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.

Estimation of gas induction in jet loop reactors: influence of nozzle designs - Sharma, D.V. (Chemical Engineering Research and Design, 2017)
Jet loop reactors are used widely for conducting gas liquid reactions because of the high mass transfer achieved in the gas–liquid ejector. Studies have shown that the mass transfer has a very strong correlation to the amount of gas induced in the ejector, and hence it is important to understand gas induction to enhance the performance of any gas–liquid nozzle. In this work, we used a single phase CFD model of the ejector with one adjustable parameter for estimating gas induction rates. After establishing that the model adequately describes the experimental data, the model was used for a quick evaluation of ejector geometries. Influence of key geometric parameters of gas–liquid ejectors like nozzle diameter, mixing tube length, distance between the nozzle outlet and mixing tube, suction chamber geometry and diffuser angle was investigated. It was found that dependence of gas induction on geometric parameters like distance between nozzle—mixing tube, suction chamber geometry, diffuser angle was either weak or had a clear maxima at or beyond a certain value of the geometric parameter. Other parameters like mixing tube length and nozzle diameter have a more complex impact on gas induction. The presented approach and results will be useful for quantifying influence of nozzle designs on gas induction rate in jet loop reactors.
Keywords: CFD; Gas Induction; Jet Loop Reactors; Nozzle Geometry

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).

Expeditious and solvent-free nickel-catalyzed C−H arylation of arenes and indoles - Jagtap, Rahul A.; Soni, Vineeta; Punji, Benudhar (ChemSusChem, 2017)
An efficient solvent-free nickel-catalyzed method for C−H bond arylation of arenes and indoles has been developed, which proceeds expeditiously through chelation assistance. The reaction is highly selective for mono-arylation and tolerates sensitive and structurally diverse functionalities, such as halides, ethers, amines, indole, pyrrole and carbazole. This reaction represents the first example of a nickel-catalyzed C−H arylation by monochelate assistance and symbolizes a rare precedent in solvent-free C−H arylation. Mechanistic investigations by various controlled reactions, kinetic studies, and deuterium labeling experiments suggest that the arylation follows a single electron transfer (SET) pathway involving the turnover-limiting C−H nickelation process.

Exploiting phosphate-starved cells of scenedesmus SP for the treatment of raw sewage - Yewalkar-Kulkarni, Swati; Gera, Gayatri; Nene, Sanjay; Pandare, Kiran; Kulkarni, Bhaskar; Kamble, Sanjay (Indian Journal of Microbiology, 2017)
Phosphate depletion is one of the favorable ways to enhance the sewage water treatment with the algae, however, detailed information is essential with respect to internal phosphate concentration and physiology of the algae. The growth rate of the phosphate-starved Scenedesmus cells was reduced drastically after 48 h. Indicating cells entered in the stationary phase of the growth cycle. Fourier Transform Infrared analysis of phosphate-starved Scenedesmus cells showed the reduction in internal phosphate concentration and an increase in carbohydrate/phosphate and carbohydrate/lipid ratio. The phosphate-starved Scenedesmus cells, with an initial cell density of, 1 x 10(6) cells mL(-1) shows 87% phosphate and 100 % nitrogen removal in 24 h. The normal Scenedesmus cells need approximately 48 h to trim down the nutrients from wastewater up to this extent. Other microalgae, Ankistrodesmus, growth pattern was not affected due to phosphate starvation. The cells of Ankistrodesmus was able to reduce 71% phosphate and 73% nitrogen within 24 h, with an initial cell density of, 1 x 10(6) cells mL(-1).
Keywords: Ankistrodesmus; Fourier Transform Infrared; Phosphate starvation; Scenedesmus; Sewage treatment

Exploiting the dual role of ethynylbenziodoxolones in gold-catalyzed C(sp)-C(sp) cross-coupling reactions - Banerjee, Somsuvra; Patil, Nitin T. (Chemical Communications, 2017)
Reported herein is the gold-catalyzed alkynylation of terminal alkynes using ethynylbenziodoxolones (EBXs), where EBXs serve a dual role as oxidants as well as alkyne transfer agents to access unsymmetrical 1,3-diynes. Hence, the catalytic system requires no external oxidants and is compatible with a broad range of substrates, including those with polar functional groups such as NH, OHand B(OH)(2).

