty acids - Janampelli, Sagar; Darbha, Srinivas (ChemistrySelect, 2017)
WOx promoted Pt/AlPO4-5 catalysts with varying Pt and W contents were prepared by wet-impregnation method and characterized. Catalysts with Pt to W weight ratio of 1: 2 exhibited higher catalytic performance than the other compositions in deoxygenation of oleic acid (OA). WOx enhanced significantly the catalytic activity of Pt and enabled quantitative conversion of OA to linear alkanes (predominantly C-18/C-17) at a temperature as low as 280 degrees C. It changed the reaction pathway from decarbonylation/ decarboxylation (DCO for Pt/AlPO4-5) to hydrodeoxygenation (HDO for Pt-WOx/AlPO4-5). It affected the particle size and redox behaviour of Pt. The enhanced H-spill over (by 14.8%) and presence of strong acid sites (300 - 500 degrees C) are the cause for the high activity of Pt-WOx/AlPO4-5 catalysts even at lower temperatures. Partially reduced WOx activates OA and leads to the HDO product (C-18). In the absence of WOx, Lewis acid sites of the support activate OA through the C=O group and Pt facilitates C-C cleavage and formation of DCO product (C-17).
Keywords: biofuels; Deoxygenation; Fatty acids; Green Diesel; Hydrocarbons

Proton conduction in a hydrogen-bonded complex of copper(II)-bipyridine glycoluril nitrate - Tayade, Sakharam B.; Dhavale, Vishal M.; Kumbhar, Avinash S.; Kurungot, Sreekumar; Loennecke, Peter; Hey-Hawkins, Evamarie; Pujari, Bhalchandra (Dalton Transactions, 2017)
Bipyridine glycoluril (BPG), a urea-fused bipyridine tecton, forms a square-pyramidal secondary building unit with copper(II) which further self-assembles to give a porous hydrogen-bonded complex. This complex displays a high proton conductivity of 4.45 x 10(-3) S cm(-1) at 90 degrees C and 95% relative humidity (RH). Chains consisting of coordinated water, solvent water and nitrate anions embedded in the complex are responsible for high proton conduction. The proton conduction pathway was corroborated by ab initio electronic structure calculations with molecular dynamics (MD) simulations using the Nudged Elastic Band (NEB) method. The theoretical activation energy estimated to be 0.18 eV is in close agreement with the experimental value of 0.15 eV which evidences a Grotthuss proton hopping mechanism. We thus demonstrate that the hydrogen-bonded complex encapsulating appropriate counter ions, coordinated water and solvent water molecules exhibts superprotonic conductivity.

Proton-coupled electron-transfer processes in ultrafast time domain: evidence for effects of hydrogen-bond stabilization on photoinduced electron transfer - Dey, Ananta; Dana, Jayanta; Aute, Sunil; Maity, Partha; Das, Amitava; Ghosh, Hirendra N. (Chemistry-A European Journal, 2017)
The proton-coupled electron-transfer (PCET) reaction is investigated for a newly synthesized imidazoleanthraquinone biomimetic model with a photoactive RuIIpolypyridyl moiety that is covalently coupled to the imidazole fragment. Intramolecular H-bonding interactions between imidazole and anthraquinone moieties favor the PCET process; this can be correlated to an appreciable positive shift in the one-electron reduction potential of the coordinated anthraquinone moiety functionalized with the imidazole fragment. This can also be attributed to the low luminescence quantum yield of the RuII-polypyridyl complex used. The dynamics of the intramolecular electron-transfer (ET) and PCET processes are studied by using femtosecond transient absorption spectroscopy. The steady- state spectroscopic studies and the results of the time- resolved absorption studies confirm that H- bonded water molecules play a major role in both ET and PCET dynamics as a proton relay in the excited state. The electron- transfer process is followed by a change in the H- bonding equilibrium between AQ and imidazole in acetonitrile solvent, and protonation of AQ(-) water leads to PCET in the presence of water. A slower forward and backward electron- transfer rate is observed in the presence of D2O compared with that in H2O. These results provide further experimental support for a detailed understanding of the PCET process.

Rapid synthesis of highly monodispersed silver nanoparticles from the leaves of Salvadora persica - Khan, Mamatha R. Shadab; Salunkhe, Pooja; Satpute, Shruti; Kendurkar, Shuchishweta; Prabhune, Asmita; Deval, Animesh; Chaudhari, Bhushan P. (Materials Letters, 2017)
We have demonstrated a one pot green protocol for the synthesis of highly monodispersed silver nanoparticles using leaves of Salvadora persica plant. When the leaf extract of Salvadora persica plant reacted with silver nitrate (AgNO3) solution it resulted in the synthesis of highly monodispersed silver nanoparticles with an average size of 3 nm. These nanoparticles were then completely characterized by UV-Visible spectroscopy, Transmission Electron Microscopy, Energy Dispersive Analysis of X-Rays, X-ray diffraction analysis and Fourier Transform Infrared analysis. (C) 2017 Elsevier B.V. All rights reserved.

Ratiometric sensor for DNA based on a dual emission Ru(dppz) light-switch complex - Walker, Michael G.; Ramu, Vadde; Meijer, Anthony J. H. M.; Das, Amitava; Thomas, Jim A. (Dalton Transactions, 2017)
Herein we describe the DNA binding properties of two new water-soluble ruthenium complexes; experimental and computational data reveal that both complexes display dual emission from MLCT and LLCT excited states. The interaction of the new complexes with DNA was also investigated. Although one of the complexes only binds DNA though groove binding, the second complex has separate ligands capable of groove binding and intercalation. Nevertheless, it was found that both complexes interact with duplex DNA with high affinity. DNA induced distinctive changes in the emission of the complexes; although the groove binding complex only displays a modest increase in emission on binding, the complex that contains the intercalating Ru-II(dppz) moiety displays a large increase in MLCT-based emission on DNA binding while emission from the LLCT excited state is unaffected. This means that the complex functions as the first ratiometric sensor for DNA.

Reactivity of difunctional polar monomers and ethylene copolymerization: a comprehensive account - Gaikwad, Shahaji R.; Deshmukh, Satej S.; Koshti, Vijay S.; Poddar, Suparna; Gonnade, Rajesh G.; Rajamohanan, Pattuparambil R.; Chikkali, Samir H. (Macromolecules, 2017)
A comprehensive picture of insertion of 1,1-disubstituted difunctional olefins, their ability to double the functional group density at the same level of incorporation as that of monofunctional olefin, and copolymerization with ethylene has been demonstrated. Exposure of a palladium complex [P boolean AND OPdMe(L)] (P boolean AND O = kappa(2)-P,O-Ar2PC6H4SO2O with Ar = 2-MeOC6H4.; L = C2H6OS) to methyl 2-acetamidoacrylate (MAAA) revealed slight preference for 1,2-insertion over 2,1-insertion (1.0:0.7). In contrast, insertion of electron-deficient 2-(trifluoromethyl)acrylic acid (TFMAA) unveiled selective 2,1-insertion {via [(P boolean AND O)PdC5H6F3O2] (11)1. The unstable intermediate 11 undergoes beta-hydride and beta-fluoride elimination to produce subsequent insertion and elimination products. The identity of elimination products (E/Z)-2-trifluoromethyl)but-2-enoic acid [17(E/Z)] and 2-(difluoromethylene)butanoic acid (13) was fully established by 1-2D NMR spectroscopy. These insertion experiments, taken together with insertion rates, suggest that MAAA and TFMAA. are amenable to insertion. Polymerization of ethylene with MAAA, TFMAA, acetamidoacrylic acid, 2-bromoacrylic acid, dimethyl allylmalonate, and allylmalonic acid was catalyzed by [P boolean AND OPdMe(L)] (L = C2H3N) (S.ACN), and the highest incorporation of 11.8% was observed for dimethyl allylmalonate (DMAM). The changes in the surface properties of the copolymers after incorporation of difunctional olefins were evaluated by measuring the water contact angle. Copolymer with highest (11.8% of DMAM) incorporation revealed a reduced water contact angle of 76 degrees. These findings demonstrate that 1,1-disubstituted difunctional olefins are amenable to polymerization, and incorporation of difunctional olefins In polyethylene backbone leads to the production of relatively hydrophilic polyethylene copolymers.

Recovery of radio-cesium from actual high level liquid waste using solvents containing calix[4]arene-crown-6 ligands - Jagasia, P.; Dhami, P. S.; Mohapatra, P. K.; Ansari, S. A.; Jadhav, S. Y.; Kalyankar, G. K.; Gandhi, P. M.; Kharul, U. K. (Journal of Environmental Chemical Engineering, 2017)
This paper gives two methods, viz. a solvent extraction method and a hollow fiber contactor based liquid membrane method, for the separation of radio-cesium from actual high level liquid waste (HLLW) solutions using calix[4]arene-crown-6 based solvent systems. While the solvent extraction method involved calix[4]arene-bis-benzo-crwon-6 (CBC) in PTMS (phenyltrifluoromethyl sulphone), the hollow fiber supported liquid membrane method used a polysulphone fiber containing contactor and bis-octyl-benzo-calix[4]arene-mono-crown-6 (CMC) in 40% iso-decanol + 60% n-dodecane. Both methods reported selective radio-cesium separation with almost no contamination from the associated fission product radionuclides. The radiolytic stability of the hollow fiber contactor was checked by keeping the contactor module in contact with the diluted HLLW for 50 days. The second run carried out after 50 days resulted in excellent reproducibility suggesting efficacy of this method for radioactive waste remediation.
Keywords: 137Cs; Calix-crown-6; Cesium; fibers; Fission products; Hollow fiber contactor; Liquid membranes; liquids; PUREX-HLLW; Radioactive wastesSolvent extraction; solvent extraction; Solvents

Repurposing Ivacaftor for treatment of staphylococcus aureus infections - Thakare, R.; Das, S.; Vasudevan, N.; Jachak, G.R.; Reddy, D.S.; Dasgupta, A.; Chopra, S. (International Journal of Antimicrobial Agents, 2017)
Drug repurposing of non-antimicrobials is a novel method to augment a seriously depleted drug pipeline for targeting drug–resistant pathogens. This article highlights the potent antimicrobial activity of Ivacaftor against Staphylococcus aureus, including vancomycin– and other multidrug–resistant strains. The potent activity of Ivacaftor in vivo is also demonstrated in a murine neutropenic thigh infection model. Taken together, these results support the potential of Ivacaftor as an antimicrobial agent for the treatment of staphylococcal infections. © 2017 Elsevier B.V. and International Society of Chemotherapy

Resistin mediates sex-dependent effects of perivascular adipose tissue on vascular function in the shrsp - McNeilly, Sarah; Small, Heather Y.; Mary, Sheon; Sheikh, Adam; Delles, Christian (20th Annual Meeting of the Scottish-Cardiovascular-Forum, 2017)

Resolution of the identity and cholesky representation of EOM-MP2 approximation: implementation, accuracy and efficiency - Kumar, Dinesh; Dutta, Achintya Kumar; Manohar, Prashant Uday (Journal of Chemical Sciences, 2017)
We present a Resolution of Identity and Cholesky Decomposition Based Implementation of EOM-MP2 approximation. The RI and CD based EOM-MP2 shows significant speed-up and less storage requirement than the conventional canonical version and can be applied to very large systems. The new algorithm used for this implementation eliminates the most storage requiring four-index quantities resulting in the decrease of storage requirement, reduction in I/O penalties and improved parallel performance, at the expense of more floating point operations. Therefore, the speed-up compared to conventional EOM-MP2 method is more prominent in case of EA, EE and SF case where the storage bottleneck is significant than the EOM-IP-MP2 method, where the storage requirement is significantly less. However, the RI/CD based EOM-IP-MP2 can be coupled with frozen natural orbitals to gain further speed-up.
Keywords: CC; CD; Cholesky decomposition; EA; EE; electron attachment; electron correlation; EOM; equation-of-motion; excited state; ionization; IP; MP2; Resolution-of-identity; RI; SF; spinflip

Revisiting HOPG superlattices: structure and conductance properties - Patil, Sumati; Kolekar, Sadhu; Deshpande, Aparna (Surface Science, 2017)
Superlattices observed on highly oriented pyrolytic graphite (HOPG) have been studied extensively by scanning tunnelling microscopy (STM). The interest in the study of graphite superlattices has seen a resurgence since the discovery of graphene. Single layer graphene, bilayer graphene, and few layer graphene can now be grown on different substrates. The adherence of graphene to various substrates often leads to a periodic out-of-plane modulation and superlattices due to lattice mismatch. In this paper, we report STM imaging and scanning tunnelling spectroscopy (STS) of different kinds of superlattices on HOPG characterized by a variation in lattice periodicities. Our study also shows evidence of the displacement of the topmost HOPG layer by scanning different areas of the same superlattice. A correlation between the lattice periodicity with its conductance properties is derived. The results of this work are important for understanding the origin of the superlattice structure on HOPG. Investigation of such superlattices may open up possible ways to modify two dimensional electron systems to create materials with tailored electronic properties.

Role of spatial inhomogenity in GPCR dimerisation predicted by receptor association-diffusion models - Deshpande, Sneha A.; Pawar, Aiswarya B.; Dighe, Anish; Athale, Chaitanya A.; Sengupta, Durba (Physical Biology, 2017)
G protein-coupled receptor (GPCR) association is an emerging paradigm with far reaching implications in the regulation of signalling pathways and therapeutic interventions. Recent super resolution microscopy studies have revealed that receptor dimer steady state exhibits sub-second dynamics. In particular the GPCRs, muscarinic acetylcholine receptor M-1 (M1MR) and formyl peptide receptor (FPR), have been demonstrated to exhibit a fast association/dissociation kinetics, independent of ligand binding. In this work, we have developed a spatial kinetic Monte Carlo model to investigate receptor homo-dimerisation at a single receptor resolution. Experimentally measured association/dissociation kinetic parameters and diffusion coefficients were used as inputs to the model. To test the effect of membrane spatial heterogeneity on the simulated steady state, simulations were compared to experimental statistics of dimerisation. In the simplest case the receptors are assumed to be diffusing in a spatially homogeneous environment, while spatial heterogeneity is modelled to result from crowding, membrane micro-domains and cytoskeletal compartmentalisation or 'corrals'. We show that a simple association-diffusion model is sufficient to reproduce M1MR association statistics, but fails to reproduce FPR statistics despite comparable kinetic constants. A parameter sensitivity analysis is required to reproduce the association statistics of FPR. The model reveals the complex interplay between cytoskeletal components and their influence on receptor association kinetics within the features of the membrane landscape. These results constitute an important step towards understanding the factors modulating GPCR organisation.

Role of the pair correlation function in the dynamical transition predicted by mode coupling theory - Nandi, Manoj Kumar; Banerjee, Atreyee; Dasgupta, Chandan; Bhattacharyya, Sarika Maitra (Physical Review Letters, 2017)
In a recent study, we have found that for a large number of systems the configurational entropy at the pair level S-c2, which is primarily determined by the pair correlation function, vanishes at the dynamical transition temperature T-c. Thus, it appears that the information of the transition temperature is embedded in the structure of the liquid. In order to investigate this, we describe the dynamics of the system at the mean field level and, using the concepts of the dynamical density functional theory, show that the dynamical transition temperature depends only on the pair correlation function. Thus, this theory is similar in spirit to the microscopic mode coupling theory (MCT). However, unlike microscopic MCT, which predicts a very high transition temperature, the present theory predicts a transition temperature that is similar to T-c. This implies that the information of the dynamical transition temperature is embedded in the pair correlation function.

Secondary interactions arrest the hemiaminal intermediate to invert the modus operandi of schiff base reaction: a route to benzoxazinones - Patel, Ketan; Deshmukh, Satej S.; Bodkhe, Dnyaneshwar; Mane, Manoj; Vanka, Kumar; Shinde, Dinesh; Rajamohanan, Pattuparambil R.; Nandi, Shyamapada; Vaidhyanathan, Ramanathan; Chikkali, Samir H. (Journal of Organic Chemistry, 2017)
Discovered by Hugo Schiff, condensation between amine and aldehyde represents one of the most ubiquitous reactions in chemistry. This classical reaction is widely used to manufacture pharmaceuticals and fine chemicals. However, the rapid and reversible formation of Schiff base prohibits formation of alternative products, of which benzoxazinones are an important class. Therefore, manipulating the reactivity of two partners to invert the course of this reaction is an elusive target. Presented here is a synthetic strategy that regulates the sequence of Schiff base reaction via weak secondary interactions. Guided by the computational models, reaction between 2,3,4,5,6-pentafluoro-benzaldehyde with 2-amino-6methylbenzoic acid revealed quantitative (99%) formation of 5-methyl-2-(perfluoropheny01,2-dihydro-4H-benzo[d][1,3]oxazin-4-one (15). Electron donating and electron withdrawing ortho-substituents on 2-aminobenzoic acid resulted in the production of benzoxazinones 936. The mode of action was tracked using low temperature NMR, IN vis spectroscopy, and isotopic (O-18) labeling experiments. These spectroscopic mechanistic investigations revealed that the hemiaminal intermediate is arrested by the hydrogen-bonding motif to yield benzoxazinone. Thus, the mechanistic investigations and DFT calculations categorically rule out the possibility of in situ imine formation followed by ring-closing, but support instead hydrogen-bond assisted ring-closing to prodrugs. This unprecedented reaction represents an interesting and competitive alternative to metal catalyzed and classical methods of preparing benzoxazinone.

Selection of reference genes for quantitative real-time RT-PCR assays in different morphological forms of dimorphic zygomycetous fungus Benjaminiella poitrasii - Pathan, Ejaj K.; Ghormade, Vandana; Deshpande, Mukund V. (Plos One, 2017)
Benjaminiella poitrasii, a dimorphic non-pathogenic zygomycetous fungus, exhibits a morphological yeast (Y) to hypha (H) reversible transition in the vegetative phase, sporangiospores (S) in the asexual phase and zygospores (Z) in the sexual phase. To study the gene expression across these diverse morphological forms, suitable reference genes are required. In the present study, 13 genes viz. ACT, 18S rRNA, eEF1a, eEF-Tu, eIF-1A, Tuba, Tub-b, Ubc, GAPDH, Try, WS-21, NADGDH and NADPGDH were evaluated for their potential as a reference, particularly for studying gene expression during the Y-H reversible transition and also for other asexual and sexual life stages of B. poitrasii. Analysis of RT-qPCR data using geNorm, normFinder and BestKeeper software revealed that genes such as Ubc, 18S rRNA and WS-21 were expressed at constant levels in each given subset of RNA samples from all the morphological phases of B. poitrasii. Therefore, these reference genes can be used to elucidate the role of morpho-genes in B. poitrasii. Further, use of the two most stably expressed genes (Ubc and WS-21) to normalize the expression of the ornithine decarboxylase gene (Bpodc) in different morphological forms of B. poitrasii, generated more reliable results, indicating that our selection of reference genes was appropriate.

Selective C-H bond oxidation catalyzed by the Fe-bTAML complex: mechanistic implications - Ghosh, M. (Inorganic Chemistry, 2017)
Nonheme iron complexes bearing tetradentate N-atom-donor ligands with cis labile sites show great promise for chemoselective aliphatic C-H hydroxylation. However, several challenges still limit their widespread application. We report a mechanism-guided development of a peroxidase mimicking iron complex based on the bTAML macrocyclic ligand framework (Fe-bTAML: biuret-modified tetraamido macrocyclic ligand) as a catalyst to perform selective oxidation of unactivated 3° bonds with unprecedented regioselectivity (3°:2° of 110:1 for adamantane oxidation), high stereoretention (99%), and turnover numbers (TONs) up to 300 using mCPBA as the oxidant. Ligand decomposition pathways involving acid-induced demetalation were identified, and this led to the development of more robust and efficient Fe-bTAML complexes that catalyzed chemoselective C-H oxidation. Mechanistic studies, which include correlation of the product formed with the FeV(O) reactive intermediates generated during the reaction, indicate that the major pathway involves the cleavage of C-H bonds by FeV(O). When these oxidations were performed in the presence of air, the yield of the oxidized product doubled, but the stereoretention remained unchanged. On the basis of 18O labeling and other mechanistic studies, we propose a mechanism that involves the dual activation of mCPBA and O2 by Fe-bTAML, leading to formation of the FeV(O) intermediate. This high-valent iron oxo remains the active intermediate for most of the reaction, resulting in high regio- and stereoselectivity during product formation.

Selective molecular separation by interfacially crystallized covalent organic framework thin films - Dey, K.; Das, A; Mukherjee, R.; Kharul, U. K.; Banerjee, R. (Journal of the American Chemical Society, 2017)
Exponential interest in the field of covalent organic frameworks (COFs) stems from the direct correlation between their modular design principle and various interesting properties. However, existing synthetic approaches to realize this goal mainly result in insoluble and unprocessable powders, which severely restrict their widespread applicability. Therefore, developing a methodology for easy fabrication of these materials remains an alluring goal and a much desired objective. Herein, we have demonstrated a bottom-up interfacial crystallization strategy to fabricate these microcrystalline powders as large-scale thin films under ambient conditions. This unique design principle exploits liquid-liquid interface as a platform, allowing simultaneous control over crystallization and morphology of the framework structure. The thin films are grown without any support in free-standing form and can be transferred onto any desirable substrate. The porous (with Tp-Bpy showing highest SBET of 1a151 m2 g-1) and crystalline thin films, having high chemical as well as thermal stability, also hold the merit to tune the thickness as low as sub-100 nm. These nanostructured thin COF films demonstrate remarkable solvent-permeance and solute-rejection performance. A prominent instance is the Tp-Bpy thin film, which displays an unprecedented acetonitrile permeance of 339 L m-2 h-1 bar-1.