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

Extraction of the very high tunneling current and extremely stable emission current from GdB6/W-tip source synthesized using arc plasma - Suryawanshi, Sachin R.; Kanhe, Nilesh; Mathe, Vikas L.; Phase, Deodatta M.; Late, Dattatray J.; More, Mahendra A. (ChemistrySelect, 2017)
Herein, we report the one step arc plasma synthesis of the GdB6 (Gadolinium hexaboride) nanoparticles and its field emission (FE) characteristics on tungsten point substrate (GdB6/ W). The SEM /TEM analysis revealed the GdB6 nanoparticles on W point substrate exhibit irregular shaped, grainy, dense, course morphology, i.e. uniformly covering the entire tip substrate surface. For GdB6/W point source, the values of the turn-on and threshold fields, defined as field required to draw an emission current density similar to 1 mA/cm(2) and similar to 100 mA/cm(2), respectively are found to be similar to 2.2 and similar to 2.7 V/mm, for anodecathode separation of similar to 1 mm. Interestingly, a very high emission current density of similar to 3.5 A/cm(2) has been drawn from the GdB6/W point emitter at relatively lower applied field of similar to 6.4 V/mm. The field enhancement factor found to be similar to 10,250. The GdB6/W point electron source exhibits a good emission current stability at similar to 10 mA for a period of 6 hr. The emission current stability is enumerated in terms of standard deviation and its magnitude has been measured to be only 1.72% with respect to the average value. The superlative field emission characteristics signify the GdB6/W point electron source as potential candidates for vacuum micro/nanoelectronics device applications.
Keywords: Arc Plasma; field emission; Thin films

Facile one-pot multi-component synthesis of spirooxindoles and 3, 3 `-disubstituted oxindoles via sp(3) C-H activation/functionalization of azaarenes - Pathan, Mohsinkhan Y.; Chavan, Santosh S.; Shaikh, Taufeekaslam M. Y.; Thorat, Shridhar H.; Gonnade, Rajesh G.; Mulla, Shafeek A. R. (Chemistryselect, 2017)
A novel one-pot multicomponent reaction (MCR) protocol has been demonstrated for the first time for sustainable and facile synthesis of spirooxindoles and 3, 3 `-disubstituted oxindoles in an excellent yield via sp(3) C-H activation/functionalization of 2-methyl azaarenes and (2-azaaryl)methanes with isatin, active methylene compounds using eco-friendly heterogeneous, reusable silica-supported dodecatungstophosphoric acid (DTP/SiO2) catalyst.
Keywords: 3; 3'-disubstituted oxindoles; azaarenes; silica-supported dodecatungstophosphoric acid (DTP/SiO2) catalyst; sp(3) C-H activation/functionalization; spirooxindoles

Facile synthesis of N-acyl 2-aminobenzothiazoles by NHC-catalyzed direct oxidative amidation of aldehydes - Premaletha, Sethulekshmi; Ghosh, Arghya; Joseph, Sumi; Reddy, Santhi Vardhan; Biju, Akkattu T. (Chemical Communications, 2017)
A mild, general, and high yielding synthesis of N-acyl 2-aminobenzothiazoles has been demonstrated by N-heterocyclic carbene (NHC)-organocatalyzed direct amidation of aldehydes with 2-aminobenzothiazoles proceeding via acyl azolium intermediates. The carbene generated from the triazolium salt under oxidative conditions was the key for the success of this reaction. The method was subsequently applied to the synthesis of various biologically important N-acyl 2-aminobenzothiazoles.

Facile synthesis of β-functionalized “push-pull” Zn(II) porphyrins for DSSC applications - Prakash, K. (Dyes and Pigments, 2017)
Three new β-substituted “push-pull” Zn(II) porphyrin dyes with various electron donors at meso-positions and cyanoacetic acid as acceptor at β-position have been designed and synthesized. These porphyrins have been characterized by UV-Vis, Fluorescence, 1H NMR and 13C NMR spectroscopic techniques and cyclic voltammetric studies. The Soret and Q band of Zn(II) porphyrin dyes were found to be red-shifted (30–35 nm) as compared to ZnTPP. The fluorescence quenching and the decrement in quantum yield and lifetime suggest intramolecular charge transfer from donor to acceptor. Zn porphyrins exhibited anodic shift in their first redox potentials (0.03–0.11 V) as compared to ZnTPP. The HOMO-LUMO energy levels of Zn porphyrin dyes were compared with the conduction band of TiO2 and the electrolyte I−/I3 −. The HOMO levels of all the dyes are sufficiently higher than the energy level of electrolyte I−/I3 − and LUMO levels significantly lower than the conduction band of TiO2 which reflect the feasibility of facile electron-transfer. ZnT(Mes)P(CN-COOH) has been co-sensitized with N719 dye to further improve the PCE efficiency. These dyes displayed power conversion efficiency (PCE) of η = 1.72–3.13% where co-sensitized ZnT(Mes)P(CN-COOH) (N719) dye demonstrated maximum PCE efficiency up to 5.35%, with a Jsc of 11.8 mA cm−2, a Voc of 630 mV and a fill factor (FF) of 72% due to better light harvesting capacity.
Keywords: charge transfer; Conduction Bands; Cyanoacetic Acid; Electrolytes; Floorescence; Redox Reaction; zinc compounds

Fluorescent metal quantum clusters: an updated overview of the synthesis, properties, and biological applications - Khandelwal, Puneet; Poddar, Pankaj (Journal of Materials Chemistry B, 2017)
Metal quantum clusters are evolving as excellent systems for a wide range of biological applications due to their small size (similar to 2 nm), tunable optical properties, including optical absorption, photoluminescence (UV to NIR), nonlinear optical properties (two-photon absorption, two-photon fluorescence, and second/third harmonic generation), ultrafast dynamics (relaxation kinetics, electron-phonon coupling, and radiative emission), and magnetism. These excellent properties have resulted in their use in a broad range of applications, including the sensing of ions (heavy metal ions, anions), biomolecules (proteins, DNA, miRNA, and enzymes), biological cells, diagnosis, and therapy. This article presents an introduction to metal quantum clusters, including a brief history of research in this system and an overview of the existing theories to understand their properties. We also discuss the synthesis methods, the various properties of quantum clusters and present a broad and updated overview of the applications of metal quantum clusters in biology.

Fluoride-mediated dephosphonylation of alpha-diazo-beta-carbonyl phosphonates - Phatake, Ravindra S.; Mullapudi, Venkannababu; Wakchaure, Vivek C.; Ramana, Chepuri V. (Organic Letters, 2017)
The possibility of fluoride-mediated selective dephosphonylation of alpha-diazo-beta-carbonyl phosphonates such as the Ohira-Bestmann reagent has been proposed and executed. The resulting alpha-diazocarbonyl intermediates undergo a (3 + 2)pcycloaddition at room temperature with conjugated olefins and benzynes. Interestingly, under the current conditions, the resulting cycloaddition products underwent either N-acylation (with excess alpha-diazo-beta-carbonyl phosphonates) or Michael addition (with conjugated olefins).

Formal [2+1] annulation (Spiro-Cyclopropanation) reaction between sulfur ylides derived from baylis-hillman bromides and arylidene indane-1,3-dione - Roy, Suparna; Piradhi, Venkatesh (Chemistryselect, 2017)
The sulfonium salts derived from the Baylis-Hillman bromides have been successfully employed for the selective cycloproporanation of arylidene indane-1,3-diones to synthesize densely substituted spiro-cyclopropanes in good to excellent yields (upto 94%). Products were obtained mostly in 1:1 diastereomeric ratio and were isolated in pure form. Diastereoselectivity has been improved by using suitably substituted starting materials. In this case a formal [2+1] annulation reaction competes over a probable [3+2] cycloaddition reaction. The reaction proceeds through a Michael initiated ring closure process of S-ylides to the activated olefins for the formation of structurally strained spiro-cyclopropanes.