Selective molecular sieving in self-Standing porous covalent-Organic-framework membranes - Kandambeth, S.; Biswal, B. P.; Chaudhari, H. D.; Rout, K. C.; Kunjattu, H. S.; Mitra, S.; Karak, S.; Das, A.; Mukherjee, R.; Kharul, U. K.; Banerjee, R. (Advanced Materials, 2017)
Self-standing, flexible, continuous, and crack-free covalent-organic-framework membranes (COMs) are fabricated via a simple, scalable, and highly cost-effective methodology. The COMs show long-term durability, recyclability, and retain their structural integrity in water, organic solvents, and mineral acids. COMs are successfully used in challenging separation applications and recovery of valuable active pharmaceutical ingredients from organic solvents.

Self - assemblies of bolaamphiphilic molecules - Dhasaiyan, Prabhu; Bhagavatula L. V. Prasad (Chemical Record, 2017)
The current buzzword in science and technology is self-assembly and molecular self-assembly is one of the most prominent fields as far as research in chemical and biological sciences is concerned. Generally, self-assembly of molecules occurs through weak non-covalent interactions like hydrogen bonding, π–π stacking, hydrophobic effects, etc. Inspired by many natural systems consisting of self-assembled structures, scientists have been trying to understand their formation and mimic such processes in the laboratory to create functional “smart” materials, which respond to temperature, light, pH, electromagnetic field, mechanical stress, and/or chemical stimuli. These responses are usually manifested as remarkable changes from the molecular (e. g., conformational state, hierarchical order) to the macroscopic level (e. g., shape, surface properties). Many molecules such as peptides, viruses, and surfactants are known to self-assemble into different structures. Among them, glycolipids are the new entries in the area of molecules that are being investigated for their self-assembly characteristics. Among the different classes of glycolipids like rhamnolipids and trehalose lipids, owing to their biological preparations and their structural novelty, sophorolipids (SLs) are evoking greater interest among researchers. Sophorolipids are a class of asymmetric bolas bearing COOH groups at one end and sophorose (dimeric glucose linked by an unusual β(1→2) linkage). The extreme membrane stability of Archaea, attributed to the membrane-spanning bolas (tetraether glycolipids), has inspired chemists to unravel the molecular designs that underpin the self-assembly of bolaamphiphilic molecules. Apart from these self-assembled structures, bolaamphiphiles find applications in many fields such as drug delivery, membrane mimicking, siRNA therapies, etc. The first part of this Personal Account presents some possible self-assembled structures of bolaamphiphiles and their mechanism of formation. The later part covers our work on one of the typical bolaamphiphiles known as sophorolipids.
Keywords: Bolaamphiphiles; gels; self-assembly; sophorolipids; vesicles

Self-assembly of fluorinated sugar amino acid derived alpha,gamma-cyclic peptides into transmembrane anion transport - Burade, Sachin S.; Saha, Tanmoy; Bhuma, Naresh; Kumbhar, Navanath; Kotmale, Amol; Rajamohanan, Pattuparambil R.; Gonnade, Rajesh G.; Talukdar, Pinaki; Dhavale, Dilip D. (Organic Letters, 2017)
Syntheses of fluorinated sugar amino acid derived alpha,gamma-cyclic tetra- and hexapeptides are reported. The IR, NMR, ESI-MS, CD, and molecular modeling studies of cyclic tetra- and hexapeptides showed C-2 and C-3 symmetric flat oval- and triangular-ring shaped, beta-strand conformations, respectively, which appear to self assemble into nanotubes. The alpha,gamma-cyclic hexapeptide (EC50 = 2.14 mu M) is found to be a more efficient ion transporter than alpha,gamma-cyclic tetrapeptide (EC50 = 14.75 mu M). The anion selectivity and recognition of alpha,gamma-cyclic hexapeptide with NO3- ion is investigated.

Silver sequestration of halides for the activation of Pd(OAc) 2 catalyzed Mizoroki-Heck reaction of 1,1 and 1,2 - Disubstituted alkenes: Ag Sequestration for Pd catalyzed Heck reaction- disubstituted alkenes - Bangar, Pronnoy G.; Jawalkar, Priyanka R.; Dumbre, Swapnil; Patil, Dharmaraj; Iyer, Suresh (Applied Organometallic Chemistry, 2017)
A ligand free catalytic system consisting of Pd(OAc)2 (cat) and stoichiometric quantities of silver salts, AgOAc or AgBF4, exhibit high efficiency in the Mizoroki-Heck arylation, transforming aryl iodides and 1,1 as well as 1,2 disubstituted alkenes into 1,1,2 – trisubstituted aryl alkenes in excellent yields in very short reaction times.
Keywords: 1; 1-disubstituted alkenes; 2-disubstituted alkenes; AgBF4; AgOAc; Mizoroki-Heck reaction

Solid base catalyzed depolymerization of lignin into low molecular weight products - Chaudhary, Richa; Dhepe, Paresh Laxmikant (Green Chemistry, 2017)
For the biorefinery concept to become commercially viable, it is essential to add value to lignin which is the only naturally available aromatic polymer. A one-pot depolymerization of lignin into reactive substituted phenolic compounds (platform chemicals and octane enhancers) with low molecular weight is of paramount importance and for that, the development of an environmentally benign method is necessary. Herein we report the depolymerization of high molecular weight lignin (60 000 Da) over various recyclable solid base catalysts at 250 degrees C over 1 h. Under these conditions, most of the zeolitic catalysts (NaX, NaY, NaP) showed very high yields of low molecular weight products compared to other catalysts (MgO, CaO, HT, HAP). But in particular, over NaX the maximum yield (51%) of low molecular weight products was achieved. Identification and quantification of products was done by GC, GC-MS, HPLC, LC-MS, CHNS, NMR and FT-IR techniques. The revelation of retention of most of the functional groups on products present in lignin was confirmed by FT-IR studies. It is observed that the efficiencies of catalysts were dependent on pH, the cation, the type and concentration of basic sites, etc. A unique study on the product adsorption capacities on solids was done and it is recognized that as the strength of basic sites increases, adsorption enhances.

Solubility limits of ceria-zirconia-lanthana solid-solutions - Abbas, Zenab; Surendran, Mythili; Anjana, P. A.; Jidev, P. K.; Dasari, Harshini; Naidu, Sudhakar N.; Anandhan, S.; Bhat, Udaya K.; Babu, Uday Bhaskar G.; Dasari, Hari Prasad (International Conference on Recent Trends in Engineering and Material Sciences (ICEMS), 2017)
We demonstrate, the solubility limits of Ceria-Zirconia-Lanthana (CZLa) solid-solutions with the increase in heat-treatment temperature from 600 degrees C to 1300 degrees C. CZLa nano-crystalline samples were successfully synthesized by EDTA-Citrate complex method and were characterized by Raman Spectroscopy (RS) and Transmission Electron Microscopy (TEM) analysis. With an increase in temperature, it is noticed that the solubility limit is decreased in CZLa system. At 600 degrees C, a very good solubility is observed in CZLa system and is confirmed from RS analysis. At higher heat-treatment temperatures (1000 and 1300 degrees C), with an increase in La content, Zr precipitated in the CZLa system and is confirmed from RS analysis. The reason for such kind of behavior in this CZLa system is clearly explained in this work. (C) 2017 Elsevier Ltd. All rights reserved.
Keywords: Ceria-Zirconia Lanthana; EDTA-Citrate method; Raman spectroscopy; solubility limit; XRD

Solvent-free synthesis of thiobarbituric acids using amberlyst-15 as a green catalyst - Dhonde, Madhukar G.; Gajbhiye, Jayant M.; Katiya, Manish M. (Current Green Chemistry, 2017)

Specific receptors and imaging reagents for certain heavy metal toxins - Anila, H. A.; Ali, F.; Das, A. (Comprehensive supramolecular chemistry II, 2017)
Among various elements, mercury (Hg) and palladium (Pd) are featured in all lists of heavy metal toxins. Mercury is xenobiotics and toxic even at trace levels of exposure either in elemental (if aerosolized) or in its two ionic forms (viz. Hg(I) and Hg(II)). Importantly, the most common oxidation state of mercury is Hg(II) and this has an appreciably high value for enthalpy of solvation in aqueous media. This fact along with a high spin-orbit coupling constant value are not conducive for designing efficient luminescence ON-based receptors for Hg(II), which are essential for either detection or imaging of such toxins inside the cells or in specific organs. Such sensors have significance in evaluating the influence of such toxins in human physiology as well as in clinical diagnostics. Analogously, Palladium (in oxidation states of 0, II, and IV) is commonly used as a catalyst for the synthesis of various drugs or active pharmaceutical intermediates. Despite best efforts in purification and elimination of palladium used in such reactions, residual concentrations of Pd are often higher than the permissible level set by the World Health Organization. The affinity of Pd toward thiol-containing amino acids, proteins, DNA, or other macromolecules is known to cause physiological disorders. All these necessitate the design and development of efficient imaging reagents that are specific toward a certain cationic analytes and allow for the real-time monitoring for assessing the adverse influences on human physiology. Recent advances in such reagents primarily for Hg(II), Pd(0), and Pd(II) are discussed.

Spectroscopic and reactivity comparisons of a pair of bTAML complexes with Fe-V=O and Fe-IV=O units - Pattanayak, Santanu; Jasniewsk, Andrew J.; Rana, Atanu; Draksharapu, Apparao; Singh, Kundan K.; Weitz, Andrew; Hendrich, Michael; Que, Lawrence, Jr.; Dey, Abhishek; Sen Gupta, Sayam (Inorganic Chemistry, 2017)
In this report we compare the geometric and electronic structures and reactivities of [Fe-V(O)](-) and [Fe-IV(O)](2-) species supported by the same ancillary nonheme biuret tetraamido macrocyclic ligand (bTAML). Resonance Raman studies show that the Fe-O vibration of the [Fe-IV(O)](2-) complex 2 is at 798 cm(-1), compared to 862 cm(-1) for the corresponding [Fe-V(O)](-) species 3, a 64 cm(-1) frequency difference reasonably reproduced by density functional theory calculations. These values are, respectively, the lowest and the highest frequencies observed thus far for nonheme high-valent Fe-O complexes. Extended X-ray absorption fine structure analysis of 3 reveals an Fe-O bond length of 1.59 angstrom, which is 0.05 angstrom shorter than that found in complex 2. The redox potentials of 2 and 3 are 0.44 V (measured at pH 12) and 1.19 V (measured at pH 7) versus normal hydrogen electrode, respectively, corresponding to the [Fe-IV(O)](2-)/[Fe-III(OH)](2-) and [Fe-V(O)](-)/[Fe-IV(O)](2-) couples. Consistent with its higher potential (even after correcting for the pH difference), 3 oxidizes benzyl alcohol at pH 7 with a second-order rate constant that is 2500-fold bigger than that for 2 at pH 12. Furthermore, 2 exhibits a classical kinteic isotope effect (KIE) of 3 in the oxidation of benzyl alcohol to benzaldehyde versus a nonclassical KIE of 12 for 3, emphasizing the reactivity differences between 2 and 3.

Stability studies of cuticle degrading and mycolytic enzymes of myrothecium verrucaria for control of insect pests and fungal phytopathogens - Chavan, S. B; Vidhate, R. P.; Kallure, G. S.; Dandawate, N. L.; Khire, J. M.; Deshpande, M. V. (Indian Journal of Biotechnology, 2017)
Myrothecium verrucaria produced extracellularly hydrolytic enzymes which can hydrolyse the insect cuticle as well as fungal cell wall. The addition of polyols, such as glycerol, sorbitol, xylitol (1 M) during ultra -filtration or freeze- drying of enzyme mixture increased the recovery of the enzymes in a concentrated form. Polyols (5 M) increased the temperature and pH stability of the enzymes, in the presence of glycerol chitinase, beta-1,3-glucanase, lipase and protease retained 50-60% of initial activities at 40 degrees C after 3 h. While xylitol (5 M) was effective in stabilizing activities at pH 5.0 and 7.5 at 25 degrees C for 7 d. In the freeze-dried powder form, > 90% at 4 degrees C for 1 year and 80-85% at 25 degrees C for 2 months enzyme activities were retained. The addition of glycerol (1 M) to the enzyme mixture protected enzyme activities under sunlight (60-65% activity at RT) for 5 d. Because of glycerol (1 M), the efficacy of M verrucaria enzyme preparation to control Helicoverpa armigera infestation in chick pea was increased to 70 +/- 19%. While without glycerol the efficacy was 55 +/- 23%. The germination of peanut seeds infected with Sclerotium rolfsii was observed to be increased (70 +/- 5%) in a pot irrigated with enzyme mixture.

Strikingly diverse reactivity of structurally identical silylene and stannylene - Parvin, Nasrina; Dasgupta, Rajarshi; Pal, Shiv; Sen, Sakya S.; Khan, Shabana (Dalton Transactions, 2017)
The reactivity of structurally identical silylene and stannylene [PhC(NtBu)(2)EN(SiMe3)(2)] (E = Si (1) and Sn (2)) towards coinage metals has been explored. While 1 has the propensity to form an adduct with coinage metals (4 and 5), 2 undergoes a ligand exchange reaction with copper halides and silver triflate leading to PhC(NtBu) 2SnX (X = Br (6), Cl (7), and OSO2CF3 (8)) with concomitant formation of [M{N(SiMe3) (2)}] (M = Cu, Ag). However, with AgSbF6 both 1 and 2 led to ion pairs, 9(+) .SbF(6)(-)and 10(+) . SbF(6)(-)displaying weaker Ag center dot center dot center dot center dot F interactions in the latter.

Structure-function relationship of a bio-pesticidal trypsin/chymotrypsin inhibitor from winged bean - Banerjee, Sayanika; Giri, Ashok P.; Gupta, Vidya S.; Dutta, Samir Kumar (International Journal of Biological Macromolecules, 2017)
Protease inhibitors are essential bio-molecules that serve as a model system for the study of protein structure and protease-protease inhibitor interaction. We here report a bi-functional serine protease inhibitor from winged bean (WBCTI) that completely retains its inhibitory property against trypsin and chymotrypsin even after heating at 70 degrees C. Detailed circular dichroism and fluorescence studies at different temperatures, 30-90 degrees C, have been performed to understand the reason behind thermal stability of the protein. On the basis of our results it appears that WBCTI maintains its canonical structure up to 70 degrees C. Above that the heat induced conformational change becomes irreversible which causes aggregation followed by precipitation of the protein. Moreover, the activity and stability of the secondary structure are found to decrease drastically in presence of dithiothreitol indicating that the protein acquires additional stability for the occurrence of two disulfide bonds. In addition to the structural characterization, an important property of WBCTI against the polyphagous pest Helicoverpa armigera has been explored in present study. WBCTI has showed reasonable inhibition of the mid-gut proteases of H. armigera. In artificial feeding trial through addition of WBCTI in diet resulted in significant growth retardation, delayed pupae formation and higher mortality of H. armigera larvae. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Disulfide reduction; Heat stable; Pesticidal; Trypsin/Chymotrypsin inhibitor; Winged bean

Study of nanofiber scaffolds of PAA, PAA/CS, and PAA/ALG for its potential use in biotechnological applications - Rodolfo, Velasco; Ricardo, Vera-Graziano; López-Maldonado, E.A.; Mercedes, Oropeza; Dastager, Syed; Adriana, Álvarez-Andrade; Ana, leticia Iglesias; Luis, Jesús Villarreal-Gómez (International Journal of Polymeric Materials, 2017)
In recent times, electrospun nanofibers have been widely studied from several biotechnological approaches; in this work, poly (acrylic acid) solutions mixed with chitosan and alginate were electrospun and characterized in order to determine the behavior of these fibers when used in combination with bacteria, different samples were incubated with the bacterial strains: Streptomyces spp., Micromonospora spp. and Escherichia coli and a OD600 test was performed. The formation of nanofibers via electrospinning and the physicochemical properties of the obtained fibers were evaluated. Results showed that the presence of Chitosan enhanced the thermal stability of poly (acrylic acid), since poly (acrylic acid)/alginate fibers lost 5% of their mass at 41°C while poly (acrylic acid)/chitosan lost this amount at around 125°C. The fibers demonstrated suitable characteristics to be used as a bacteria bioreactor.

Sulfamic acid-catalyzed, environmentally benign synthesis of bis-tetronic acids at ambient temperature - Pandit, Kapil S.; Desai, Uday V.; Wadgaonkar, Prakash P.; Kodam, Kisan M. (Research on Chemical Intermediates, 2017)
An enviro-economic protocol has been described for the synthesis of bis-tetronic acids by pseudo-three-component condensation between aldehydes/isatins and tetronic acid using sulfamic acid as a solid acid catalyst. Easy commercial availability of the catalyst at extremely low cost, excellent yields and avoidance of conventional purification procedures are the main merits of this energy efficient protocol.

Super-resolution probe to monitor HNO levels in the endoplasmic reticulum of cells - Ali, Firoj; Sreedharan, Sreejesh; Ashoka, Anila Hoskere; Saeed, Hiwa K.; Smythe, Carl G. W.; Thomas, Jim A.; Das, Amitava (Analytical Chemistry, 2017)
Selective detection of nitroxyl (HNO), which has recently been identified as a reactive nitrogen species, is a challenging task. We report a BODIPY-based luminescence ON reagent for detection of HNO in aqueous solution and in live RAW 264.7 cells, based on the soft nucleophilicity of the phosphine oxide functionality toward HNO. The probe shows high selectivity to HNO over other reactive oxygen/nitrogen and sulfur species. Luminescence properties of the BODIPY-based chemodosimetric reagent make it an ideal candidate for use as a reagent for super-resolution structured illumination microscopy. The viability of the reagent for biological in vivo imaging application was also confirmed using Artemia as a model.

Surface disordered rutile TiO2-graphene quantum dot hybrids: a new multifunctional material with superior photocatalytic and biofilm eradication properties - Biswas, A.; Salunke, G.; Khandelwal, P.; Das, R.; Poddar, P. (New Journal of Chemistry, 2017)
The controlled introduction of defects in semiconductors has contributed to the development of electronic devices and technologies. Recently, chemical control over defects, formation of new hybrid materials and multifunctional nanostructures have been sought in energy, health, and environment related technologies. Surface-disordered anatase-TiO2 has received wide attention due to its exceptional photocatalytic performance. Herein, we demonstrate, for the first time, a one-step aqueous-phase synthesis of a surface-disordered rutile TiO2-graphene quantum dot (TG) hybrid material. The TG-hybrid is a rutile-TiO2 matrix in which homogeneous in situ insertion of GQDs occurs during the growth of the TiO2 particles. The TG-hybrid material showed superior photocatalytic performance with similar to 98% solar light driven photo-degradation of methylene blue (MB) dye within 6 min and similar to 86% of rhodamine-B (RhB) within 4 min which is much better than the photocatalytic performance shown by the rutile-TiO2 (similar to 30% and similar to 20%, respectively) and GQDs (similar to 15% and similar to 8%, respectively), themselves. Moreover, the TG-hybrid also showed enhanced toxicity to Gram-positive (S. aureus) as well as Gram-negative (E. coli, P. aeruginosa) bacterial cells. The growth-curves of E. coli cells, after incubating them with increasing concentrations of the TG-hybrid, showed that the TG-hybrid could effectively inhibit the growth of E. coli cells at a concentration of 60 mu g mL(-1). The effect of UV-light exposure on the bacterial-biofilm disruption by the TG-hybrid material was also investigated. It was observed that in the presence of UV-light, the biofilm disruption done by the TG-hybrid was larger in comparison to the TiO2 and GQDs alone, under the same conditions. The increase in the formation of reactive oxygen species (ROS) in the presence of sunlight for the TG-hybrid may be the reason behind its superior antibacterial and biofilm eradication properties. We believe that the TG-hybrid material will have applications in energy, health and environment related technologies.

Synthesis and antimycobacterial screening of new thiazolyl-oxazole derivatives - Abhale, Yogita K.; Sasane, Amit V.; Chavan, Abhijit P.; Shekh, Saddam Husen; Deshmukh, Keshav K.; Bhansali, Sujit; Nawale, Laxman; Sarkar, Dhiman; Mhaske, Pravin C. (European Journal of Medicinal Chemistry, 2017)
In the present study a series of 4-methyl-2-aryl-5-(2-aryl/benzyl thiazol-4-yl) oxazole (4a-v) have been synthesized and evaluated for their preliminary antitubercular, antimicrobial and cytotoxicity activity. Among all the synthesized compounds, 4v reported comparable activity against dormant M. tuberculosis H37Ra and M. bovis BCG strains with respect to standard drug rifampicin. The active compounds from the antitubercular study were further tested for anti-proliferative activity against HeLa, A549 and PANC-1 cell lines using MU assay and showed no significant cytotoxic activity at the maximum concentration evaluated. Further, the synthesized compounds were found to have potential antibacterial activities with MIC range of 2.1-26.8 mu g/mL. High potency, lower cytotoxicity and promising antimycobacterial activity suggested that these compounds could serve as good leads for further optimisation and development. (C) 2017 Elsevier Masson SAS. All rights reserved.

Synthesis and antitubercular activity of new thiazolidinones with pyrazinyl and thiazolyl scaffolds - Dhumal, Sambhaji T.; Deshmukh, Amarsinh R.; Khillare, Lalit D.; Arkile, Manisha A.; Sarkar, Dhiman; Mane, Ramrao A. (Journal of Heterocyclic Chemistry, 2017)
Emergence of multidrug resistant and extensively drug resistant tuberculosis has prompted to develop new molecular entities to treat the disease. A series of new 4-thiazolidinones with pyrazinyl and thiazolyl scaffolds has been synthesized, and their antitubercular activity is reported. The title 4-thiazolidinones, N-(pyrazinyl substituted thiazoloylamino)-2-aryl-4-thiazolidinones () have been first time prepared using pyrazinamide as a starting material via five successive steps. The purity and the structures of the intermediates (carboethoxythiazole, acid hydrazide, and azomethines) and title thiazolidinones () have been confirmed by TLC and spectral analyses, respectively. An antitubercular screening of the new 4-thiazolidinones has been performed on bacterial strains, Mycobacterium tuberculosis H37Ra and Mycobacterium BCG using the solutions of different concentrations of the compounds () and the screening results are presented. Compound has displayed notable antitubercular activity.

Synthesis and biological evaluation of new fluconazole β-lactam conjugates linked via 1,2,3-triazole - Divse, Jaisingh M.; Mhaske, Santosh B.; Charolkar, Chaitanya R.; Sant, Duhita G.; Tupe, Santosh G.; Deshpande, Mukund V.; Khedkar, Vijay M.; Nawale, Laxman U.; Sarkar, Dhiman; Pore, Vandana S. (New Journal of Chemistry, 2017)
Novel 1,2,3-triazole-linked β-lactam–fluconazole conjugates 12(a–l) were designed and synthesized. The compounds showed potent antifungal activity against two pathogenic Candida strains; Candida albicans ATCC 24433 and Candida albicans ATCC 10231 with MIC values in the range of 0.0625–2 μg mL−1. Compounds 12h, 12j and 12k showed promising antifungal activity against all the tested fungal pathogens except C. neoformans ATCC 34554 compared to fluconazole. Compound 12j in which the β-lactam ring was formed using para-anisidine and benzaldehyde was found to be more potent than fluconazole against all the fungal strains with an IC50 value of <0.015 μg mL−1 for Candida albicans (ATCC 24433). Mechanistic studies for active compounds revealed that the antifungal action was due to ergosterol inhibition. Compounds 12h and 12j at a concentration of 0.125 μg mL−1 caused 91.5 and 96.8% ergosterol depletion, respectively, compared to fluconazole which at the same concentration caused 49% ergosterol depletion. The molecular docking study revealed that all the fluconazole β-lactam conjugates 12(a–l) could snugly fit into the active site of lanosterol 14α-demethylase (CYP51) with varying degrees of affinities. As anticipated, the binding energy for compound 12j (−58.961 kcal mol−1) was much smaller than that for fluconazole (−52.92 kcal mol−1). The synthesized compounds have therapeutic potential for the control of candidemia.

Synthesis, antimycobacterial screening and molecular docking studies of 4-aryl-4′-methyl-2′-aryl-2,5′-bisthiazole derivatives - Abhale, Yogita K.; Shinde, Abhijit D.; Deshmukh, Keshav K.; Nawale, Laxman U.; Sarkar, Dhiman; Choudhari, Prafulla B.; Kumbhar, Santosh S.; Mhaske, Pravin C. (Medicinal Chemistry Research, 2017)
A series of 4-aryl-4′-methyl-2′-aryl-2,5′-bisthia- zole derivatives (5a–o) were synthesized and screened for inhibitory activity against Mycobacterium tuberculosis H37Ra (ATCC 25177) and Mycobacterium bovis BCG (ATCC 35743) strains. Five lead compounds (5e, 5f, 5g, 5h, and 5o) were further confirmed from their dose dependent effect against MTB and Bovine–Calmette–Guerin. The most promising compounds 5f (MIC90: 11.32 μg/mL), 5h (MIC90: 11.59 μg/mL), and 5o (MIC90: 23.64 μg/mL) showed strong antitubercular activity against dormant MTB and BCG as well as almost insignificant cytotoxicity up to 100μg/mL against HeLa, A549, and PANC-1 human cancer cell lines. Further, the synthesized compounds were found to have potential antibacterial activity against Gram-negative bac- teria, Escherichia coli, Pseudomonas flurescence and Gram- positive bacteria, Staphylococcus aureus, Bacillus subtilis. Most of the synthesized compounds showed moderateactivity against fungal strain Candida albicans. Molecular docking studies of these compounds showed significant interactions with crystal structure of the cytochrome P45014α-sterol demethylase (CYP51) PDB ID: 1E9X. Hydrogen bond interactions with SER261 and VAL395 are important interactions for selective inhibition of designed inhibitors. Compounds 5f, 5h, and 5o showed significant interactions with 1E9X. All the experimental results promote us to consider this series as a starting point for the devel- opment of novel, selective and more potent antitubercular agents in the future.

Synthesis, antitubercular and antimicrobial potential of some new thiazole substituted thiosemicarbazide derivatives - Abhale, Y. K.; Shinde, A.; Deshmukh, K. K.; Nawale, L.; Sarkar, D.; Mhaske, P. C. (Medicinal Chemistry Research, 2017)
The increase in antibiotic resistance due to multiple factors has warranted the need for the search of new compounds which are active against multidrug resistant pathogens. In this context a small focused library of thiosemicarbazide derivatives of 2-arylthiazole-4-carbaldehyde, 4-methyl-2-arylthiazole-5-carbaldehyde and 1-(4-methyl-2-arylthiazol-5-yl) ethanone, (5a–l) has been synthesized. The title compounds were screened for inhibitory activity against Mycobacterium tuberculosis H37Ra (ATCC 25177) and Mycobacterium bovis Bacille Calmette Guerin (ATCC 35743) strains. The synthesized compounds, 5a–l were further assayed for their cytotoxic activity against the two human cancer cell lines, HeLa and human colon carcinoma 116 cell lines and showed no significant cytotoxic activity against these two cell lines at the maximum concentration evaluated. Further, the synthesized compounds were found to have potential antibacterial activity against Gram-negative bacteria, Escherichia coli, Pseudomonas flurescence and Gram-positive bacteria, Staphylococcus aureus, Bacillus subtilis. Most of the synthesized compounds showed moderate activity against fungal strain Candida albicans. This study provides valuable directions to our ongoing endeavor of rationally designing more potent antimycobacterial agent. © 2017, Springer Science+Business Media, LLC.
Keywords: Antimicrobial activity; Antitubercular activit; Cytotoxicity; Thiazole; Thiosemicarbazide

Synthesis of amphiphilic isoindigo co-polymers for organic field effect transistors: A comparative study - Dharmapurikar, Satej S.; Arulkashmir, Arulraj; Mahale, Rajashree Y.; Chini, Mrinmoy Kumar (Journal of the apllied polymer science, 2017)
In this work, the amphiphilic isoindigo (am-iInd) based conjugated polymers namely poly(am-iInd-DT) and poly(am-iInd-TT) and their regular counterpart poly(reg-iInd-DT) and poly(reg-iInd-TT) were synthesized to compare their opto-electronic and charge transport properties. They were used to fabricate organic field effect transistors. Charge transport properties in conjugated polymers depend upon intermolecular interaction which is strongly affected by the nature of side chains. The amphiphilic nature of the conjugated polymers has little impact on the charge transport properties. The charge carrier mobility of amphiphilic conjugated polymers was comparable with the regular polymers except poly(reg-iInd-DT) which can be correlated by X-ray diffraction and thin film morphology. (c) 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45461.
Keywords: Alkyl; Applications; Conducting polymers; Copolymers; Optical and Photovoltaic applications; conjugated polymers; High-performance; mobility; Packaging; Semicondoctors; Side-chains; Solar-cells; Thin-film Transformer

Synthesis of extended conjugated indolyl chalcones as potent anti-breast cancer, anti-inflammatory and antioxidant agents - Bhale, Pravin S.; Chavan, Hemant V.; Dongare, Sakharam B.; Shringare, Sadanand N.; Mule, Yoginath B.; Nagane, Samadhan S.; Bandgar, Babasaheb P. (Bioorganic & Medicinal Chemistry Letters, 2017)
In the present investigation, synthesis of a series of extended conjugated delta-chloro-alpha-cyano substituted indolyl chalcones (5a-p) was accomplished by reacting 3-cyanoacetylindole 2 with 3-chloro-3-phenylpropenal 4 in the presence of piperidine. The structural interpretations of newly synthesized compounds were based on chemical and spectroscopic evidences. Anti-tumor evaluation of the synthesized compounds in vitro against MCF-7 (breast carcinoma) cell line revealed that they possess high anti-tumor activities. Among them, compound 5e and 5a demonstrated excellent activity against breast carcinoma (GI(50) <0.1 and mu M respectively) as good as adriamycin (GI(50) <0.1 mu M). The compounds were also screened against the normal Vero monkey cell line, which showed moderate selectivity against inhibition of cancer cells. The effect of extended conjugation on activity authenticated by comparing activity profile of compound 5a, 5i and 5m with their simple analogues. Among the synthesized compounds, 5i and 51 were found to be active anti-inflammatory agents in addition to having noteworthy antioxidant potential. These results suggest the possible use of these compounds for the design and development of novel anti breast cancer agents. (C) 2017 Elsevier Ltd. All rights reserved.

Synthesis of gamma-WO3 thin films by hot wire-CVD and investigation of its humidity sensing properties - Jadkar, Vijaya; Pawbake, Amit; Waykar, Ravindra; Jadhavar, Ashok; Date, Abhijit; Late, Dattatray; Pathan, Habib; Gosavi, Suresh; Jadkar, Sandesh (Physica Status Solidi A-Applications and Materials Science, 2017)
In this study, monoclinic tungsten oxide (gamma-WO3) have been grown in a single step using HW-CVD method by resistively heating W filaments in a constant O-2 pressure. The formation of gamma-WO3 was confirmed using low angle-XRD and Raman spectroscopy analysis. Low angle-XRD analysis revealed that as-deposited WO3 film are highly crystalline and the crystallites have preferred orientation along the (002) direction. HRTEM analysis and SAED pattern also show the highly crystalline nature of WO3 with d spacing of similar to 0.38 nm, having an orientation along the (002) direction. Surface topography investigated by SEM analysis shows the formation of a uniform and homogeneous cauliflower like morphology throughout the substrate surface without flaws and cracks. A humidity sensing device incorporating WO3 is also fabricated, which shows a maximum humidity sensitivity factor of similar to 3954% along with a response time of similar to 14 s and a recovery time of similar to 25 s. The obtained results demonstrate that it is possible to synthesize WO3 in a single step by HW-CVD method and to fabricate a humidity sensor by using it. (C) 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Synthesis of meta-substituted monodentate phosphinite ligands and implication in hydroformylation - Deshmukh, Satej S.; Gaikwad, Shahaji R.; Pandey, Swechchha; Mali, Pramod S.; Chikkali, Samir H. (Journal of Chemical Sciences, 2017)
Synthesis of meta-substituted phosphinite ligands 3,3'-(methoxyphosphanediyl) bis(N, N-diethylaniline) (4a) and methoxybis(3-methoxyphenyl) phosphane (4b), in high yields, has been demonstrated. Typical phosphorus chemical shift between 110-120 ppm, appearance of methoxy protons and corresponding carbon, as well as ESI-MS spectra unambiguously confirmed the existence of phosphinite ligands 4a and 4b. To demonstrate the synthetic usefulness of 4a and 4b, these ligands were tested in the rhodium catalyzed hydroformylation of 1-octene. The diethylamine substituted ligand 4a was found to be highly active, whereas 4bwas less reactive but revealed slightly better regioselectivity of 62% under optimized conditions. Additionally, 4a and 4b were found to catalyze the hydroformylation of styrene, 1-undecenol and 1,1-disubstituted functional olefin, methyl methacrylate. Both the ligands displayed excellent conversion of styrene, and 4b revealed an excellent branch selectivity of 75%. Although 1-undecenol proved to be amenable to hydroformylation (85-90% conversion to aldehyde), both the ligands failed to discriminate between the linear and branched products. Substrate methyl methacrylate proved to be highly challenging and reduced conversion (between 33-42%) was observed under optimized conditions. Ligand 4a was found to be highly selective towards linear aldehyde (81% linear selectivity).

Synthesis of orthorhombic-molybdenum trioxide (α-MoO3) thin films by hot wire-CVD and investigations of its humidity sensing properties - Jadkar, Vijaya; Pawbake, Amit S.; Waykar,Ravindra G.; Jadhavar, Ashok Arjun; Mayabadi, Azam; Date, Abhijit; Late, Dattatray J.; Pathan, Habib M.; Gosavi, Suresh W.; Jadkar, Sandesh R. (Journal of Materials Science Materials in Electronics, 2017)
In present work, we report synthesis of orthorhombic-molybdenum trioxide (α-MoO 3) thin films using home-build hot wire-CVD (HW-CVD) method simply by heating the Mo filament in a controlled O 2 atmosphere. The formation of α-MoO 3 was confirmed by low angle-XRD and Raman spectroscopy. Low angle-XRD analysis revealed that α-MoO 3 crystallites have orientations along (110), (101) and (111) directions while Raman spectroscopy analysis shows two prominent vibrational modes ~819 and ~994 cm −1 associated with Mo 2–O and Mo=O respectively. SEM and TEM analysis show the formation of nano-sheets like morphology of α-MoO 3 thin films. The SAED pattern shows highly crystalline nature of α-MoO 3. The humidity-sensing properties were investigated at room temperature by fabricating the two probe device. The humidity sensing results showed n-type behavior of α-MoO 3. The maximum humidity sensitivity of ~6957% along with response time of ~66 s and recovery time of ~5 s were observed for α-MoO 3 thin film humidity sensor device. Our results have opened up a new avenue to grow α-MoO 3 for humidity sensor applications.

Synthesis route to pyrrolones from -cyano ,-unsaturated ketones and -isocyano esters by oxidative dearomatization of 2-aminofuran intermediates - Mahida, Anil K.; Kale, Someshwar B.; Das, Utpal (European Journal of Organic Chemistry, 2017)
An efficient method for the catalyst/promoter-free synthesis of tetrasubstituted furan derivatives proceeding through the [4+1] cycloaddition of isocyanoacetates with electron-deficient olefins was developed. The products were obtained in good to excellent yields without any column chromatography. Oxidative dearomatization of these furans was achieved only in the presence of oxygen, which led to pyrrolones in high yields.

Targeted drug delivery in covalent organic nanosheets (CONs) via sequential postsynthetic modification - Mitra, Shouvik; Sasmal, Himadri Sekhar; Kundu, Tanay; Kandambeth, Sharath; Math, Kavya; Diaz Diaz, David; Banerjee, Rahul (Journal of the American Chemical Society, 2017)
Covalent organic nanosheets (CONs) have emerged as a new class of functional two-dimensional (2D) porous organic polymeric materials with a high accessible surface, diverse functionality, and chemical stability. They could become versatile candidates for targeted drug delivery. Despite their many advantages, there are limitations to their use for target specific drug delivery. We anticipated that these drawbacks could be overturned by judicious postsynthetic modification steps to use CONs for targeted drug delivery. The postsynthetic modification would not only produce the desired functionality, it would also help to exfoliate to CONs as well. In order to meet this requirement, we have developed a facile, salt-mediated synthesis of covalent organic frameworks (COFs) in the presence of p-toluenesulfonic acid (PTSA). The COFs were subjected to sequential postsynthetic modifications to yield functionalized targeted CONs for targeted delivery of 5-fluorouracil to breast cancer cells. This postsynthetic modification resulted in simultaneous chemical delamination and functionalization to targeted CONs. Targeted CONs showed sustained release of the drug to the cancer cells through receptor mediated endocytosis, which led to cancer cell death via apoptosis. Considering the easy and facile COF synthesis, functionality based postsynthetic modifications, and chemical delamination to CONs for potential advantageous targeted drug delivery, this process can have a significant impact in biomedical applications.

Transcriptional transitions in alphonso mango (Mangifera indica L.) during fruit development and ripening explain its distinct aroma and shelf life characteristics - Deshpande, Ashish B.; Anamika, Krishanpal; Jha, Vineet; Chidley, Hemangi G.; Oak, Pranjali S.; Kadoo, Narendra Y.; Pujari, Keshav H.; Giri, Ashok P.; Gupta, Vidya S. (Scientific Reports, 2017)
Alphonso is known as the "King of mangos" due to its unique flavor, attractive color, low fiber pulp and long shelf life. We analyzed the transcriptome of Alphonso mango through Illumina sequencing from seven stages of fruit development and ripening as well as flower. Total transcriptome data from these stages ranged between 65 and 143 Mb. Importantly, 20,755 unique transcripts were annotated and 4,611 were assigned enzyme commission numbers, which encoded 142 biological pathways. These included ethylene and flavor related secondary metabolite biosynthesis pathways, as well as those involved in metabolism of starch, sucrose, amino acids and fatty acids. Differential regulation ( p-value <= 0.05) of thousands of transcripts was evident in various stages of fruit development and ripening. Novel transcripts for biosynthesis of mono-terpenes, sesqui-terpenes, di-terpenes, lactones and furanones involved in flavor formation were identified. Large number of transcripts encoding cell wall modifying enzymes was found to be steady in their expression, while few were differentially regulated through these stages. Novel 79 transcripts of inhibitors of cell wall modifying enzymes were simultaneously detected throughout Alphonso fruit development and ripening, suggesting controlled activity of these enzymes involved in fruit softening.

Transition metal catalysis-a unique road map in the stereoselective synthesis of 1,3-polyols - Kumar, Pradeep; Tripathi, Divya; Sharma, Brijesh M.; Dwivedi, Namrata (Organic & Biomolecular Chemistry, 2017)
The present review summarizes recent diverse reactions employed in the formation of 1,3-polyols providing an overview of the mechanistic pathway and the enantioselectivity obtained, in terms of the properties of transition metals directly involved in the catalytic transformations and their interaction with various ligands.

Transition metal free catalytic hydroboration of aldehydes and aldimines by amidinato silane - Bisai, Milan; Pahar, Sanjukta; Das, Tamal; Sen, Sakya S. (Dalton Transactions, 2017)
The transition metal free catalytic hydroboration of aldehydes and ketones is very limited and has not been reported with a well-defined silicon(iv) compound. Therefore, we chose to evaluate the previously reported silicon(iv) hydride [PhC(NtBu)2SiHCl2], (1) as a single component catalyst and found that it catalyzes the reductive hydroboration of a range of aldehydes with pinacolborane (HBpin) under ambient conditions. In addition, compound 1 can catalyze imine hydroboration. DFT calculation was carried out to understand the mechanism.

Ultra small nanoclusters to nanoparticles: fine tuning of particle size in water dispersible cation functionalized thiolate protected Pd system - Dhanraj, Prakriti; Samanta, Anupam; Devi, R. Nandini (Materials Today-Proceedings, 2017)
Monolayer protected noble metal nanoparticles have attracted considerable attention in the past decade with potential applications in fields ranging from catalysis to biosensors [1, 2,]. We have developed a novel procedure for the synthesis of water dispersible Pd nanoparticles based on a bifunctional ligand, N,N,N-tripropyl(11-mercaptoundecyl) ammonium chloride in which thiol group binds to the metal, hydrophobic middle alkyl chain acts as capping agent and provides steric stability and on the other end the ammonia group helps in making nanoparticles hydrophilic. In this paper, we report the fine-tuning of size of water dispersible Pd nanosystems ranging from clusters to nanoparticles by adjusting the synthetic parameters and their characterization. (C) 2017 Elsevier Ltd. All rights reserved.

Ultrahigh ionic conduction in water-stable close-packed metal-carbonate frameworks - Manna, Biplab; Desai, Aamod V.; Illathvalappil, Rajith; Gupta, Kriti; Sen, Arunabha; Kurungot, Sreekumar; Ghosh, Sujit K. (Inorganic Chemistry, 2017)
Utilization of the robust metal-carbonate backbone in a series of water-stable, anionic frameworks has been harnessed for the function of highly efficient solid-state ion conduction. The compact organization of hydrophilic guest ions facilitates water-assisted ion-conduction in all the compounds. The dense packing of the compounds imparts high ion-conducting ability and minimizes the possibility of fuel crossover, making this approach promising for design and development of compounds as potential components of energy devices. This work presents the first report of evaluating ion-conduction in a purely metal-carbonate framework, which exhibits high ion-conductivity on the order of 10(-2) S cm(-1) along with very low activation energy, which is comparable to highly conducting well-known crystalline coordination polymers or commercialized organic polymers like Nafion.

Understanding alloy structure and composition in sinter-resistant AgPd@SiO2 encapsulated catalysts and their effect on catalytic properties - Mondal, Sourik; Rajesh, Thattarathody; Dhar, Basab B.; Snellman, Markus; Li, Junjie; Deepak, Francis Leonard; Devi, R. Nandini (New Journal of Chemistry, 2017)
The extent of alloying and the alloy composition, which are crucial in determining the activity and selectivity of bimetallic catalysts, were studied in porous silica encapsulated AgPd catalysts using XRD, HRTEM and HAADF-STEM. Water-dispersible ligand protected Pd ultra-small clusters and Ag nanoparticles of three different sizes were used as the precursors. The high reactivity of Pd ultra-small clusters enhanced the alloying of larger Ag nanoparticles to some extent. Encapsulation appeared to have minimised the sintering of the resultant nanoparticles. The earlier suggestions of the role of d-band positions with respect to adsorption energies holds good for the AgPd system and alloying enhances the activity. Alloy with the composition of Ag50Pd50 was found to be the most active with the reaction rate enhanced two fold compared to that in other compositions. Other factors like particle size and sinter-resistance also played important roles in enhancing the activity of these catalysts.