Fruit peel waste: characterization and its potential uses - Pathak, Pranav D.; Mandavgane, Sachin A.; Kulkarni, Bhaskar D. (Current Science, 2017)
Globally, India is the leading producer of fruits. Fruits after consumption leave a peel which is a nuisance to the environment as a solid waste. In this article, commonly available large volume-fruit peels (FP) (viz. banana, orange, citrus, lemon and jackfruit) were investigated for surface, physical and chemical characteristics with a view to propose their valorization in detail. Each FP was characterized by proximate and ultimate analysis, porosity, particle density, bulk density, point of zero charge (pH(pzc)), surface pH, surface charges, water absorption capacity, BET surface area, scanning electron microscopy, Fourier transform infrared spectroscopy and TGA/derivative of thermogravimetric. The BET surface area of FP is very less, between 0.60 and 1.2 m(2)/g. The pH(pzc) and surface pH values of orange peel (OP), citrus peel (CP), lemon peel (LP) and jackfruit peels (JFP) are in the range of 3-4. The pH(pzc) value and surface pH of banana peel (BP) is closer to 7. The order of surface acidity is OP > LP > CP > JFP > BP. From TG curves it is clear that FPs are stable below 150 degrees C. The results will be useful for rational design, when FP is used as a substrate for bioactive compounds, phenolic antioxidants, organic acids, enzymes, biofertilizer, production of energy and as adsorbents.

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.

General nickel-catalyzed method for C-H bond alkynylation of heteroarenes through chelation assistance - Punji, Benudhar; Khake, Shrikant manmathappa; Soni, Vineeta; Gonnade, Rajesh Ghanshyam (Chemistry - A European Journal, 2017)
A general nickel-catalyzed method for the alkynylation of heteroarenes through monodentate chelation assistance is described. Many heterocycles, including indoles, pyrroles, imidazoles and pyrazole, efficiently coupled with (triisopropylsilyl)alkynyl bromide, and synthetically important functional groups, such as halides, ether, nitrile, nitro were tolerated. Synthetic applicability of this Ni-catalyzed method is demonstrated by the removal of triisopropylsilyl (-SiiPr₃) group, and further functionalization into triazolyl, benzofuranyl and alkynyl arene derivatives. Preliminary mechanistic investigations on the alkynylation of indole suggest that the reaction proceeds through kinetically relevant C-H activation and follows the two-electron redox pathway. A catalytically competent Ni-species, [(Phen)₃Ni].NiBr₄ has been isolated and structurally characterized.

Genetic programming based drag model with improved prediction accuracy for fluidization systems - Sonolikar, R. R.; Patil, M. P.; Mankar, R. B.; Tambe, S. S.; Kulkarni, B. D. (International journal of Chemical Reactor Engineering, 2017)

Genetic variability in Indian populations of banana corm weevil [Cosmopolites sordidus (Coleoptera: Curculionidae)] assessed by RAPDs and AFLPs - Yadav, Sweta Kumari U.; Singh, Jyotsna; Padmanaban, B.; Kumar, Lalitha Sunil (International Journal of Tropical Insect Science, 2017)
Cosmopolites sordidus (Germar), commonly known as banana corm weevil, is an important economic pest in Asia that can cause severe yield loss depending upon the stage at which infestation occurs. In spite of its economic importance, little is known about the population structure of this pest in India. Random amplified polymorphic DNA (RAPD) and amplified fragment length polymorphism (AFLP) were used to characterize the population genetic structure of C. sordidus collected from five hot spot locations in India. Nineteen RAPD primers and five selective AFLP primer combinations generated 147 and 304 amplification products, respectively. UPGMA dendrograms generated with both marker systems failed to reveal populations clustered based on geographic distance, which was confirmed by the Mantel test, which did not show a strong correlation between genetic distance and geographic distance. Values of indices of genetic identity showed that the populations were closely related. Though the gene flow estimate (Nm) between the populations was 0.469, suggesting restricted gene flow, the populations are not genetically distinct. These observations suggest that the range expansion of this banana pest in India has taken place through transport of infested corms and plant material, resulting in genetically close populations that are geographically distinct. These results provide important information on the population structure of this pest in India, which will aid in designing suitable strategies for its control and management, especially with respect to insecticide resistance.
Keywords: Aflps; Arbitrary Primers; Bemisia-tabaci; Cosmopolites Sordidus; diversity; Genetic diversity; Germar Coleoptera; insecticide resistance; Markers; Musa Spp.; Pcr; Rapds; Restricted Gene Flow Natural-populations; Scirpophaga-incertulas