Understanding the factors influencing quality of writing and wiping for chalk and board system - Thakur, Rajendra S.; Shukla, Jignesh J.; Desale, Girish R.; Ghosh, Pushpito K. (Current Science, 2017)
This article reports the properties of a calcium carbonate-based writing chalk prepared at the CSIR-Central Salt and Marine Chemicals Research Institute (CSIR-CSMCRI) and, further, our efforts to understand the process of writing with the chalk on two different boards. The optimum density of the chalk was found to be 1.52 g ml(-1), keeping in mind the careful balancing act between strength and dust-free nature of the chalk on one hand, and the ease of particle transfer onto the board on the other. Writing with the chalk yielded thin and compact appearance on a ceramic board, while that on a polymeric board was relatively broad and dispersed. Atomic force and scanning electron microscopic studies were carried out to rationalize the observation by correlating roughness on the board with the distribution of chalk particles. Wiping efficiency of the polyurethane-based duster prepared at CSIR-CSMCRI was compared with commercial duster, and the observations rationalized again with the scanning electron microscopy.

Unprecedented solvent induced inter-conversion between monomeric and dimeric silylene-zinc iodide adducts - Yadav, Sandeep; Sangtani, Ekta; Dhawan, Diksha; Gonnade, Rajesh G.; Ghosh, Debashree; Sen, Sakya S. (Dalton Transaction, 2017)
<div class="block-record-info" style="margin: 0px 22px 22px; list-style: none; padding: 0px; line-height: 20px; font-size: 13px; color: rgb(51, 51, 51); font-family: arial, helvetica, sans-serif; background-color: rgb(248, 248, 248);"> Usually, when a silylene reacts with a transition metal Lewis acid, it forms an adduct which could be either monomeric or dimeric. However, we present here that a silylene, [PhC(NtBu)(2)SiN(SiMe3)(2)] can form both monomeric [PhC(NtBu)(2)Si{N(SiMe3)(2)} -> ZnI2]center dot THF (1) and dimeric [{PhC(NtBu)(2)}(N(SiMe3)(2))SiZnI,(mu-I)](2) (2) adducts upon reaction with ZnI2. The formation of 1 and 2 relies upon the solvent used for the reaction or crystallization. When the crystallization is carried out in THF complex 1 is formed, however, when the reaction and crystallization are performed in acetonitrile complex 2 is obtained. Both 1 and 2 were structurally authenticated and the nature of the Si-Zn bond in these complexes was determined by quantum chemical calculations. In addition, a spontaneous inter-conversion between 1 and 2 just by changing the solvents has been also observed; a feature presently not known for silylene-transition metal Lewis adducts.
Keywords: Bis(Silylene ); Carbene Complexes; Crystal -structure Determination; Dative bond; Lewis acid base reaction; Ligands; Main- group compounds; Reactivity; Silicon(II) Bis(Trimethylsilyl)Amide; Carbonyl-Complexes

Viable alternative in vitro system and comparative metabolite profiling of different tissues for the conservation of ceropegia karulensis - Pandey, M.; Jayaramaiah, R.H.; Dholakia, B.B; Punekar, S.A.; Giri, A.P. (Plant Cell, Tissue and Organ Culture, 2017)
Abstract: Ceropegia karulensis is an endemic and critically endangered plant of the Western Ghats from India. Exploitation of the tubers and poor regeneration from seed has narrowed distribution and propagation of the species. There is a need to develop in vitro propagation methods for C. karulensis to alleviate these problems. Here, we optimized callus induction, somatic embryogenesis and microtuberization from different seedling explants viz. cotyledonary leaf and root. The environmental scanning electron microscopy was used to observe somatic embryonic origin and their developmental stages. Highest callus proliferation was recorded with 2 µM 6-benzylaminopurine and 1 µM 2,4-dichlorophenoxyacetic acid. Somatic embryos derived from cotyledonary leaf explants were more proliferative than root explants. The combination of 2 µM 6-benzylaminopurine, 2 µM naphthalene acetic acid and 7% sucrose in MS media resulted in highest microtuberization. Further, gas chromatography-mass spectrometry based metabolic profiling was carried out from native wild plants and in vitro callus tissues which identified various phytochemicals such as alkaloids, fatty acids, esters alcohols, etc. Multivariate analysis revealed the chemical disparities, where considerable variations were observed between native wild type and in vitro tissues, but no significant differences were found among in vitro callus from both root and cotyledonary explants. Overall, our results suggested that the production of various secondary metabolites found in C. karulensis was not affected by in vitro propagation and could be utilized in the conservation strategies for this plant. Graphical Abstract: [Figure not available: see fulltext.]
Keywords: alkaloids; Metabolites

ZnO–ZnS heterojunctions: a potential candidate for optoelectronics applications and mineralization of endocrine disruptors in direct sunlight - Perumal Devaraji; Maitri Mapa; Hasna M. Abdul Hakkeem; Vediappan Sudhakar; Kothandam Krishnamoorthy; Chinnakonda S. Gopinath (ACS Omega, 2017)
Simple solution combustion synthesis was adopted to synthesize ZnO–ZnS (ZSx) nanocomposites using zinc nitrate as an oxidant and a mixture of urea and thiourea as a fuel. A large thiourea/urea ratio leads to more ZnS in ZSx with heterojunctions between ZnS and ZnO and throughout the bulk; tunable ZnS crystallite size and textural properties are an added advantage. The amount of ZnS in ZSx can be varied by simply changing the thiourea content. Although ZnO and ZnS are wide band gap semiconductors, ZSx exhibits visible light absorption, at least up to 525 nm. This demonstrates an effective reduction of the optical band gap and substantial changes in its electronic structure. Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and secondary-ion mass spectrometry results show features due to ZnO and ZnS and confirm the composite nature with heterojunctions. The above mentioned observations demonstrate the multifunctional nature of ZSx. Bare ZSx exhibits a promising sunlight-driven photocatalytic activity for complete mineralization of endocrine disruptors such as 2,4-dichlorophenol and endosulphan. ZSx also exhibits photocurrent generation at no applied bias. Dye-sensitized solar cell performance evaluation with ZSx shows up to 4% efficiency and 48% incident photon conversion efficiency. Heterojunctions observed between ZnO and ZnS nanocrystallites in high-resolution transmission electron microscopy suggest the reason for effective separation of electron–hole pairs and their utilization.

Active and durable alkaline earth metal substituted perovskite catalysts for dry reforming of methane - Dama, Srikanth; Ghodke, Seema R.; Bobade, Richa; Gurav, Hanmant R.; Chilukuri, Satyanarayana (Applied Catalysis B - Environmental, 2018)
Dry reforming of methane is an important process for the utilization of CO2 and to get valuable synthesis gas. Alkaline earth metal substituted MZr1-xNixO3-delta perovskites were synthesized by citrate gel method, characterized and evaluated for dry reforming methane. Characterization results show that the type of alkaline earth substituted at the A site of the perovskite oxide plays an important role in terms of structure, basicity, oxygen deficiency and Ni dispersion. Calcium substituted CaZr0.8Ni0.2O3-delta catalyst shows superior activity in terms of high CH4 and CO2 conversion, while maintaining the activity even after 500 h of reaction. Mechanistic investigations were carried out using transient pulse experiments and insitu FTIR-diffuse reflectance spectroscopy. These experiments reveal that redox property and basicity play important role in activation and sustaining the reforming reaction. Insitu FTIR measurements show that surface hydroxyl groups of the support are vital for high activity and durability of CaZr0.8Ni0.2O3-delta catalyst. XRD and TGA analysis of catalysts after reaction show the structures are retained, but peaks pertaining to coke were observed on SrZr0.8Ni0.2O3-delta and BaZr0.8Ni0.2O3-delta catalysts. On the otherhand, CaZr0.8Ni0.2O3-delta catalyst had only amorphous carbon even after 500 h of reaction. HRTEM studies revealed that SrZr0.8Ni0.2O3-delta and BaZr0.8Ni0.2O3-delta catalysts deactivated mostly due to the formation of carbon nanotubes with Ni embedded in them. Raman and XPS analysis helped in identifying types of coke precursors present on the catalysts. The investigation also illustrate that type of carbon formed depends on the basicity of perovskite oxide, metal to support interaction, Ni crystallite size, surface hydroxyl groups and oxygen defects. This study clearly demonstrated that CaZr0.8Ni0.2O3-delta is an excellent catalyst for dry reforming reaction with long life.

Alkaline earth metal compounds of methylpyridinato beta-diketiminate ligands and their catalytic application in hydroboration of aldehydes and ketones - Yadav, Sandeep; Dixit, Ruchi; Bisai, Milan Kumar; Vanka, Kumar; Sen, Sakya S. (Organometallics, 2018)
Ever increasing demand for green and sustainable chemical processes has set up a drive to replace transition metals with earth-abundant, nontoxic, and environmentally benign alternatives. In this regard, the alkaline earth metal complexes have attracted significant attention. Herein, we have used a beta-diketiminato ligand with methyl-pyridine side arm to synthesize magnesium (1) and calcium (2) compounds. The constitutions of 1 and 2 have been confirmed by single crystal X-ray studies, which show that the magnesium and calcium atom in 1 and 2 possesses octahedral geometry. Subsequently, we have used them as catalysts (1 mol %) for hydroboration of a wide range of aldehydes using pinacolborane (HBpin) at room temperature. The strategy has further been extended to ketones with 2 mol % catalyst loading. DFT calculations have been performed to understand the mechanism.

Beyond hydrofunctionalisation: a well-defined calcium compound catalysed mild and efficient carbonyl cyanosilylation - Yadav, Sandeep; Dixit, Ruchi; Vanka, Kumar; Sen, Sakya S. (Chemistry-A European Journal, 2018)
Organocalcium compounds have been reported as efficient catalysts for various transformations, for cases in which one of the substrates contained an E-H (E=B, N, Si, P) bond. Here, we look at the possibility of employing an organocalcium compound for a transformation in which none of the precursors has a polar E-H bond. This study demonstrates the utilization of a well-defined amidinatocalcium iodide, [PhC(NiPr)(2)CaI] (1) for cyanosilylation of a variety of aldehydes and ketones with Me3SiCN under ambient conditions without the need of any co-catalyst. The reaction mechanism involves a weak adduct formation between 1 and Me3SiCN leading to the activation of the Si-C bond, which subsequently undergoes sigma-bond metathesis with a C=O moiety. Such a mechanistic pathway is unprecedented in alkaline earth metal chemistry. Experimental and computational studies support the mechanism.
Keywords: Ca catalysis; carbonyls; cyanosilylation; Density functional calculations; transition-metal free

Bifunctional role of Pd/MMT-K 10 catalyst in direct transformation of furfural to 1,2-pentanediol - Date, Nandan S.; Chikate, Rajeev C.; Roh, Hyun-Seog; Rode, Chandrashekhar V. (Catalysis Today, 2018)
The acid functionality of montmorillonite clay K 10 (MMT-K 10) was found to play a key role to give 1,2-pentanediol (1,2-PeDO) in Pd catalysed furfural hydrogenation. Among various Pd loadings on MMT-K 10, 3% Pd/MMT-K 10 catalyst exhibited excellent performance giving almost complete conversion of FFR and the highest selectivity of 66% to 1,2-PeDO. Py-IR of the catalyst evidenced the presence of Brønsted acidity which was responsible in C5-O cleavage of furan ring after the formation of furfuryl alcohol which is the first step intermediate in FFR hydrogenation. At a lower temperature of 140 °C, highest selectivity of 56% was achieved for FAL while increase in temperature to 220 °C, enhanced the selectivity to 1,2-PeDO. Keeping the temperature constant at 220 °C, with increase in H2 pressure from 500 to 750 psig, resulted in decrease in 1,2-PeDO selectivity from 66 to 34% with proportionate increase in THFAL selectivity. Thus as per the requirement, the product selectivities can be tailored by varying the reaction parameters suitably. Several control experiments were also performed the results of which combined with the characterization data allowed to propose a plausible reaction pathway for the formation of 1,2-PeDO.

Bimetallic Au-Ag/Al2O3 as efficient catalysts for the hydrocarbon selective reduction of NOx from lean burn engine exhaust - More, P. M.; Dongare, M. K.; Umbarkar, S. B.; Granger, P.; Dujardin, C. (Catalysis Today, 2018)
Catalytic properties of Au-Ag/Al2O3 catalysts, prepared by successive impregnation, have been investigated for the hydrocarbon selective catalytic reduction (HC-SCR) of NOx. The performances of pre-reduced and aged catalysts were evaluated on synthetic reaction mixtures with gas compositions representative of the exhaust of Diesel powered engines. An optimal 2 wt.% Ag loading was chosen and the order of introduction during sequential impregnation of Ag or Au on respectively pre-impregnated Au/Al2O3 and Ag/Al2O3 substrates was investigated revealing drastic changes on the catalytic properties after aging. XPS analysis shows a significant silver enrichment irrespective of the preparation route and aging conditions whereas ex situ UV-vis DRS analysis reveals significant electronic disturbances which reflect different interactions between Au and Ag in fresh and aged Au-Ag/Al2O3 and Ag-Au/Al2O3 catalysts. As a consequence, significant rate enhancements in NOx conversion were observed with the superior performance of Au-Ag/Al2O3 but a lower resistance to deactivation at high temperature explained by different behaviour towards redispersion/agglomeration processes highlighted from TEM observations. (C) 2016 Elsevier B.V. All rights reserved.

Biomass-mediated synthesis of Cu-doped TiO2 nanoparticles for improved-performance lithium-ion batteries - Kashale, Anil A.; Dwivedi, Pravin K.; Sathe, Bhaskar R.; Shelke, Manjusha V.; Chang, Jia-Yaw; Ghule, Anil V. (ACS Omega, 2018)
Pure TiO2 and Cu-doped TiO2 nanoparticles are synthesized by the biomediated green approach using the Bengal gram bean extract. The extract containing biomolecules acts as capping agent, which helps to control the size of nanoparticles and inhibit the agglomeration of particles. Copper is doped in TiO2 to enhance the electronic conductivity of TiO2 and its electrochemical performance. The Cu-doped TiO2 nanoparticle-based anode shows high specific capacitance, good cycling stability, and rate capability performance for its envisaged application in lithium-ion battery. Among pure TiO2, 3% Cu-doped TiO2, and 7% Cu-doped TiO2 anode, the latter shows the highest capacity of 250 mAh g(-1) (97.6% capacity retention) after 100 cycles and more than 99% of coulombic efficiency at 0.5 A g(-1) current density. The improved electrochemical performance in the 7% Cu-doped TiO2 is attributed to the synergetic effect between copper and titania. The results reveal that Cu-doped TiO2 nanoparticles might be contributing to the enhanced electronic conductivity, providing an efficient pathway for fast electron transfer.

Carbon fabric based solar steam generation for waste water treatment - Higgins, M. W.; Rahmaan, Shakeel A. R.; Devarapalli, Rami Reddy; Shelke, Manjusha V.; Jha, Neetu (Solar Energy, 2018)
Decontamination of waste water is one of the most practical techniques to tackle the worldwide clean water shortage. In recent times, solar steam based decontamination of contaminated water has been attested as a potential sustainable strategy to get clean water using renewable resources. Herein, we report the utilization of Carbon fabric and Titanium Nanorods on Carbon Fabric for solar steam based water purification techniques. The performance of Carbon Fabric was tested under different conditions and the results proved that Carbon Fabric has excellent light to heat conversion capabilities in both real and ideal conditions. Owing to the excellent performance of Carbon Fabric, it was used for purification of different types of contaminated water. About 99.9% of salt and 87% of organic contaminants were removed from saline water and organic waste water respectively, using a simple low cost carbon fabric based homemade prototype. We also present the application of Titanium Nanorods on carbon fabric for the efficient removal of dye molecules like Rhodamine B from contaminated water using solar driven interfacial steam generation mechanism.
Keywords: Desalination; Dye degradation; Solar steam; Waste water treatment

Cascade synthesis of 5-(Acetoxymethyl) furfural from carbohydrates over Sn-mont catalyst - Shinde, Suhas; Deval, Kashmira; Chikate, Rajeev; Rode, Chandrashekhar (ChemistrySelect, 2018)
The 5-(Acetoxymethyl)furfural (AcMF) is emerged as an important alternative for 5-(hydroxymethyl)furfural (HMF). It is also a starting material for those products which are typically prepared from HMF. The growing importance of AcMF encouraged us to prepare it directly from cheap and abundant carbohydrates. The production AcMF from glucose and glucose-like carbohydrates is an exigent assignment, owing to tough isomerisation of glucose to fructose. The Sn-Mont catalyst having a unique combination of Lewis as well as Bronsted acid sites was employed for direct glucose conversion into AcMF. Lewis acid sites of Sn-Mont facilitate the isomerisation of glucose to fructose. At the same time, dehydrative-esterification of fructose to AcMF is catalyzed by Bronsted acid sites of Sn-Mont. Different concentrations of Sn containing Sn-Mont catalysts were by prepared mixing montmorillonite clay with different molar concentration (e.g. 0.1 M-0.4 M) of aqueous solutions of SnCl4 center dot 5H(2)O. AcMF was produced in as high as 43% yield directly from glucose over Sn-Mont(0.3 M) catalyst owing to its highest acid strength. The efficacy of Sn-Mont(0.3 M) catalyst was also probed for sucrose and fructose that resulted in 53% and 58% yield of AcMF, respectively. The critical properties of all the prepared Sn-Mont catalysts were investigated through XRD, BET surface area, ICP-OES, temperature-programmed desorption of NH3 and pyridine-FTIR and XPS techniques.
Keywords: 5-(Acetoxymethyl)furfural; Bronsted/Lewis acid; carbohydrates; Dehydrative-esterification; Sn-Mont

Catalyst-free oxidation of sulfides to sulfoxides and diethylamine catalyzed oxidation of sulfides to sulfones using Oxone as an oxidant (vol 43, pg 6875, 2017) - Kupwade, R. V.; Khot, S. S.; Lad, U. P.; Desai, U. V.; Wadgaonkar, P. P. (Research on Chemical Intermediates, 2018)

Characterization of mineral phosphate solubilizing and plant growth promoting bacteria from termite soil of arid region - Chakdar, Hillol; Dastager, Syed G.; Khire, Jayant M.; Rane, Digeshwar; Dharne, Mahesh S. (3 Biotech, 2018)
Five highly efficient phosphate solubilizing bacteria, viz., Pantoea sp. A3, Pantoea sp. A34, Kosakonia sp. A37, Kosakonia sp. B7 and Bacillus sp. AH9 were isolated from termitorial soils of Sanjivani island of southern Maharashtra, India. These isolates were characterized and explored for phosphate solubilization and plant growth promotion. Among these, Bacillus sp. AH9 showed highest phosphate solubilization index (3.5) and solubilization efficiency (250%) on Pikovskaya agar. Interestingly, Pantoea sp. A34 displayed maximum mineral phosphate solubilization (1072.35mg/L) in liquid medium and during this period the pH dropped to 3.13. All five isolates had highest P solubilization at 48h after inoculation. During mineral phosphate solubilization, both gluconic acid and 2-keto gluconic acid were produced by Kosakonia and Bacillus isolates, while only 2-keto gluconic acid was detected in Pantoea isolates. Highest organic acid (39.07 +/- 0.04g/L) production was envisaged in Bacillus sp. AH9, while Pantoea sp. A34 produced the least amount (13.00 +/- 0.01g/L) of organic acid. Seed bacterization with Pantoea sp. A3 and Kosakonia sp. A37 resulted in 37% and 53% increase in root length of tomato seedlings, respectively, while Pantoea sp. A34 and Kosakonia sp. B7 had deleterious effects on root length as well as overall growth of the seedlings. To our knowledge, this is the first report of plant growth promoting potential of microorganisms isolated from termitorial soil of Sanjivani island, which is a drought-prone area. Therefore, such efficient growth promoting P solubilizers can offer an effective solution for sustainable agriculture in arid, dryland farming and drought-prone regions.

Chemical oxidative and solid state synthesis of low molecular weight polymers for organic field effect transistors - Mahale, Rajashree Y.; Dharmapurikar, Satej S.; Chini, Mrinmoy Kumar (Chemical Physics Letters, 2018)
Solution processability of the precursor molecules is a major issue owing to their limited solubility for the synthesis of conjugated polymers. Therefore, we favour the solvent free solid state chemical oxidative polymerization route for the synthesis of diketopyrrolopyrrole (DPP) based donor-acceptor (D-A) type conjugated polymers. D-A type polymer Poly(S-OD-EDOT) which contains DPP coupled with EDOT donor units is synthesized via solid state polymerization method. The polymer is employed as an active layer for organic field-effect transistors to measure charge transport properties. The Polymer shows good hole mobility 3.1 x 10(-2) cm(2) V-1 s(-1), with a on/off ratio of 1.1 x 10(3). (C) 2018 Elsevier B.V. All rights reserved.

Close loop separation process for the recovery of Co, Cu, Mn, Fe and Li from spent lithium-ion batteries - Dutta, Deblina; Kumari, Archana; Panda, Rekha; Jha, Soni; Gupta, Divika; Goel, Sudha; Jha, Manis Kumar (Separation and Purification Technology, 2018)
Lithium-ion batteries (LIBs) are essential energy source used in advanced electronic gadgets for getting constant and continuous power supply. Huge amount of spent LIBs are generated after their end use. LIBs contain metals, organics and plastics which require proper treatment before disposal. Keeping in view of stringent environmental regulations, limited natural resources and energy crisis, adopting recycling will not only protect the environment and pacify the gap between demand and supply but also conserve the natural resources. Present paper reports a complete process for the recycling of LIBs to recover metals and materials as value added products fulfilling zero waste concept. Initially, the spent LIBs were crushed and beneficiated by wet scrubbing process to separate cathodic material, plastic and metallic fractions. The cathodic material contained 20% Co and 2.4% Li along with other impurities (Mn, Fe, Cu). The cathodic material obtained from different LIBs were homogenized and put to leaching studies to optimize various process parameters viz. effect of leachant concentration, temperature, time, etc. About 97% Co and 99.99% Li were leached using 2 M H2SO4 and 10% H2O2 at room temperature, in 2 h maintaining pulp density 75 g/L. Kinetics for leaching of Co fitted well with Chemical reaction control dense constant size cylindrical particles model, i.e. 1 - (1 - X)(1/2) = Kct. The leach liquor obtained was further processed to recover Mn and Fe using (NH4)(2)S2O8 as a precipitant whereas 99.99% Cu was extracted using LIX 84 IC at eq. pH 2, O/A ratio 1/1 and mixing time 5 min. Further, from the leach liquor depleted with Mn, Fe and Cu, similar to 98% Co was extracted using 20% Cyanex 272 at pH 4.8 in 10 min maintaining phase ratio (O/A) 1/1 in two stages, leaving Li in the raffinate. From the pure Co solution, value added products as metal and salt were produced using electrowinning/evaporation/precipitation techniques. The TCLP test of leached residue shows the presence of metals within permissible limit and the effluent generated was treated in an effluent treatment plant (ETP) with standard procedure and recycled to the system. The developed clean process is economical as well as environment friendly and has potential to be translated in industry after scale-up studies.

Cobalt-doped Ba2In2O5 brownmillerites: an efficient electrocatalyst for oxygen reduction in alkaline medium - Jijil, C. P.; Patil, I. M.; Kakade, B.; Nandini Devi, R. (ACS omega, 2018)
A series of compounds with cobalt doping in the indium site of Ba2In2O5 brownmillerites exhibited excellent oxygen reduction activity under alkaline conditions. Doping (25%) retains the brownmillerite structure with disorder in the O3 site in the two-dimensional alternate layer along the ab plane. Further substitution of cobalt in the indium site leads to the loss of a brownmillerite structure, and the compound attains a perovskite structure. Cobalt-doped samples exhibited far better oxygen reduction reaction (ORR) activity when compared to the parent Ba2In2O5 brownmillerite. Among the series of compounds, BaIn0.25Co0.75O3−δ with the highest Co doping and oxygen vacancies randomly distributed in the lattice exhibited the best ORR activity. BaIn0.25Co0.75O3−δ showed a 40 mV positive shift in the onset potential with better limiting current density and a nearly four-electron-transfer reduction pathway when compared to the parent Ba2In2O5 brownmillerite.

Co-gasification of high ash coal–biomass blends in a fluidized bed gasifier: experimental study and computational intelligence-based modeling - Tiwary, Shishir; Ghugare, Suhas B.; Chavan, Prakash D.; Saha, Sujan; Datta, Sudipta; Sahu, Gajanan; Tambe, Sanjeev S. (Waste and Biomass Valorization, 2018)
Co-gasification (COG) is a clean-coal technology that uses a binary blend of coal and biomass for generating the product gas; it is environment-friendly since it emits lesser quantities of pollutants compared to the coal gasification process. Although coals found in many countries contain high percentages of ash, co-gasification studies involving such coals, and the process modeling thereof, are rare. Accordingly, this study presents results of the co-gasification experiments conducted in a fluidized-bed gasifier (FBG) pilot plant using as a feed the blends of high ash Indian coals with three biomasses, namely, rice husk, press mud, and sawdust. Since the underlying physicochemical phenomena are complex and nonlinear, modeling of the COG process has been performed using three computational intelligence (CI)-based methods namely, genetic programming, artificial neural networks, and support vector regression. Each of these formalisms was employed separately to develop models predicting four COG performance variables, namely, total gas yield, carbon conversion efficiency, heating value of product gas, and cold gas efficiency. All the CI-based models exhibit an excellent prediction accuracy and generalization performance. The co-gasification experiments and their modeling presented here for a pilot-plant FBG can be gainfully utilized in the efficient design and operation of the corresponding commercial scale co-gasifiers utilizing high ash coals.
Keywords: Artificial neural networks; Co-gasification; Computational intelligence; Fluidized bed gasifier; genetic programming; support vector regression

Covalent organic frameworks: chemistry beyond the structure - Kandambeth, S.; Dey, K.; Banerjee, R. (Journal of the American Chemical Society, 2018)
Covalent organic frameworks (COFs) represent a new field of rapidly growing chemical research that takes direct inspiration from diverse covalent bonds existing between atoms. The success of linking atoms in two and three dimensions to construct extended framework structures moved the chemistry of COFs beyond the structures to methodologies, highlighting the possibility of prospective applications. Although structure to property relation in COFs has led to fascinating properties, chemical stability, processability and scalability were some of the important challenges that needed to be overcome for their successful implementation. In this Perspective, we take a closer look at the growth of COFs from mere supramolecular structures to potential industrializable materials.

CRC handbook of terpenoids: triterpenoids volume I: acyclic, monocyclic, bicyclic, tricyclic, and tetracyclic terpenoids - Dev, S.; Nagasampagi, B.A. (CRC Press, Inc., 2018)
This Handbook, pinpoints salient features of known information about Terpenoids in a readily accessible and readable format. Terpenoids have singularly enriched organic chemistry by its variety of structural types, by its wealth of“unexpected” reactions, rearrangements and spectral features, and by offering exciting targets for synthesis. Much imaginative experimental work has been invested in exploring their natural pathways. Recent years have revealed an increasingly important biological and ecological role for several of its members.

CRC handbook of terpenoids: triterpenoids: Volume ii: pentacyclic and hexacyclic triterpenoids - Dev, S.; Gupta, A.S. (CRC Press, 2018)
A compilation of all the known information on terpenoids specifically triterpenoids, is presented in these volumes. The most important available information on a particular compound is discussed, such as its isolation/occurence, available spectral data, and leading references on structural determination. Additionally, triterpenoids synthesis, biosynthesis, proven pharmacological properties, and any known applications are explained. A comprehensive general introduction has been included which surveys the development of triterpenoid chemistry from the beginning to the present. Extremely helpful is the selected list of references to books and reviews dealing with various aspects of triterpenoid chemistry

CSGID solves structures and identifies phenotypes for five enzymes in toxoplasma gondii - Lykins, Joseph D.; Filippova, Ekaterina V; Halavaty, Andrei S.; Minasov, George; Zhou, Ying; Dubrovska, Ievgeniia; Flores, Kristin J.; Shuvalova, Ludmilla A.; Ruan, Jiapeng; El Bissati, Kamal; Dovgin, Sarah; Roberts, Craig W.; et al. (Frontiers in Cellular and Infection Microbiology, 2018)
Toxoplasma gondii, an Apicomplexan parasite, causes significant morbidity and mortality, including severe disease in immunocompromised hosts and devastating congenital disease, with no effective treatment for the bradyzoite stage. To address this, we used the Tropical Disease Research database, crystallography, molecular modeling, and antisense to identify and characterize a range of potential therapeutic targets for toxoplasmosis. Phosphoglycerate mutase II (PGMII), nucleoside diphosphate kinase (NDK), ribulose phosphate 3-epimerase (RPE), ribose-5-phosphate isomerase (RPI), and ornithine aminotransferase (OAT) were structurally characterized. Crystallography revealed insights into the overall structure, protein oligomeric states and molecular details of active sites important for ligand recognition. Literature and molecular modeling suggested potential inhibitors and druggability. The targets were further studied with vivoPMO to interrupt enzyme synthesis, identifying the targets as potentially important to parasitic replication and, therefore, of therapeutic interest. Targeted vivoPMO resulted in statistically significant perturbation of parasite replication without concomitant host cell toxicity, consistent with a previous CRISPR/Cas9 screen showing PGM, RPE, and RPI contribute to parasite fitness. PGM, RPE, and RPI have the greatest promise for affecting replication in tachyzoites. These targets are shared between other medically important parasites and may have wider therapeutic potential.

Cyclohexylation of resorcinol with cyclohexanol catalyzed by tungstophosphoric acid supported zirconia catalysts - Balasubramanian, V. V.; Devassay, B. M.; Halligudi, S. B.; Deepika, R.; Umbarakar, S. B.; Vinu, A. (Journal of Nanoscience and Nanotechnology, 2018)
We demonstrate a highly active and reusable heterogeneous catalyst system, tungstophosphoric acid (TPA) supported on zirconia (ZrO2), for the cyclohexylation of resorcinol by cyclohexanol to produce value added chemicals such as 2-cyclohexyl resorcinol, 4-cyclohexyl resorcinol and 3-Hydroxy cyclohexyl phenyl ether under liquid phase reaction condition. TPA/ZrO2 catalysts prepared with different TPA loadings (5-30 wt.%) by wet impregnation method and calcined in the temperature range of 650-850 degrees C were characterized by Nitrogen sorption analysis, XRD, FTIR, DTG and DTA, and P-31 MAS NMR spectroscopy. Among the catalysts studied, 15 wt.% TPA/ZrO2 catalyst calcined at 750 degrees C gave the highest conversion of resorcinol (51.2%) with the selectivities for 3-Hydroxy cyclohexyl phenyl ether (53.9%) and 2-cyclohexyl resorcinol and 4-cyclohexyl resorcinol together (46.1%) under optimum reaction conditions. However, the selectivity of the products were controlled by varying the reaction conditions. At higher conversion of resorcinol (78.9%), only C-alkylated products were formed at 200 degrees C with 15 wt.% TPA/ZrO2 catalyst calcined at 750 degrees C. The combination of TPA and ZrO2 coupled with calcination temperature offered an excellent platform for the conversion of resorcinol into O- or C-alkylated products.
Keywords: 15% TPA/ZrO2; Cyclohexanol; Cyclohexylation; Keggin TPA; Resorcinol

Cyclometallation of a germylene ligand by concerted metalation-deprotonation of a methyl group - Bakthavachalam, K.; Dutta, Sayan; Arivazhagan, C.; Raghavendra, Beesam; Haridas, Anagha; Sen, Sakya S.; Koley, Debasis; Ghosh, Sundargopal (Dalton Transactions, 2018)
The reaction of [CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)]GeCl with LiN(SiMe3)(2) was previously reported, which led to the formation of a hetero-fulvene type germylene, [CH{(CMe)(C?CH2)(2,6-iPr(2)C(6)H(3)N)}(2)]Ge through the deprotonation of the C-H bond from the methyl substituents. In this paper, we attempted the analogous reaction with (Dipp)NCMeCHCOMeGeCl using LiN(SiMe3)(2) which gave rise to a metathesis product, (Dipp)NCMeCHCOMeGeN(SiMe3)(2) (2). However, the reactions of 2 with [M2Cl2(-Cl)(2)((5)-Cp*)(2)] (M = Rh and Ir) resulted in cyclometallated Rh and Ir complexes through the activation of the C-H bond from the germylene ligand. The complexes were characterized by single crystal X-ray analysis, which authenticated the presence of Ge-Rh and Ge-Ir bonds. DFT studies have been performed to understand the mechanism.

Dephytinizing and probiotic potentials of saccharomyces cerevisiae (NCIM 3662) strain for amelioration of nutritional quality of functional foods - Kumar Raja Puppala; Kumar , V. Ravi; Khire, Jayant; Dharne, Mahesh (Probiotics and Antimicrobial Proteins, 2018)
Increase of undigested complexes of phytic acid in food is gaining serious attention to overcome nutritional challenges due to chelation effects. We investigated soil-borne yeast phytase from Saccharomyces cerevisiae (NCIM 3662) for dephytinization of foods, probiotic properties, and process development. The strain produced 45 IU/DCG by cell-bound phytase in an unoptimized medium was increased fourfold (164 IU/DCG) in 12 h using statistical media optimization. The process was scaled-up up to 10-L fermenter scale with increased phytase productivity of 6.4 IU/DCG/h as compared to the lab scale. The strain displayed probiotic characteristics like tolerance to artificial gastric acid conditions, hydrophobicity, autoaggregation, coaggregation, and bile salt hydrolase (BSH) activity. Further, it could dephytinize (removal of phytic acid; an anti-nutritional factor) functional foods like ragi (finger millet) flour, soya flour, chickpea flour, and poultry animal feed. A combination of cell-bound dephytinizing phytase and nutrition-ameliorating probiotic traits of S. cerevisiae (NCIM 3662) presents profound applications in food technology sector.

Deposition of Au nanoparticles inside porous CeO2 nanocubes using Langmuir-Blodgett technique - Das, Subhasis; Bhattacharjee, Gourab; Satpati, Biswarup; Kumar, Mukesh; Deka, Sasanka; Ghosalya, Manoj Kumar; Gopinath, Chinnakonda S.; Bala, Tanushree (New Journal of Chemistry, 2018)
Porous 3D CeO2 nanocubes were synthesized using hot injection technique. These nanocubes were able to form a stable monolayer over water and HAuCl4 subphase in Langmuir-Blodgett (LB) trough due to the presence of surface capped oleic acid and oleylamine. CeO2-Au nanocomposites were synthesized exploiting the ability of oleylamine to reduce AuCl4 ions to Au-0, via LB method. CeO2 nanocubes gave rise to excellent long-range assembly at air/water interface and gold nanoparticles were formed inside these porous nanocubes without disturbing this arrangement. The formation of a stable monolayer was evidenced from the surface pressure-area (P-A) isotherm. The development of Au nanoparticles was confirmed with great effort from a comprehensive study using UV-Vis spectroscopy, XRD, XPS, FTIR, TEM, STEM, EDX, tomography and chemical mapping.

Design and development of a test rig to investigate the load deflection characteristics of helical spring lock washers - Wagh, Hemant; Desale, Girish R. (International Journal of Structural Integrity, 2018)
Purpose The helical spring lock washer is a part of nut-bolt joint assembly used in different industries like automobile, aerospace, mechanical, chemical, electrical, electronics, etc. It works as a part of temporary joint and plays important role in loosening behavior of assembly under dynamic (vibrations) conditions. Thus, it is necessary to investigate the performance of helical spring lock washer under different controlled operating conditions in order to satisfy its functional requirement. Design/methodology/approach In the present investigation, a novel test rig is designed and developed to determine the load deflection characteristics of helical spring lock washers. The test rig facilitates the controlled linear displacement of the Helical Spring Lock (HSL) washer with predetermined angular rotation of the handle gives the corresponding reaction load on the display. Additionally, the repeatability and reproducibility of the test rig was carried out. Findings The newly designed and developed test rig is enough capable to differentiate the load deflection characteristics during compressive loading and unloading of helical spring lock washers. Additionally, the loss of strain energy can be determined from the load deflection characteristics of helical spring lock washer. Originality/value The present test rig is designed and developed to investigate the load deflection characteristics under compressive loading and unloading of Helical spring lock washer. The test rig has least count of 0.4905N for load measurement and 0.01389 mm for linear displacement.

Design, synthesis, and pharmacological evaluation of fluorinated azoles as anti-tubercular agents - Gholap, Somnath; Tambe, Macchindra; Nawale, Laxman; Sarkar, Dhiman; Sangshetti, Jaiprakash; Damale, Manoj (Archiv Der Pharmazie, 2018)
Design, synthesis, and biological screening of 2,2-dimethyl-2,3-dihydrobenzofuran tethered 1,3,4-oxadiazole derivatives as anti-tubercular agents were described. The synthesis of the target compounds was conducted by a series of reaction schemes. All the synthesized compounds were characterized by IR, H-1 NMR, C-13 NMR, and mass spectrometry. The therapeutic potential of the synthesized compounds was confirmed by molecular docking studies. Among the synthesized compounds, 12a, 12c, 12d, 12e, 12g, and 12j were found to be more active against non-replicating than against replicating cultures of Mycobacterium tuberculosis H37Ra ex vivo and in vitro. These compounds exhibit minimum inhibitory concentration (MIC) values in the range of 2.31-23.91g/mL. The cytotoxicity study was conducted against the cell lines THP-1, A549 and PANC-1, and the compounds were observed to be non-toxic to host cells. Molecular docking was conducted with InhA (FabI/ENR) and suggested the antimycobacterial potential of the synthesized compounds. The investigation presented here was found to be adventitious for the development of new therapeutic agents against Mycobacterium infection.
Keywords: 1; 2; 2-dimethyl-2; 3; 3-dihydrobenzofuran; 4-Oxadiazole; anti-tubercular agents; Cytotoxicity; Molecular docking

Detection of ciprofloxacin residues in cow milk: a novel and rapid optical beta-galactosidase-based screening assay - Kalunke, Raviraj M.; Grasso, Gerardo; D'Ovidio, Renato; Dragone, Roberto; Frazzoli, Chiara (Microchemical Journal, 2018)
Ciprofloxacin (a member of the fluoroquinolone class) is one of the most widely used antibacterial agents for the treatment of bacterial infections in livestock. The improper use of such antibacterial agents could lead to the presence of residues in animal origin foods (including milk) and consequently harmful effects for health of consumers, together with the spread of antibiotic-resistant bacterial strains. Therefore, in order to support good farming practices and to ensure food safety, antimicrobial (in particular fluoroquinolones) residues surveillance through improved monitoring techniques is crucial. However, commercial available kits for the detection of fluoroquinolones residues in food samples are time-consuming and still fail to detect MRL concentrations for fluoroquinolones (e.g. 0.1 mg/kg for the sum of enrofloxacin and ciprofloxacin residues). Here a novel and rapid assay for ciprofloxacin residual detection through optical microbiological screening in commercially pasteurized cow's milk samples is described. Escherichia coli ATCC 11303 cell proliferation was optically monitored by measuring endogenous (beta-gal activity that was determindd through colorimetric assay in the presence of a chromogenic beta-gal artificial substrate. Optical density of E. coli cell culture (linked to cell proliferation) was positively correlated with endogenous beta-gal activity. As the presence of ciprofloxacin residues inhibits the E. coli cell proliferation in tested samples, (3-gal levels decreased more in exposed samples than in control. The essential step of beta-gal induction (usually obtained by IPTG) was obtained by exploiting the lactose present in the milk. Our findings show a detection of ciprofloxacin residues at 1 MRL concentration after 1 h using ONPG as chromogenic 3 gal artificial substrate and lactose as (3-gal inducer. Compared to previously described methods, this assay proved to be a rapid, proficient and more eco-friendly (i.e. minimizing the use of additional reagents) system that could be potentially employed as screening method for detection ciprofloxacin residues in cow's milk. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Antibiotic resistance; Farm animals; Fluoroquinolones; HACCP; One health; Primary production; Risk assessment and management

Determination of the effect of polyamines on an oil-degrading strain of Yarrowia lipolytica using an odc minus mutant - Campos-Gongora, E.; Palande, A. S.; Leon-Ramirez, C.; Pathan, E. K.; Ruiz-Herrera, J.; Deshpande, M. V. (Fems Yeast Research, 2018)
Yarrowia lipolytica is an ascomycetous dimorphic yeast with immense potential for industrial applications, including bioremediation of crude oil-contaminated environments. It has been shown that a dimorphic marine isolate of Y. lipolytica (var. indica) has significant capacity to degrade fatty acids and alkanes, when in its yeast morphology. It has also been demonstrated that polyamines play an important role in the yeast-to-mycelium transition of different strains of Y. lipolytica that are unable to utilize those carbon sources. To determine the role of polyamines on their capacity to utilize oils and hydrocarbons, on the dimorphic transition, and also on other characteristics of the var. indica strain of Y. lipolytica, we proceeded to obtain ornithine decarboxylase minus (odc(-)) mutants. These mutants behaved as yeasts independently of the concentrations of putrescine added. Further, they conserved the oil-degrading capacity of the parent strain. The odc(-) mutant can thus be used in fatty acid degradation, and oil spill remediation with distinct advantages.

Dihedral angle control to improve the charge transport properties of conjugated polymers in organic field effect transistors - Dharmapurikar, Satej S.; Chithiravel, Sundaresan; Mane, Manoj V.; Deshmukh, Gunvant; Krishnamoorthy, Kothandam (Chemical Physics Letters, 2018)
Diketopyrrolopyrrole (DPP) and i-Indigo (i-Ind) are two monomers that are widely explored as active materials in organic field effect transistor and solar cells. These two molecules showed impressive charge carrier mobility due to better packing that are facilitated by quadrupoles. We hypothesized that the copolymers of these monomers would also exhibit high charge carrier mobility. However, we envisioned that the dihedral angle at the connecting point between the monomers will play a crucial role in packing as well as charge transport. To understand the impact of dihedral angle on charge transport, we synthesized three copolymers, wherein the DPP was sandwiched between benzenes, thiophenes and furans. The copolymer of i-Indigo and furan comprising DPP showed a band gap of 1.4 eV with a very high dihedral angle of 179 degrees. The polymer was found to pack better and the coherence length was found to be 112 angstrom. The hole carrier mobility of these polymer was found to be highest among the synthesized polymer i. e. 0.01 cm(2)/vs. The copolymer comprising benzene did not transport hole and electrons. The dihedral angle at the connecting point between i and Indigo and benzene DPP was 143 angstrom, which the packing and consequently charge transport properties. (C) 2018 Elsevier B. V. All rights reserved.

Direct synthesis of diethyl carbonate from ethanol and carbon dioxide over ceria catalysts - Giram, Ganesh G.; Bokade, Vijay V.; Darbha, Srinivas (New Journal Of Chemistry, 2018)
Direct synthesis of diethyl carbonate (DEC) by carboxylation of ethanol with CO2 was investigated over ceria catalysts. 2-Cyanopyridine (2-CP) was used for trapping water formed in the reaction and to shift the equilibrium towards the product side. An optimal dependence (volcanic plot) of the catalytic activity on the acidity/basicity molar ratio was observed. Neat ceria (procured from Daiichi Kigenso Kagaku Kogyo Co. Ltd, Japan) showed higher catalytic activity than metal incorporated ceria catalysts. CeO2 had the right kind of acidity/basicity ratio to activate ethanol and CO2 simultaneously, yielding DEC. The catalyst was reusable. The yield of DEC obtained in this study using the commercial catalyst was higher than that reported by others using ceria catalysts prepared by other methods. Under optimum conditions (ethanol:2-CP molar ratio = 2:1, catalyst = 2.17 wt% with respect to ethanol, CO2 pressure = 40 bar, reaction temperature = 150 degrees C and reaction time = 3 h) in a batch reaction, a DEC yield as high as 45 mol% (i.e., 38.7 mmol mmol(-1) of CeO2) was obtained.