Genomic and functional characterization of coleopteran insect-specific alpha-amylase inhibitor gene from amaranthus species - Bhide, Amey J.; Channale, Sonal M.; Yadav, Yashpal; Bhattacharjee, Kabita; Pawar, Pankaj K.; Maheshwari, V. L.; Gupta, Vidya S.; Ramasamy, Sureshkumar; Giri, Ashok P. (Plant Molecular Biology, 2017)
The smallest 32 amino acid alpha-amylase inhibitor from Amaranthus hypochondriacus (AAI) is reported. The complete gene of pre-protein (AhAI) encoding a 26 amino acid (aa) signal peptide followed by the 43 aa region and the previously identified 32 aa peptide was cloned successfully. Three cysteine residues and one disulfide bond conserved within known alpha-amylase inhibitors were present in AhAI. Identical genomic and open reading frame was found to be present in close relatives of A. hypochondriacus namely Amaranthus paniculatus, Achyranthes aspera and Celosia argentea. Interestingly, the 3'UTR of AhAI varied in these species. The highest expression of AhAI was observed in A. hypochondriacus inflorescence; however, it was not detected in the seed. We hypothesized that the inhibitor expressed in leaves and inflorescence might be transported to the seeds. Sub-cellular localization studies clearly indicated the involvement of AhAI signal peptide in extracellular secretion. Full length rAhAI showed differential inhibition against alpha-amylases from human, insects, fungi and bacteria. Particularly, alpha-amylases from Helicoverpa armigera (Lepidoptera) were not inhibited by AhAI while Tribolium castaneum and Callosobruchus chinensis (Coleoptera) alpha-amylases were completely inhibited. Molecular docking of AhAI revealed tighter interactions with active site residues of T. castaneum alpha-amylase compared to C. chinensis alpha-amylase, which could be the rationale behind the disparity in their IC50. Normal growth, development and adult emergence of C. chinensis were hampered after feeding on rAhAI. Altogether, the ability of AhAI to affect the growth of C. chinensis demonstrated its potential as an efficient bio-control agent, especially against stored grain pests.

Global conformation of Tau protein mapped by Raman spectroscopy - Gorantla, N.V.; Khandelwal, P.; Poddar, P.; Chinnathambi, S. (Methods in Molecular Biology, 2017)
Alzheimer’s disease (AD) is one of the neurodegenerative disease characterized by progressive neuronal loss in the brain. Its two major hallmarks are extracellular senile plaques and intracellular neurofibrillary tangles (NFTs), formed by aggregation of amyloid β-42 (Aβ-42) and Tau protein respectively. Aβ-42 is a transmembrane protein, which is produced after the sequential action of β- and γ-secretases, thus obtained peptide is released extracellularly and gets deposited on the neuron forming senile plaques. NFTs are composed of microtubule-associated protein-Tau (MAPT). Tau protein’s major function is to stabilize the microtubule that provides a track on which the cargo proteins are shuttled and the stabilized microtubule also maintains shape and integrity of the neuronal cell. Tau protein is subjected to various modifications such as phosphorylation, ubiquitination, glycation, acetylation, truncation, glycosylation, deamination, and oxidation; these modifications ultimately lead to its aggregation. Phosphorylation is the major modification and is extensively studied with respect to Tau protein. Tau protein, however, undergoes certain level of phosphorylation and dephosphorylation, which regulates its affinity for microtubule and ultimately leading to microtubule assembly and disassembly. Our main aim was to study the native state of longest isoform of Tau (hTau40WT-4R2N) and its shortest isoform, (hTau23WT-3R0N), at various temperatures such as 10, 25, and 37 °C. Raman spectroscopic results suggested that the proportion of random coils or unordered structure depends on the temperature of the protein environment. Upon increase in the temperature from 10 to 37 °C, the proportion of random coils or unordered structures increased in the case of hTau40WT. However, we did not find a significant effect of temperature on the structure of hTau23WT. This current approach enables one to analyze the global conformation of soluble Tau in solution.