Disintegrable NIR light triggered gold nanorods supported liposomal nanohybrids for cancer theranostics - Chauhan, Deepak S.; Prasad, Rajendra; Devrukhkar, Janhavi; Selvaraj, Kaliaperumal; Srivastava, Rohit (Bioconjugate Chemistry, 2018)
In this work, facile synthesis and application of targeted, dual therapeutic gold nanorods-liposome (GNR-Lipos) nanohybrid for imaging guided photothermal therapy and chemotherapy is investigated. The dual therapeutic GNR-Lipos nanohybrid consists of GNR supported, and doxorubicin (DOX) loaded liposome. GNRs not only serve as a photothermal agent and increase the drug release in intracellular environment of cancer cells, but also provide mechanical strength to liposomes by being decorated both inside and outside of bilayer surfaces. The designed nanohybrid shows a remarkable response for synergistic chemophotothermal therapy compared to only chemotherapy or photothermal therapy. The NIR response, efficient uptake by the cells, disintegration of GNR-Lipos nanohybrid, and synergistic therapeutic effect of photothermal and chemotherapy over breast cancer cells MDA-MB-231 are studied for the better development of a biocompatible nanomaterial based multifunctional cancer theranostic agent.

Draft genome sequence of Marinomonas fungiae strain AN44T (JCM 18476T), isolated from the coral Fungia echinata from the Andaman Sea - Kumari, Prabla; Badhai, Jhasketan; Das, Subrata K. (Genome Announcements, 2018)
Marinomonas fungiae strain AN44Twas isolated from mucus of the coralFungia echinataOptimum growth occurs at 3 to 5% NaCl. The draft genome is 4.2 Mb, with 3,776 protein-coding genes. It harbors genes for the degradation of aromatic compounds, such as quinate, ferulate,p-coumarate, protocatechuate, andp-hydroxyphenylacetate.

Dynamics of loops at the substrate entry channel determine the specificity of iridoid synthases - Sandholu, Anand S.; Mohole, Madhura; Duax, William L.; Thulasiram, Hirekodathakallu V.; Sengupta, Durba; Kulkarni, Kiran (Febs Letters, 2018)
Iridoid synthases belong to the family of short-chain dehydrogenase reductase involved in the biosynthesis of iridoids. Despite having high sequence and structural homology with progesterone 5 beta- reductase, these enzymes exhibit differential substrate specificities. Previously, two loops. L1 and L2 at substrate-binding pocket, were suggested to be involved in generating substrate specificity. However, the structural basis of specificity determinants was elusive. Here, combining sequence and structural analysis, site-directed mutagenesis, and molecular dynamics simulations, we have shown that iridoid synthase contains two channels for substrate entry whose geometries are altered by L1-L2 dynamics, primarily orchestrated by interactions of residues Glu161 and Gly162 of L1 and Asn358 of L2. A complex interplay of these interactions confer the substrate specificity to the enzyme.
Keywords: iridoid synthase; iridoids; Molecular dynamics simulations; progesterone 5 beta-reductase; Substrate specificity

Easily accessible lithium compound catalyzed mild and facile hydroboration and cyanosilylation of aldehydes and ketones - Bisai, Milan; Das, Tamal; Vanka, Kumar; Sen, Sakya S. (Chemical Communications, 2018)
Simple and readily accessible lithium compounds such as 2,6-ditertbutyl phenolate lithium (1a), 1,1' dilithioferrocene (1b) and nacnac lithium (1c) are found to be efficient single site catalysts for hydroboration of...

Effect of structural properties of organosolv lignins isolated from different rice husks on their liquefaction using acidic ionic liquids - Singh, Sandip K.; Dhepe, Paresh L. (Clean Technologies and Environmental Policy, 2018)
Lignin is the only naturally available sustainable resource of aromatic compound on the Earth. Depending on the properties of lignin and the reaction conditions employed for the liquefaction, it is observed that the product distribution alters. Since ionic liquids (ILs) are considered as green and have tuneable properties, in the current work, imidazolium-based acidic ILs were employed to liquefy organosolv lignins derived from different varieties of rice husks. When liquefaction was carried out at 120 A degrees C for 1 h 36% yield for EtOAc- and DEE-soluble products with high mass balance (97 +/- 3%) was observed. The detailed characterisations of lignins and organic solvent-soluble products were done by variety of techniques [GC-MS, FT-IR, UV-Vis, 2D (HSQC) NMR], and based on this, the correlation between activity and properties of catalyst and lignin was established. Depolymerisation of organosolv lignin (derived from three rice husks) into aromatic product was done, and experimental correlation studies were performed in both.

Effect of support on the catalytic activity of WOx promoted Pt in green diesel production - Janampelli, Sagar; Darbha, Srinivas (Molecular Catalysis, 2018)
Platinum and WOx-promoted platinum supported on SiO2-Al2O3, Al2O3, AlPO4-5 and ZrO2 catalysts were prepared by wet impregnation method and investigated for deoxygenation of oleic acid (OA, a representative fatty acid) producing diesel-range hydrocarbons. Support and WOx influenced the textural, electronic and catalytic properties of Pt. WOx promoted the deoxygenation activity through hydrodeoxygenation pathway. Structure-activity correlations revealed that metallicity of Pt and acidity of the catalyst are crucial in determining the catalytic performance and product selectivity. Among the catalysts tested, 4Pt-8WO(x)/ZrO2, having adequate metal dispersion and electron rich Pt (desired for hydrogen splitting), reduced WOx species (W5+;-desired for OA activation) and less amount of strong acid sites (desired to avoid hydrocracking) showed highest catalytic deoxygenation performance (OA conversion = 100 mol% and C18 hydrocarbon selectivity = 89.4% at 260 degrees C and 20 bar H-2 pressure). The study reveals that support plays a crucial role in determining the catalytic performance of platinum. (C) 2017 Elsevier B.V. All rights reserved.

Effects of constant kinetic energy of different impacting particles on slurry erosion wear of AA 6063 - Nandre, Bhushan D.; Desale, Girish R. (Journal of Tribology-Transactions of the ASME, 2018)
The present experimental study investigates the effect of constant kinetic energy on erosion wear of aluminum alloy 6063. Three different natural erodents (quartz, silicon carbide, and alumina) with different particle sizes are used to impact at 45 deg and 90 deg impact angles. For calculating the number of particles in the slurry pot, it is assumed that the solid particles are of spherical shape. The total numbers of impacting solid particles were kept constant by adjusting the solid concentration, velocity, and test duration. The scanning electron microscope (SEM) images of the three erodents show that the alumina particles have sharp edges with more angularity, and silicon carbide particles have subangular nature while quartz particles are blocky in shape. The mass loss per particle at 45 deg impact angle is observed higher than at normal impact angle. It may be due to the change in material removal mechanism with changing the impact angle. It is also found that the mass loss per particle from the target material having different particle size with constant kinetic energy remains constant for respective erodents. This indicates that the velocity exponent of impacting particles is around 2. The SEM images of eroded surfaces reveal the different mechanisms of material removal at 45 deg impact angle and at normal impact angle.

Efficient method for cyclopentanone synthesis from furfural: understanding the role of solvents and solubility in a bimetallic catalytic system - Dohade, Manisha; Dhepe, Paresh L. (Catalysis Science & Technology, 2018)
The platform chemical, furfural (FAL), is obtained from C5 stream of biomass, and effective conversion into various chemicals including cyclopentanone (CPO) would find many industrial applications. It is desirable to convert FAL to CPO under low H-2 pressure with high selectivity. In the current work, bimetallic catalysts with Pt as the base metal supported on carbon are evaluated in the synthesis of CPO using a biphasic solvent system. By tuning the solvent ratio, with toluene/water (3:4 v/v), 75% yield of CPO is achieved under 1 MPa H-2 at 180 degrees C. The difference in solubility of the substrate, intermediates and products, along with the optimum ratio of Pt and Co metals plays a crucial role in achieving better yields.

Electrochemical capacitive energy storage in PolyHIPE derived nitrogen enriched hierarchical porous carbon nanosheets - Deshmukh, Ashvini B.; Nalawade, Archana C.; Karbhal, Indrapal; Qureshi, Mohammed Shadbar; Shelke, Manjusha V. (Carbon, 2018)
Porous and interconnected electrodes based on carbon nanoarchitectures offer comprehensive advantages of large specific surface area and high porosity consequently increasing the specific capacitance of ultracapacitor energy storage systems. Emulsion-templated polymers, PolyHIPEs (Polymerized High Internal Phase Emulsions) are highly porous polymers with a structure of cages interconnected by windows thus provide suitable framework to create such porous carbon nanostructures. Herein, nitrogen enriched porous carbon nanosheets are synthesized by pyrolysis of polymer-silica hybrid PolyHIPE and subsequent silica removal. This nitrogen enriched porous carbon nanosheets when tested as an electrode for ultracapacitor, showed specific capacitance as high as 209 F/g at a current density of 1 A/g in 1 M H2SO4 with excellent capacity retention over long cycling. (c) 2017 Elsevier Ltd. All rights reserved.
Keywords: Energy storage; Nitrogen enriched porous carbon nanosheets; PolyHIPE template; Ultracapacitor

Electron transfer rate analysis of a site-specifically wired copper oxidase - Schlesinger, Orr; Pasi, Mor; Dandela, Rambabu; Meijler, Michael M.; Alfonta, Lital (Physical Chemistry Chemical Physics, 2018)
Electron transfer kinetic parameters of site-specifically wired copper oxidase were investigated. The enzyme's orientation towards the electrode was controlled by incorporation of propargyl-L-lysine as a site-specific anchoring point. Herein, we demonstrate the importance of immobilization orientation and how it affects electron transfer efficiency and kinetics to each of the enzyme's two active sites.

Enhanced microwave absorption property of reduced graphene oxide (RGO)-strontium hexaferrite (SF)/poly (vinylidene) fluoride (PVDF) - Acharya, Sanghamitra; Gopinath, Chinnakonda S.; Alegaonkar, Prashant; Datar, Suwarna (Dimond and Related Materials, 2018)
Enormous growth in the use of electronic gadgets presents a challenge to develop efficient electromagnetic interference (EMI) shielding materials specifically using composites with properties such as light weight and high shielding due to absorption. In the present work we have synthesized a composite material with three components; Reduced Graphene Oxide (RGO) and Strontium Hexaferrite (SrFe12O19) (SF) bound together by polymer Poly (Vinylidene) Fluoride (PVDF). Composite RGO/SF (RGOSF) was prepared by facile one port chemical reduction method. Surface anchoring of similar to 500 nm of magnetic particles over the graphene sheet was confirmed by Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Crystal structure of SF particles was analyzed before and after composite formation with RGO. Effective crystallite size was estimated from both XRD and Raman Spectroscopy which showed similar trend moving from SF to RGOSF to RGOSFPVDF. Polymer composite films of RGOSFPVDF were prepared by hot pressing. Both real and imaginary part of magnetic and dielectric parameters were studied. It was observed that enhancement of interfacial polarization and anisotropic heat loss in PVDF matrix was generated by RGOSF which ultimately created more scattering center and helped in absorption of electromagnetic radiation. Critical film thickness of 3 mm was capable to shield up to 33 dB EM energy of which > 99.9% was due to absorption.

Enhanced selectivity of 3-D ordered macroporous Pt/Al2O3 catalysts in nitrites removal from water - Sekhar, A. C. Sunil; Zaki, A.; Troncea, S.; Casale, S.; Vinod, C. P.; Dacquin, J. P.; Granger, P. (Applied Catalysis A-General, 2018)
Tailored macroporous mesoporous alumina supports have been successfully prepared using a single hard templating approach. Pt nanoparticles, showing similar physico-chemical properties, were homogeneously dispersed throughout the different alumina frameworks as catalytic active phase for drinking water treatment. We demonstrated that careful modification of pore properties of the catalyst (size and connectivity) by pseudomorphic transformation can strongly modulate the reaction rate and selectivity through the limited access to Pt active sites within the alumina porous particles. Specifically, 3-D Ordered Macroporous Pt-Al2O3 catalysts with a high degree of interconnectivity yield to superior catalytic properties (enhanced activity and selectivity) over pure mesoporous counterparts in the hydrogenation of nitrites in water. We found that large pores (240 nm) interconnected with windows (110 nm) alleviate mass transfer limitations and clearly improve NZ selectivity. The findings of this study further suggest the possibility of engineering the pore architecture of the support to fine tune the selectivity for a particular reaction rather than investigating more on tuning the properties of the costly active metallic phase.

Enhancement of field electron emission in topological insulator Bi2Se3 by Ni doping - Mazumder, K.; Sharma, A.; Kumar, Y.; Bankar, P.; More, M. A.; Devan, R.; Shirage, P. M. (Physical Chemistry Chemical Physics, 2018)
Nanostructures of bismuth selenide (Bi2Se3), a 3D topological insulator material, and nickel (Ni) doped Bi2Se3 samples were prepared by a hydrothermal method to explore the field emission properties. An enrichment in the field electron emission (FE) properties in terms of the threshold and turn-on field values of Bi2Se3 and Ni doped Bi2Se3 nanostructures was measured at a base pressure of ∼1 × 10−8 mbar. Using the background of the Fowler–Nordheim (FN) theory a field enhancement factor (β) of 5.7 × 103 and a threshold field value of 2.5 V μm−1 for 7.5% Ni doped Bi2Se3 were determined by investigating the J–E plot of the FE data. The value of β is three times higher than that of pure Bi2Se3 confirming the superior FE properties. The emission current was found to be very stable with the property of long standing durability as a negligible amount of variation was observed when measured at a constant value of 5 mA for 3 hours. The experimental results signify many opportunities for potential applications of Ni doped Bi2Se3 as a source of electrons in scanning as well as transmission electron microscopy, flat panel displays and as an X-ray generator, etc.

Enzymatic formation of a skipped methyl‐substituted octaprenyl side chain of longestin (KS‐505a): involvement of homo‐IPP as a common extender unit - Taro Ozaki; Shinde, Sandip S.; Gao, Lei; Okuizumi, Ryo; Liu, Chengwei; Ogasawara, Yasushi; Lei, Xiaoguang; Dairi, Tohru; Minami, Atsushi; Oikawa, Hideaki (Angewandte Chemie, 2018)
Longestin (KS‐505a), a specific inhibitor of phosphodiesterase, is a meroterpenoid that consists of a unique octacyclic terpene skeleton with branched methyl groups at unusual positions (C1 and C12). The biochemical analysis of Lon23, a methyltransferase involved in the biosynthesis of longestin, demonstrated that methylation of IPP afforded 3Z‐3‐methyl IPP. This compound as well as IPP was selectively accepted as extender units by Lon22, a geranylgeranyl diphosphate (GGPP) synthase homolog, to yield dimethylated GGPP (dmGGPP). Absolute configuration of dmGGPP was determined to be (4R, 12R) by degradation and chiral GC analysis. These findings led us to propose key steps of the biosynthetic pathway of the unusual homoterpenoid longestin.

Erratum to: catalyst-free oxidation of sulfides to sulfoxides and diethylamine catalyzed oxidation of sulfides to sulfones using oxone as an oxidant - Kupwade, R. V. (Research on Chemical Intermediates, 2018)
We describe here our journey from the failure of our attempts in controlled oxidation of sulfides to sulfoxides using an Oxone®–KBr combination to our success in the development of a catalyst-free protocol for the oxidation of sulfides to sulfoxides using Oxone as an oxidant. We also describe the failure of our attempts at the oxidation of sulfides to sulfones using an excess of Oxone–KBr as well as Oxone, and our success towards the development of a rapid, scalable and chromatography-free protocol for the oxidation of sulfides to sulfones using diethylamine–Oxone as an unprecedented catalyst–oxidant combination.
Keywords: diethylamine; organocatalysis; Oxidation; Oxone; Sulfones; Sulfoxides

Evaluation of Candida tropicalis (NCIM 3321) extracellular phytase having plant growth promoting potential and process development - Puppala, Kumar Raja; Naik, Tejali; Shaik, Alfina; Dastager, Syed; Kumar, V. Ravi; Khire, Jayant; Dharne, Mahesh (Biocatalysis and Agricultural Biotechnology, 2018)
Phytase is known to provide a solution for depletion of phosphorus (P). It helps it by hydrolyzing the insoluble P source in soil which is phytate. In this study, provides insight on yeast Candida tropicalis (NCIM 3321) which produces cell bound and extracellular thermostable phytase. The media components were optimized to enhance the enzyme production and checked for plant growth promoting activity. On optimization the isolate exhibited enhanced cell bound and extracellular phytase activity by four folds (from 236 to 1024 IU DCG⁻¹) and by five folds (from 0.46 to 1.95 IU ml⁻¹) respectively in 36 h. The production time decreased to 24 h compare to shake flask on Up-scaling the production process upto 10 L scale, thus increasing the productivity of cell bound (1810 IU DCG⁻¹day⁻¹) and extracellular phytase (6.08 IU ml⁻¹ day⁻¹). The crude phytase (12 IU) from NCIM 3321 strain was studied for plant growth promotion activity in lab scale and field level experiments with maize crop. Findings of the study revealed that the extracellular phytase derived from non pathogenic C. tropicalis (NCIM 3321) was found to be plant growth stimulating by increasing the available P in soil. Our findings of phytase isolated from non-pathogenic yeast C. tropicalis NCIM 3321 exhibited dephytinization potential. Therefore, current study may have profound application in sustainable agriculture.

Experimental evidences for existence of varying moieties and functional groups in assorted crop waste derived organosolv lignins - Singh, Sandip K.; Dhepe, Paresh L. (Industrial Crops and Products, 2018)
Isolation of organosolv lignins (ORGLs, water:ethanol, 180 degrees C, 1 h, 93 +/- 5% mass balance) from various lignocellulosic materials like rice husk (RH), wheat straw (WS), bagasse (BG) & wood chips (WC) was done and experimental evidences are provided to perceive the differences in the structures of isolated lignins. To achieve this on bulk level, lignins were characterized by XRD, GPC, TGA & elemental analysis and on molecular level using UV-vis, ATR, 1D/2D HSQC NMR techniques. Besides isolated lignins, crop wastes and pulps were also characterized to divulge details on their properties. It was revealed that lignins have varying concentrations of sinapyl (S), coniferyl (G) and p-coumaryl alcohols (H) and tricin (T) moieties. While, Tricin (T) type lignin moieties are observed only in RH and WS derived lignins, RH derived lignin has higher concentration of side chains than other isolated lignins. Additionally, it is discovered that most lignins have G as main moiety.

Exploring the biological roles of Dothideomycetes ABC proteins: leads from their phylogenetic relationships with functionally-characterized Ascomycetes homologs - Dube, Gaurav; Kadoo, Narendra; Prashant, Ramya (PLoS One, 2018)
Background The ATP-binding cassette (ABC) superfamily is one of the largest, ubiquitous and diverse protein families in nature. Categorized into nine subfamilies, its members are important to most organisms including fungi, where they play varied roles in fundamental cellular processes, plant pathogenesis or fungicide tolerance. However, these proteins are not yet well-understood in the class Dothideomycetes, which includes several phytopathogens that infect a wide range of food crops including wheat, barley and maize and cause major economic losses. Results We analyzed the genomes of 14 Dothideomycetes fungi (Test set) and seven well-known Ascomycetes fungi (Model set-that possessed gene expression/functional analysis data about the ABC genes) and predicted 578 and 338 ABC proteins from each set respectively. These proteins were classified into subfamilies A to I, which revealed the distribution of the subfamily members across the Dothideomycetes and Ascomycetes genomes. Phylogenetic analysis of Dothideomycetes ABC proteins indicated evolutionary relationships among the subfamilies within this class. Further, phylogenetic relationships among the ABC proteins from the Model and the Test fungi within each subfamily were analyzed, which aided in classifying these proteins into subgroups. We compiled and curated functional and gene expression information from the previous literature for 118 ABC genes and mapped them on the phylogenetic trees, which suggested possible roles in pathogenesis and/or fungicide tolerance for the newly identified Dothideomycetes ABC proteins. Conclusions The present analysis is one of the firsts to extensively analyze ABC proteins from Dothideomycetes fungi. Their phylogenetic analysis and annotating the clades with functional information indicated a subset of Dothideomycetes ABC genes that could be considered for experimental validation for their roles in plant pathogenesis and/or fungicide tolerance.

Facile and solvent-free domino synthesis of new quinolidinyl-2,4-thiazolidinones: antifungal activityand molecular docking - Subhedar, Dnyaneshwar D.; Shaikh, Mubarak H.; Tupe, Santosh G.; Deshpande, Mukund V.; Khedkar, Vijay M.; Jha, Prakash C.; Shingate, Bapurao B. (Mini-Reviews in Medicinal Chemistry, 2018)
Objective: We have synthesized new quinolidinyl-thiazolidinones via Knoevenagel condensation-alkylation reaction, catalyzed by [Et3NH][HSO4]. The present approach offers several advantages such as higher yields, eco-friendly reaction condition and economic availability of the catalyst. Method: The newly synthesized compounds were evaluated for their in vitro antifungal activity against six fungal strains. Some of the synthesized conjugates displayed good to moderate antifungal activity. Conclusion: Again, the molecular docking study performed against the fungal sterol 14 alpha-demethylase (CYP51) showed an excellent binding affinity towards the enzyme which could rationalize the promising antifungal activity portrayed by these derivatives and provides a platform for structure based drug design.

Facilitated lithium storage in hierarchical microsphere of Cu2S-MoS2 ultrathin nanosheets - Kadam, Sunil R.; Kalubarme, Ramchandra S.; Deshmukh, Shrutika P.; Panmand, Rajendra P.; Kawade, Ujjwala, V.; Kulkarni, Milind, V.; Deo, Shriniwas S.; Gosavi, Suresh W.; Kale, Bharat B. (ChemistrySelect, 2018)
Considering the high energy density Lithium ion batteries have become one of the best option for next-generation energystorage technologies. Transition metal chalcogenide nanomaterials are promising electrodes for Lithium-ion batteries. Molybdenum based layered chalcogenide materials wisely studied for rechargeable Li-ion batteries, due to its two-dimensional (2D) layered structure and better specific capacity. The three-dimensional (3D) synthesis of microsphere by ultrathin nanosheets is necessary for practical applications. Herein, the fabrication of a unique hierarchical 2D layered Cu2S-MoS2 nanostructure was (ultrathin nanosheets) demonstrated via in situ assembling of two-dimensional (2D) growths in facile solvothermal technique. The structural study reveals the existence of Cubic Cu2S and Rhombohedral MoS2 phase. Morphological study by FESEM and TEM shows unique ultrathin nanosheets of similar to 10 nm thickness self-assembled in the form of layered microsphere. In Li- ion storage testing, Cu2S-MoS2 electrode exhibited good specific discharge capacity of 651 mAhg(-1) at 50 mAg(-1) applied current and maintained 320 mAhg(-1) after 100 cycles. The facilitated advanced electrochemical performance attributed to layered ultrathin Cu2S-MoS2 composite nanosheets.

Fluorescent chemodosimeter for quantification of Cystathionine-y-synthase activity in plant extracts and imaging of endogenous biothiols - Agarwalla, Hridesh; Hoskere, Anila A.; Ali, Firoj; Pradhan, Swaraj Rashmi; Ganguly, Bishwajit; Pramanik, Sumit kumar; Das, Amitava (Chemical Communications, 2018)
A new reagent for quantification of CgS in plant extracts using a generalized methodology suitable for recognition of homocysteine (Hcy) with luminescence ON response.

From a helix to a small cycle: metadynamics-inspired alpha v beta 6 integrin selective ligands - Di Leva, Francesco Saverio; Tomassi, Stefano; Di Maro, Salvatore; Reichart, Florian; Notni, Johannes; Dangi, Abha; Marelli, Udaya Kiran; Brancaccio, Diego; Merlino, Francesco; Wester, Hans-Juergen; Novellino, Ettore; Kessler, Horst; et al. (Angewandte Chemie-International Edition, 2018)
The RGD-recognizing alpha v beta 6 integrin has only recently emerged as a major target for cancer diagnosis and therapy. Thus, the development of selective, low-molecular-weight ligands of this receptor is still in great demand. Here, a metadynamics-driven design strategy allowed us to successfully convert a helical nonapeptide into a cyclic pentapeptide (6) showing remarkable potency and alpha v beta 6 specificity. NMR and docking studies elucidated the reasons for the high affinity and selectivity of this compound, setting the ground for the rational design of new alpha v beta 6-specific small peptides or even peptidomimetics. In vivo PET imaging studies demonstrated the potential use of 6 for medical applications.

Glucose isomerization catalyzed by bone char and the selective production of 5-hydroxymethylfurfural in aqueous media - Matsagar, Babasaheb M.; Van Nguyen, Chi; Hossain, Md. Shahriar A.; Islam, Md. Tofazzal; Yamauchi, Yusuke; Dhepe, Paresh L.; Wu, Kevin C. -W. (Sustainable Energy & Fuels, 2018)
The selective production of 5-hydroxymethylfurfural (HMF) is important, and it is difficult with glucose substrates in a water solvent. Here we demonstrate a selective method for glucose-to-HMF conversion using the combined catalysis of bone char and 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate acidic ionic liquid catalysts with a high HMF selectivity (54%) in water.

High surface area nanoporous carbon derived from high quality jute from Bangladesh - Khan, Junayet Hossain; Lin, Jianjian; Young, Christine; Matsagar, Babasaheb M.; Wu, Kevin C. W.; Dhepe, Paresh L.; Islam, Md Tofazzal; Rahman, Md Mahbubur; Shrestha, Lok Kumar; Alshehri, Saad M.; Ahamad, Tansir; Salunkhe, Rahul R.; et al. (Materials Chemistry and Physics, 2018)
We report an economically viable and environment-friendly strategy for the preparation of nanoporous carbon (NC) from jute which is one of the most abundant natural fibers produced in Bangladesh and some South Asian countries. Nitrogen adsorption-desorption isotherms, X-ray diffraction, Raman spectroscopy, UV spectroscopy, and scanning/transmission electron microscopy were performed to characterize the obtained NC. Three different types of jute-derived NCs have been synthesized at three different temperatures, 700 degrees C, 800 degrees C and 900 degrees C. The NC prepared at 800 degrees C resulted in a high surface area (981 m(2) g(-2)) and was associated with the retention of the original fibrous shapes. This study shows a promising future for jute as a natural precursor for NCs for a myriad of applications ranging from water purification to gas separation to energy conversion and storage.
Keywords: Adsorbents; Graphitization; Jute; Nanoporous carbons; porous materials

High yield production of cellulose by a komagataeibacter rhaeticus PG2 strain isolated from pomegranate as a new host - Thorat, M.N.; Dastager, S.G. (RSC Advances, 2018)
Gluconacetobacter xylinus is a well-known organism that produces bacterial cellulose (BC). The present study was undertaken to find an alternative bacteria from a collection of 216 bacterial isolates, which were isolated from different rotten fruits and fermented beverages, to find a better producer of bacterial cellulose. We obtained a potent strain, which produced a high yield of BC from a rotten pomegranate sample, and was further identified as Komagataeibacter rhaeticus strain PG2 using 16S rRNA gene sequence analysis. To date, only two strains of Komagataeibacter rhaeticus are known to produce BC, and these were mainly isolated from a fermented beverage, kombucha. For the first time, we have isolated a BC producing Komagataeibacter rhaeticus strain PG2 from a rotten pomegranate sample. The new host environment and the substrate utilization pattern of strain PG2 reveal efficient bacterial cellulose production. Hestrin–Schramm (HS) liquid media containing glycerol as a carbon source resulted in the highest BC production (∼6.9 g L−1). A further increased yield of BC (∼8.7 g L−1) was obtained by using 3% (w/v) glycerol concentration, and this BC yield is the highest reported among any of the known Komagataeibacter rhaeticus strains reported. A detailed physico-chemical characterization of the BC membrane obtained from glycerol (Gly-BC) and glucose (Glc-BC) was performed. Interestingly, Gly-BC is found to be more compact and more crystalline in its nature compared to Glc-BC. The present study reveals the isolation of an efficient BC synthesizing strain using glycerol as a low-cost carbon source, confirming the economic feasibility of BC production. The structural characteristics of the BC membrane produced by glycerol were found to be more suitable for various applications.

Highly reactive crystalline-phase-embedded strontium-bioactive nanorods for multimodal bioactive applications - Durgalakshmi, D.; Ajay Rakkesh, R.; Kesavan, M.; Ganapathy, S.; Ajithkumar, T.G.; Karthikeyan, S.; Balakumar, S. (Biomaterials Science, 2018)
In the present work, a crystallization-induced strontium-bioactive material, with a composition similar to Bioglass 45S5 system, was obtained using a sol-gel-assisted microwave method with nanorod morphologies of 30-80 nm in size. The effect of crystallization induced in the glass network, and its influence on the bioactivity and mechanical properties of bone and dentin regeneration, were the main novel findings of this work. Rietveld analysis of X-ray diffraction spectra showed the best fit with sodium (combeite, Na2Ca2Si3O9) and calcium (clinophosinaite, Ca2Na6O14P2Si2; calcium strontium silicate, Ca1.5O4SiSr0.5; and calcium carbonate, CaCO3) enriched crystal systems. Multinuclear solid-state NMR studies provided detailed atomistic insight into the presence of crystalline mineral phases in the bioactive material. The dentin matrix and antibacterial studies showed good results for 5% strontium-substituted calcium compared with basic 45S5 composition due to its smaller particle size (30 nm), which suggested applications to dentin regeneration. Simulation studies have been demonstrated with clinophosinaite crystal data from the XRD spectra, with the glycoprotein salivary metabolites also showing that 5% strontium-substituted calcium has a higher binding affinity for the salivary compound, which is suitable for dentin regeneration applications. In vitro apatite formation studies showed that this material is suitable for bone regeneration applications.

Hydrothermally synthesized fluorescent Zn2SnO4 nanoparticles for dye sensitized solar cells - Das, Partha Pratim; Roy, Anurag; Agarkar, Shruti; Devi, Parukuttyamma Sujatha (Dyes and Pigments, 2018)
In this work, we have investigated the interaction of hydrothermally synthesized Zn2SnO4 (ZTO) nanoparticles (NPs) with two different commercial photo sensitizers such as N719 and N3 dye molecules and studied their performance in dye sensitized solar cells (DSSC). Interestingly, the ZTO NPs exhibited band edge emission in the mid UVA region and as a result possibility of enhanced light harvesting in the terminal UVA region was anticipated in the device due to the efficient energy transfer observed in case of the sensitizer N719 than N3. The dye sensitization property has been found to be higher for the N3 dye molecules than the N719 dye molecules as based on the time dependent dye loading study. The devices fabricated with ZTO-N719 exhibited improved photovoltaic performance compared to the ZTO-N3 based devices exhibiting an overall conversion efficiency of 2.56% by the former compared to the later (1.90%) under 1SUN 1.5AM illumination and sensitization for 12 h.

Impact of half-crown/two carbonyl:-Ca2+ metal ion interactions of a low molecular weight gelator (LMWG) on its fiber to nanosphere morphology transformation with a gel-to-sol phase transition - Maity, Arunava; Dey, Ananta; Si, Mrinal Kanti; Ganguly, Bishwajit; Das, Amitava (Soft Matter, 2018)
We report here a smart functional low molecular weight gelator (LMWG) L, containing an unusual metal ion coordination site, i.e. ``half-crown/two carbonyl''. The gelator L shows excellent gelation behavior with typical fibrillar morphology in acetonitrile, methanol and ethanol media. Upon Ca2+ ion binding with its ``half-crown/two carbonyl'' coordination site, the acetonitrile gel of L exhibits a fiber to nanosphere morphology transformation along with a gel-to-sol phase transition as confirmed by microscopic investigation and by direct naked eye visualization, respectively. The mechanism involved in this morphology transformation and gel-to-sol phase transition process was studied thoroughly with the help of computational calculations and various spectroscopic experiments and discussed.

Impact of stereochemistry on sharing chemical structures - Banik, Gregory; Karthikeyan, Muthukumarasamy; Nedwed, Karl; Kunitsky, Keith; D'Souza, Michelle; Abshear, Ty (255th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nexus of Food, Energy, and Water, 2018)

Incorporation of carbon nanofibers into a matrimid polymer matrix: effects on the gas permeability and selectivity properties - Dohade, Manisha (Applied Polymer, 2018)
Composite membranes containing carbon nanofibers (CNFs) and Matrimid were prepared by a solution-casting method. Prepared Matrimid–CNF composite membranes were characterized with X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and mechanical testing techniques. The mechanical properties of the composite membranes increased over that of the pristine polymeric membranes. To develop a broad fundamental understanding of the connection between the composite architecture and gas-transport properties, both the gas-permeability and gas-separation characteristics were evaluated. The gas-transport properties of the Matrimid–CNF composite membrane was measured with a single gas-permeation setup (He, H<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2, N<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2, CH<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">4 and CO<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2) at ambient temperature with the variable-volume method. The incorporation of CNFs (0.5–10 wt %) into the Matrimid matrix resulted in approximately a 22% reduction in the gas permeation of various gases, (H<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2, He, CO<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2, N<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2, and CH<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">4). Moreover, an improvement of 1.5 times in the gas selectivity was observed for CO<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2/CH<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">4, H<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2/CH<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">4, He/CH<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">4, and H<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2/N<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2 compared to pristine polymeric membrane. Hence, such polymer–CNF composite membranes could be suitable for gas-separation applications with high purity requirements. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. <span style="margin: 0px; padding: 0px; border: 0px; outline: 0px; font-size: 16px; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); font-weight: 700; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2018, <em style="margin: 0px; padding: 0px; border: 0px; outline: 0px; font-size: 16px; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">135, 46019.

Influence of chain length of long-chain fatty acid surfactant on the thermal conductivity of magnetite nanofluids in a magnetic field - Dadwal, Arun; Dadwal, Arun (Colloids and Surfaces A-Physicochemical and Engineering Aspects, 2018)
Stable magnetic nanofluids are prepared by dispersing long-chain fatty acid surfactants coated magnetite (Fe3O4) nanoparticles in toluene and investigated the effect of chain length of the surfactant molecules on the thermal conductivity of the magnetite nanofluids in a magnetic field. Superparamagnetic magnetite nanoparticles having a comparable particle size (similar to 10 nm) are coated with three different long-chain fatty acid surfactants; myristic acid (C13H27COOH), palmitic acid (C15H31COOH) and stearic acid (C17H35COOH). The thermal conductivity of the nanofluids, in a magnetic field, is found to decrease with increasing the chain length of the surfactant molecule. Among the three fluids, the shorter chain myristic acid coated nanofluid showed larger enhancement in the thermal conductivity at smaller fields as compared to the other fluids. The results indicated that the chain length of the surfactant molecule present on the surface of the magnetite nanoparticles affect the thermal conductivity of the magnetic nanofluid in an external magnetic field, due to the difference in the extent of interdigitation of the surfactant molecules.

Integrated transcriptomic and proteomic analyses suggest the participation of endogenous protease inhibitors in the regulation of protease gene expression in helicoverpa armigera - Lomate, Purushottam R.; Dewangan, Veena; Mahajan, Neha S.; Kumar, Yashwant; Kulkarni, Abhijeet; Wang, Li; Saxena, Smita; Gupta, Vidya S.; Giri, Ashok P. (Molecular & Cellular Proteomics, 2018)
Insects adapt to plant protease inhibitors (PIs) present in their diet by differentially regulating multiple digestive proteases. However, mechanisms regulating protease gene expression in insects are largely enigmatic. Ingestion of multi-domain recombinant Capsicum annuum protease inhibitor-7 (CanPI-7) arrests growth and development of Helicoverpa armigera (Lepidoptera: Noctuidae). Using de novo RNA sequencing and proteomic analysis, we examined the response of H. armigera larvae fed on recombinant CanPI-7 at different time intervals. Here, we present evidence supporting a dynamic transition in H. armigera protease expression on CanPI-7 feeding with general down-regulation of protease genes at early time points (0.5 to 6 h) and significant up-regulation of specific trypsin, chymotrypsin and aminopeptidase genes at later time points (12 to 48 h). Further, coexpression of H. armigera endogenous PIs with several digestive protease genes were apparent. In addition to the differential expression of endogenous H. armigera PIs, we also observed a distinct novel isoform of endogenous PI in CanPI-7 fed H. armigera larvae. Based on present and earlier studies, we propose potential mechanism of protease regulation in H. armigera and subsequent adaptation strategy to cope with anti-nutritional components of plants.

Integrative analysis of rewired central metabolism in temozolomide resistant cells - Immanuel, Selva Rupa C.; Ghanate, Avinash D.; Parmar, Dharmeshkumar S.; Marriage, Fiona; Panchagnula, Venkateswarlu; Day, Nap J.; Raghunathan, Anu (Biochemical and Biophysical Research Communications, 2018)
An authenticated U87MG clonal glioblastoma cell line was investigated to identify a sub-population of neurospheroidal (NSP) cells within the main epithelial population (U87MG). The NSP cells sorted using Fluorescence Assisted Cell Sorting (FACS) showed varied morphology, 30% lower growth rates, 40% higher IC50 values for temozolomide drug and could differentiate into the glial cell type (NDx). Metabolite profiling using HR-LCMS identified glucose, glutamine and serine in both populations and tryptophan only in U87MG as growth limiting substrates. Glycine, alanine, glutamate and proline were secreted by U87MG, however proline and glycine were re-utilized in NSP. Exo-metabolite profiling and phenotypic microarrays identified differential metabolism of primary carbon sources glucose and derived pyruvate for U87MG; glutamine and derived glutamate metabolism in NSP. Differential mRNA abundance of AKT1, PTEN, PIK3CA controlling metabolism, drug efflux, nutrient transport and epigenetic control MDM2 are potentially critical in shaping DNA methylation effects of temozolomide. Our study provides a new insight into the combined effect of these factors leading to temozolomide resistance in NSP. (C) 2017 Elsevier Inc. All rights reserved.
Keywords: Glutamine; Metabolic rewiring; Metabolite profiling; mRNA abundances; Temozolomide resistance; U87MG

Interconverting hydrogen-bonding and weak n -> pi* interactions in aqueous solution: A direct spectroscopic evidence - Deb, Pranab; Jin, Geun Young; Singh, Santosh K.; Moon, Juran; Kwon, Hyejin; Das, Aloke; Bagchi, Sayan; Kim, Yung Sam (Journal of Physical Chemistry Letters, 2018)
Molecular structure and function depend on myriad noncovalent interactions. However, the weak and transient nature of noncovalent interactions in solution makes them challenging to study. Information on weak interactions is typically derived from theory and indirect structural data. Solvent fluctuations, not revealed by structure analysis, further complicate the study of these interactions. Using 2D infrared spectroscopy, we show that the strong hydrogen bond and the weak n -> pi* interaction coexist and interconvert in aqueous solution. We found that the kinetics of these interconverting interactions becomes faster with increasing water content. This experimental observation provides a new perspective on the existence of weak noncovalent interactions in aqueous solution.

Intrinsically microporous polyimides containing spirobisindane and phenazine units: synthesis, characterization and gas permeation properties - Shrimant, Bharat; Dangat, Yuvraj; Kharul, Ulhas K.; Wadgaonkar, Prakash P. (Journal of Polymer Science Part A - Polymer Chemistry, 2018)
A new diamine containing spirobisindane and phenazine units, namely, 3,3,3,3-tetramethyl-2,2,3,3-tetrahydro-1,1-spirobi[cyclopenta[b]phen azine]-7,7-diamine (TTSBIDA) was synthesized starting from commercially available 5,5,6,6-tetrahydroxy-3,3,3,3-tetramethyl-1,1-spirobisindane (TTSBI). TTSBI was oxidized to 3,3,3,3-tetramethyl-2,2,3,3-tetrahydro-1,1-spirobi[indene]-5,5,6,6-tet raone (TTSBIQ) which was subsequently condensed with 4-nitro-1,2-phenylenediamine to obtain 3,3,3,3-tetramethyl-7,7-dinitro-2,2,3,3-tetrahydro-1,1-spirobi[cyclope nta[b]phenazine] (TTSBIDN). TTSBIDN was converted into TTSBIDA by reduction of the nitro groups using hydrazine hydrate in the presence of Pd/C as the catalyst. A series of new polyimides of intrinsic microporosity (PIM-PIs) were synthesized by polycondensation of TTSBIDA with commercially available aromatic dianhydrides. PIM-PIs exhibited amorphous nature, high thermal stability (T-10>480 degrees C) and intrinsic microporosity (BET surface area=59-289 m(2)/g). The gas permeation characteristics of films of selected PIM-PIs were evaluated and they exhibited appreciable gas permeability as well as high selectivity. The CO2 and O-2 permeability of PIM-PIs were in the range 185.4-39.2 and 30.6-6.2 Barrer, respectively. Notably, polyimide derived from TTSBIDA and 4,4-(hexafluoroisopropylidene)diphthalic anhydride (PIM-PI-6FDA) exhibited high CO2 and O-2 permeability of 185.4 and 30.6 Barrer with CO2/CH4 and O-2/N-2 selectivity of 43.1 and 5.1, respectively. The data of PIM-PI-6FDA for CO2/CH4 and O-2/N-2 gas pairs were located near Robeson upper bound. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 766-775
Keywords: Gas permeability; intrinsic microporosity; polyimides; spirobisindane

Investigation of disorder in mixed phase, sp(2)-sp(3) bonded graphene-like nanocarbon - Patil, Sumati; Kolekar, Sadhu; Kumar, Arvind; Alegaonkar, Prashant; Datar, Suwarna; Dharmadhikari, C. V. (Journal of Nanoscience and Nanotechnology, 2018)
Disorder in a mixed phase, sp(2)-sp(3) bonded graphene-like nanocarbon (GNC) lattice has been extensively studied for its electronic and field emission properties. Morphological investigations are performed using scanning electron microscopy (SEM) which depicts microstructures comprising of atomically flat terraces (c-planes) with an abundance of edges (ab planes which are orthogonal to c-planes). Scanning tunneling microscopy (STM) is used to observe the atomic structure of basal planes whereas field emission microscopy (FEM) is found to be suitable for resolving nanotopography of edges. STM images revealed the hexagonal and non-hexagonal atomic arrangements in addition to a variety of defect structures. Scanning tunneling spectroscopy is carried out to study the effect of this short-range disorder on the local density of states. Current versus voltage (I-V) characteristics have been recorded at different defect sites and are compared with respect to the extent of the defect. As sharp edges of GNC are expected to be excellent field emitters, because of low work function and high electric field, enhancement in current is observed particularly when applied electric field is along basal planes. Therefore, it is worthwhile to investigate field emission from these samples. The FEM images show a cluster of bright spots at low voltages which later transformed into an array resembling ledges of ab-planes with increasing voltage. Reproducible I-V curves yield linear Fowler-Nordheim plots supporting field emission as the dominant mechanism of electron emission. Turn on field for 10 mu A current is estimated to be similar to 3 V/mu m.
Keywords: Field emission microscopy; Graphene-Like Nanocarbon; Scanning tunneling microscopy; Scanning Tunneling Spectroscopy

Investigations on optical properties of ZnO decorated graphene oxide (ZnO@GO) and reduced graphene oxide (ZnO@r-GO) - Kumar, Pushpendra; Som, Sudipta; Pandey, Mukesh K.; Das, Subrata; Chanda, Anupama; Singh, Jai (Journal of Alloys and Compounds, 2018)
The present investigation is based on the production of reduced graphene oxide (r-GO) from the graphene oxide using Hummer's (GO) and improved Hummer's methods (IGO) at elaborated conditions, named as GO and IGO, respectively hereafter. In contrast to previously known techniques, the presented process does not generate toxic gas. Meanwhile, the reduction temperature can be easily controlled. This approach provides a more significant amount of hydrophilic oxidized graphene as compared to GO and IGO with the use of additional KMnO4. Thus synthesized IGO was used to produce r-GO by thermal treatment. The morphological characteristics show that the obtained samples have a wrinkled paper-like morphology with severely folded lines. However, r-GO has double layers and multilayer at the edges. All the products (GO, IGO, and r-GO) have been decorated with ZnO nanoparticles (NPs). The XRD patterns of ZnO@GO composites have confirmed the characteristic peaks of wurtzite ZnO indicating the formation of ZnO nanoparticles onto the surface of graphene. The microscopic studies confirm the random growth/decoration of ZnO NPs on the surface of GO/IGO/r-GO sheets. However, in IGO and r-GO, loading/growth of ZnO NPs are less as compared to ZnO@GO. Overall structural studies indicate the oxidation of graphite and reduction of graphene oxide into r-GO sheets and ZnO decoration. Upon UV excitations, a bright blue emission has been exhibited by the GO that originates from geminate recombination of localized e-h pairs in sp(2) clusters those primarily act as the luminescent centers. The noteworthy enhancement in the emission intensities after the incorporation of ZnO nanoparticles on the surface of GO is observed. The improved synthesis method and low-temperature reduction technique of GO may be essential for the large-scale production of r-GO as well as the construction of devices composed of ZnO@GO/IGO/r-GO. (C) 2018 Elsevier B.V. All rights reserved.

KLTL-MCM-41 micro-mesoporous composite as a solid base for the hydrogenation of sugars - Tangale, Nilesh P.; Niphadkar, Prashant S.; Joshi, Praphulla N.; Dhepe, Paresh L. (Catalysis Science & Technology, 2018)
An approach to the synthesis of KLTL-MCM-41 micro-mesoporous composites of varying SiO2/Al2O3 molar ratio (20-8) was designed by following green technology. The synthesis was based on the recycling of waste mother liquor containing preformed KLTL zeolite crystals and unutilized reagents. The micro-mesoporous composites consist of KLTL zeolite crystals preformed through hydrothermal treatment in the first step. In the second step, the siliceous mother liquor was transformed into mesoporous MCM-41. The physico-chemical properties of the KLTL-MCM-41 micro-mesoporous composites were determined by PXRD, ICP-OES, FTIR, CO2-TPD, Al-27 MAS-NMR, TEM-EDX, HRTEM, and N-2 adsorption-desorption measurements. The mesopores properties of the KLTL-MCM-41 composites depended on the SiO2/Al2O3 molar ratio. The characterization results led to the following conclusions with decreasing SiO2/Al2O3 molar ratio: 1) decreasing order of the mesophase, 2) decreasing wall thickness of the mesopores, and 3) decreasing BET surface area and pore volume. Al-27 MAS-NMR spectra showed that only tetrahedrally coordinated aluminium was contained in zeolite KLTL. Moreover, the total amount and the strength of the basic sites of the KLTL-MCM-41 micro-mesoporous composites owing to the exchangeable potassium content (Al/K ratio approximate to 1) decreased in the order: 8 MMC > 10 MMC > 15 MMC > 20 MMC. The catalytic activity of the synthesized micro-mesoporous samples as a solid base was tested for the hydrogenation of xylose to sugar alcohols

Ligand/additive/base-free C(sp(2))-H activation and isocyanide insertion in PEG-400: synthesis of indolizine/imidazoline-fused heterocycles - Kumar, K. Shiva; Rajesham, Bandari; Kumar, N. Praveen; Ramulu, Meesa Siddi; Dandela, Rambabu (ChemistrySelect, 2018)
A ligand/base/metal oxidant free Pd-catalyzed C(sp(2))-H activation, followed by isocyanide insertion to synthesize indolizine/imidazoline fused heterocyclics in PEG-400 as a recyclable solvent. The present transformation is greener and an efficient strategy using oxygen as external oxidant. The spectroscopic properties of selected indolizine/imidazoline fused heterocyclics were studied by UV-visible and fluorescence spectroscopy.

Lower scaling approximation to EOM-CCSD: a critical assessment of the ionization problem - Dutta, Achintya Kumar; Vaval, Nayana; Pal, Sourav (International Journal of Quantum Chemistry, 2018)
In this article, we investigate the performance of different approximate variants of the EOM-CCSD method for calculation of ionization potential (IP), as compared to EOM-CCSDT reference values. None of the lower scaling approximations to the EOM-CCSD method give a consistent performance for valence, inner valence, and core ionization, favoring one, or the other depending on the nature of the approximation used. The parent EOMIP-CCSD method gives superior performance for valence IP but can show large errors for inner valence and core ionization. The problem is particularly severe for core-ionization, where even the EOMIP-CCSDT method cannot provide quantitative accuracy.
Keywords: EOM-CCSD; Ionization potential; lower scaling

Machine learning prediction of interaction energies in rigid water clusters - Bose, Samik; Dhawan, Diksha; Nandi, Sutanu; Sarkar, Ram Rup; Ghosh, Debashree (Physical Chemistry Chemical Physics, 2018)
Classical force fields form a computationally efficient avenue for calculating the energetics of large systems. However, due to the constraints of the underlying analytical form, it is sometimes not accurate enough. Quantum mechanical (QM) methods, although accurate, are computationally prohibitive for large systems. In order to circumvent the bottle-neck of interaction energy estimation of large systems, data driven approaches based on machine learning (ML) have been employed in recent years. In most of these studies, the method of choice is artificial neural networks (ANN). In this work, we have shown an alternative ML method, support vector regression (SVR), that provides comparable accuracy with better computational efficiency. We have further used many body expansion (MBE) along with SVR to predict interaction energies in water clusters (decamers). In the case of dimer and trimer interaction energies, the root mean square errors (RMSEs) of the SVR based scheme are 0.12 kcal mol(-1) and 0.34 kcal mol(-1), respectively. We show that the SVR and MBE based scheme has a RMSE of 2.78% in the estimation of decamer interaction energy against the parent QM method in a computationally efficient way.

Mechanism of the formation of microphase separated water clusters in a water-mediated physical network of perfluoropolyether tetraol - Deshpande, Ashwini A.; Torris, Arun A. T.; Pahari, Swagata; Menon, Shamal K.; Badiger, Manohar V.; Rajamohanan, P. R.; Wadgaonkar, Prakash P.; Roy, Sudip; Tonelli, Claudio (Soft Matter, 2018)
Perfluoropolyether tetraol (PFPE tetraol) possesses a hydrophobic perfluoropolyether chain in the backbone and two hydroxyl groups at each chain terminal, which facilitates the formation of hydrogen bonds with water molecules resulting in the formation an extended physical network. About 3 wt% water was required for the formation of the microphase separated physical network of PFPE tetraol. The mechanism responsible for the microphase separation of water clusters in the physical network was studied using a combination of techniques such as NMR spectroscopy, molecular dynamics (MD) simulations and DSC. MD simulation studies provided evidence for the formation of clusters in the PFPE tetraol physical network and the size of these clusters increased gradually with an increase in the extent of hydration. Both MD simulations and NMR spectroscopy studies revealed that these clusters position themselves away from the hydrophobic backbone or vice versa. The presence of intra-and inter-chain aggregation possibility among hydrophilic groups was evident. DSC results demonstrated the presence of tightly and loosely bound water molecules to the terminal hydroxyl groups of PFPE tetraol through hydrogen bonding. The data from all the three techniques established the formation of a physical network driven by hydrogen bonding between the hydrophilic end groups of PFPE tetraol and water molecules. The flexible nature of the PFPE tetraol backbone and its low solubility parameter favour clustering of water molecules at the terminal groups and result in the formation of a gel.

Mechano-responsive room temperature luminescence variations of boron conjugated pyrene in air - Wakchaure, Vivek C.; Ranjeesh, Kayaramkodath C.; Goudappagouda; Das, Tamal; Vanka, Kumar; Gonnade, Rajesh; Babu, Sukumaran S. (Chemical Communications, 2018)
Stimuli responsive tunable luminescence is a promising field of research. Even though mechanofluorescence is widely studied, mechanophosphorescence remains unexplored. Here we report the mechano-driven fluorescence and phosphorescence variations of a pyrene tetraboronic ester derivative. The fluorochromic and room temperature phosphorescence features are supported by theoretical studies and single crystal analysis. The mechanically ground fluorescence active but phosphorescence inactive pyrene tetraboronic ester exhibits room temperature phosphorescence in air withmechanical force. The efficient intermolecular electronic coupling in the dimer formed upon scratching enables a good communication between singlet and triplet states, hence resulting in room temperature mechanophosphorescence.

Mesoporous shell@macroporous core aluminosilicates as sustainable nanocatalysts for direct N-alkylation of amines - Sekhar, Anandakumari C. Sunil; Ashokkumar, Anumol Erumpukuthickal; Cygnet, Choorapoikayil T.; Lakshmi, Saseendranpillai Vidhya; Deepak, Francis Leonard; Vinod, Chathakudath P. (Chemnanomat, 2018)
Aluminosilicate spheres with a macroporous core and mesoporous shell (Si/Al ratio of 11) is synthesised by a sol-gel method utilizing cetyltrimethyl ammonium bromide (CTAB) as a structure directing agent in basic medium. The selective incorporation of aluminium in the silica matrix results in the formation of aluminosilicates with an overall acidity of 0.32mmol/g with interconnected pores. Direct N-alkylation reaction is a prototype of C-N bond formation reaction and meso- macroporous aluminosilicate is shown to catalyze this reaction with excellent yield. The catalyst is tested and found sustainable for five catalytic cycles even without any high temperature regeneration step.
Keywords: Aluminosilicates; macroporous; Mesoporous; N-alkylation; nanocatalysis

Metal oxide-promoted hydrodeoxygenation activity of platinum in pt-mox/al2o3 catalysts for green diesel production - Janampelli, Sagar; Darbha, Srinivas (Energy & Fuels, 2018)
Catalytic deoxygenation of fatty acids into renewable hydrocarbons (green diesel) was investigated over 4Pt-8MO(x)/Al2O3 (M = Mo, Re, W, and Sn) catalysts prepared by the wet impregnation method. Platinum deposited on MOx-modified gamma-Al2O3 showed higher catalytic hydrodeoxygenation activity than that of the "neat" Pt/Al2O3 catalyst. The promotional effect of metal oxides (MOx) decreased in the following order: MoOx > ReOx > WOx > SnOx. Characterization studies revealed that metal oxides affect the textural and electronic properties of Pt. Supported Pt facilitated the reduction of these metal oxides. Synergy and electronic contact between Pt and MOx determined the catalytic deoxygenation performance. Fatty acid conversion increased with increasing metallic nature (decreasing binding energy) of Pt. Hydrodeoxygenation product selectivity correlated with the extent of metal oxide reduction. Among the catalysts, 4Pt-8MoO(x)/Al2O3 had the optimum dispersion, electron-rich Pt, and reduced Mo5+ species, enabling quantitative conversion of oleic acid with 93.5% octadecane selectivity at a temperature as low as 220 degrees C and 20 bar hydrogen pressure. Metal oxide switched the mechanism of deoxygenation from decarbonylation/decarboxylation to hydrodeoxygenation. Fatty acids, methyl oleate, and vegetable oil were deoxygenated with equal efficiency over this catalyst. Catalysts were reusable in recycling studies only at higher temperature (320 degrees C) and not at lower temperature (260 degrees C), perhaps due to strong sticking of reactant molecules at lower temperature on the catalyst surface than at higher temperature.

Metamagnetism in nanosheets of Co-II-MOF with T-N at 26 K and a giant hysteretic effect at 5 K - Gupta, Kriti; Dadwal, Arun; Rana, Shammi; Jha, Plawan Kumar; Jain, Anil; Yusuf, S. M.; Joy, Pattayil A.; Ballav, Nirmalya (Inorganic Chemistry, 2018)
Herein, we have synthesized at room-temperature two-dimensional nanosheets of a MOF comprised of cobalt(II) ion with benzenedicarboxylic acid ligand, which exhibited unusual magnetic properties. Direct-current magnetic susceptibility revealed an anti-ferromagnetic (AFM) transition at 26 K (Neel temperature, T-N) followed by a canting of the spin moments along with the concomitant appearance of a sigmoidal-shaped magnetization versus field (M-H) curve at 15 K. Such a canted AFM ordering led to nonzero remnant magnetization with a remarkably high coercive field of similar to 10 kOe at 5 K. Metamagnetism was further: substantiated by the alternating-current magnetic susceptibility measurements.

Method for identification of sensitive nodes in boolean models of biological networks - Dnyane, Pooja A.; Puntambekar, Shraddha S.; Gadgil, Chetan J. (IET Systems Biology, 2018)
Biological systems are often represented as Boolean networks and analysed to identify sensitive nodes which on perturbation disproportionately change a predefined output. There exist different kinds of perturbation methods: perturbation of function, perturbation of state and perturbation in update scheme. Nodes may have defects in interpretation of the inputs from other nodes and calculation of the node output. To simulate these defects and systematically assess their effect on the system output, two new function perturbations, referred to as not of function' and function of not', are introduced. In the former, the inputs are assumed to be correctly interpreted but the output of the update rule is perturbed; and in the latter, each input is perturbed but the correct update rule is applied. These and previously used perturbation methods were applied to two existing Boolean models, namely the human melanogenesis signalling network and the fly segment polarity network. Through mathematical simulations, it was found that these methods successfully identified nodes earlier found to be sensitive using other methods, and were also able to identify sensitive nodes which were previously unreported.
Keywords: biological networks; Boolean functions; Boolean models; fly segment polarity network; human melanogenesis signalling network; perturbation methods; Perturbation theory; physiological models

Microbacterium telephonicum sp nov., isolated from the screen of a cellular phone - Rahi, Praveen; Kurli, Rashmi; Pansare, Aabeejjeet N.; Khairnar, Mitesh; Jagtap, Shubhangi; Patel, Nisha B.; Dastager, Syed G.; Lawson, Paul A.; Shouche, Yogesh S. (International Journal of Systematic and Evolutionary Microbiology, 2018)
A cultivation-based study of the microbial diversity of cellular phone screens led to the isolation of a Gram-stain-positive, aerobic, rod-shaped and non-endospore-forming bacterium, designated S2T63(T), exhibiting phenotypic and genotypic characteristics unique to the type strains of closely related species. Phylogenetic analysis based on 16S rRNA gene sequences indicated that the strain is a member of Microbacterium, and most closely related to Microbacterium aurantiacum IFO 15234(T) and Microbacterium kitamiense Kitami C2(T). The DNA-DNA relatedness values of the strain S2T63(T) to M. aurantiacum KACC 20510(T), M. kitamiense KACC 20514(T) and Microbacterium laevaniformans KACC 14463(T) were 65% (+/- 4), 29.5% (+/- 3) and 55.9% (+/- 4), respectively. The genomic DNA G+C content was 71.8 mol%. The major fatty acids were anteiso C-15:0, iso-C-16 : 0, C-16 : 0 and anteiso-C-17 : 0. The main polar lipids were diphosphatidylglycerol, phosphatidylethanolamine, phosphatidylglycerol and two unidentified polar lipids. The peptidoglycan contained the amino acids glycine, lysine, alanine and glutamic acid, with substantial amounts of hydroxy glutamic acid detected, which is characteristic of peptidoglycan type B1 alpha. The predominant menaquinones were MK-12 and MK-13. Rhamnose, fucose and galactose were the whole-cell sugars detected. The strain also showed biofilm production, estimated by using crystal violet assay. Based on the results of the phenotypic and genotypic characterizations, it was concluded that the new strain represents a novel species of the genus Microbacterium, for which the name Microbacterium telephonicum is proposed, with S2T63(T) (=MCC 2967 T = KACC 18715 T = LMG 29293(T)) as the type strain.
Keywords: actinobacteria; bio-film; MALDI-TOF MS; mobile phone

Mixed bacterial culture mediated direct conversion of bio-glycerol to diols - Parate, Roopa; Mane, Rasika; Dharne, Mahesh; Rode, Chandrashekhar (Bioresource Technology, 2018)
Direct and economic transformation of biodiesel derived crude glycerol is gaining more significance. During screening of bacterial cultures Klebsiella pneumoniae and Enterobacter aerogenes were able to convert crude bio-glycerol to 2,3-butanediol (2,3-BDO) and 1,3-propanediol (1,3-PDO), as major compounds, ethanol and acetoin as minor compounds, with a conversion of 69% and 79% respectively. Process optimization could achieve maximum conversion at pH 7.0, 37 degrees C, 30-40 g/L glycerol and 1.5 g of inoculum until 120 h. Mixed cultures led to complete glycerol conversion with optimal yield and productivity. An innovative approach of using crude glycerol for sustained growth and tolerance of bacteria as source of carbon and energy makes this study more significant. In addition to this, a mixed culture concept introduced here is expected to make impact in process economics for industrial scale synthesis for direct transformation of glycerol into C3 and specifically, C4 diols.
Keywords: 1; 2; 3-Butanediol; 3-Propanediol; Bioconversion; Bioglycerol; Mixed culture

Morphology and thermophysical properties of non-aqueous titania nanofluids - Murshed, S. M. S.; Santos, F. J. V.; Nieto de Castro, C. A.; Patil, V. S.; Patil, K. R. (Heat and Mass Transfer, 2018)
This work deals with the experimental investigation on thermophysical properties of TiO2-nanofluids and characterization of morphology and structure of TiO2 nanoparticles. Non-aqueous liquids like silicone oil and ethylene glycol are used as base fluids to prepare the nanofluids. Thermophysical properties including viscosity and thermal conductivity of these nanofluids are measured at different concentrations and temperatures. Results showed that silicone oil-based TiO2 nanofluid is Newtonian and the viscosity of this nanofluid increases with the loading of nanoparticles but it decreases nonlinearly with increasing temperature. Existing viscosity models are found unable to predict the viscosity of nanofluids. Although the effective thermal conductivities of both the silicone oil and ethylene glycol-based nanofluids increased with the TiO2 concentration, their enhanced thermal conductivity was found to decrease with increasing temperature.

Ni(OH)(2)-Fe2O3/CNOs ternary nanocomposite designed as an anode with complementary properties for high-performance li-ion battery - Dwivedi, Pravin Kumari; Muniraj, Vedi Kuyil Azhagan; Devarapalli, Rami Reddy; Shelke, Manjusha V. (Chemistryselect, 2018)
Synthesis of the new ternary hybrid composite with excellent electrochemical performances for Li-ion battery is demonstrated. The ternary hybrid composite of Ni(OH)(2)-Fe2O3/Carbon Nano Onions (NFOC) is synthesized by using two-step solution phase method delivers a high reversible discharge capacity of 928 mAhg(-1) at 50 mAg(-1) and 673 mAhg(-1) at a higher current density of 1000 mAg(-1) with excellent rate performance. Additionally, it shows to have stable cycle life up to 1000 cycles with 96% capacity retention and more than 99% of coulombic efficiency. The synergetic effect between Ni(OH)(2), Fe2O3 and carbon nano onions (CNOs) as well as the unique feature of heterostructures are responsible for the improved electrochemical performance of the battery. The reversible reaction of Fe2O3 and Ni(OH)(2) with Li, maintains its long cycle life with higher reversible discharge capacity and CNOs improve the efficient electronic transfer, accommodate substantial volume expansion and maintain the structural integrity of the material during lithiation-delithiation process.
Keywords: Heterostructures; Long cycle stability; Superior rate capability; Ternary Composite; Transition metal oxides

N-Methylation of isoDGR peptides: discovery of a selective alpha 5 beta 1-integrin ligand as a potent tumor imaging agent - Kapp, Tobias G.; Di Leva, Francesco Saverio; Notni, Johannes; Raeder, Andreas F. B.; Fottner, Maximilian; Reichart, Florian; Reich, Dominik; Wurzer, Alexander; Steiger, Katja; Novellino, Ettore; Marelli, Udaya Kiran; Wester, Hans-Juergen; et al. (Journal of Medicinal Chemistry, 2018)
Specific targeting of the integrin subtype alpha 5 beta 1 possesses high potential in cancer diagnosis and therapy. Through sequential N-methylation, we successfully converted the biselective alpha 5 beta 1/alpha v beta 6 peptide c(phg-isoDGR-k) into a potent peptidic RGD binding aSfil subtype selective ligand c(phg-isoDGR-(NMe)k). Nuclear magnetic resonance spectroscopy and molecular modeling clarified the molecular basis of its improved selectivity profile. To demonstrate its potential in vivo, c(phg-isoDGR-(NMe)k) was trimerized with the chelator TRAP and used as a positron-emission tomography tracer for monitoring alpha 5 beta 1 integrin expression in a M21 mouse xenograft.