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.

Glycoprotein alpha-amylase inhibitor from Withania somnifera differentially inhibits various alpha-amylases and affects the growth and development of Tribolium castaneum - Kasar, Sainath S.; Marathe, Kiran R.; Bhide, Amey J.; Herwade, Abhijeet P.; Giri, Ashok P.; Maheshwari, Vijay L.; Pawar, Pankaj K. (PEST Management Science, 2017)
BACKGROUND: Identification and characterisation of plant defensive molecules enrich our resources to design crop protection strategies. In particular, plant-derived proteinaceous inhibitor(s) of insect digestive enzymes appear to be a safe, sustainable and attractive option. RESULTS: A glycoprotein having non-competitive alpha-amylase inhibitory activity with a molecular weight of 8.3 kDa was isolated and purified from seeds of Withania somnifera alpha-amylase inhibitor (WSAI). Its mass spectrometry analysis revealed 59% sequence coverage with Wrightide II-type alpha-amylase inhibitor from Wrightia religiosa. A dose-dependent inhibition of alpha-amylases from Aspergillus oryzae, Bacillus subtilis, Helicoverpa armigera and Tribolium castaneumwas recorded. Interestingly, WSAI did not inhibit human salivary alpha-amylase significantly. When adults of T. castaneum were fed with WSAI (1.6mg g(-1)), decrease inconsumption, growthandefficiency of conversion of ingested foodwas evident, along withover fourfold increases in feedingdeterrence index. Adecline inlarval residual alpha-amylase activity after feedingofWSAI resulted ina reduction in longevity of T. castaneum. CONCLUSION: The study reflects the significance of WSAI in affecting the overall growth and development of T. castaneum. Pre-and post-harvest pest resistive capability makes WSAI a potential candidate for insect pest management. Further, the effectiveness of this inhibitor could be explored either in formulations or through a transgenic approach. (C) 2016 Society of Chemical Industry

Gold-catalyzed dehydrazinative C(sp)-S coupling reactions of arylsulfonyl hydrazides with ethynylbenziodoxolones for accessing alkynyl sulfones - Shinde, Popat S.; Patil, Nitin T. (European Journal of Organic Chemistry, 2017)
A gold(III)-catalyzed dehydrazinative coupling reaction between arylsulfonyl hydrazides and ethynylbenziodoxolone reagents was realized for the synthesis of alkynyl sulfones. The scope and versatility of the reaction were demonstrated by the efficient synthesis of 23 derivatives with diverse structural features.

Growth of flower-like patterns of TiO2 nanorods over FTO substrate - Issar, Sheetal; Poddar, Pankaj; Mehra, N. C.; Mahapatro, Ajit K. (International Conference on Technologically Advanced Materials (ICTAM), 2017)
Nanostructures such as nanoparticles, nanowires, nanorods, nanotubes have attracted great interest with the understanding of shape and size dependence in the electronic and sensing properties. This work demonstrates growth and characterization of one-dimensional nanorods of titanium-dioxide (TiO2) on the fluorine doped tin oxide (FTO) substrate by using hydrothermal method. Field effect scanning electron microscopy shows flower-like morphology, and energy-dispersive X-ray spectroscopy confirms the presence of Ti and O. The X-ray diffraction peaks agree well with the JCPDS data. Initially, the 1D nanorods are formed and high concentration of precursor assists evolution of the short branches to form flower-like structures.

H-Bonding assisted self-assembly of anionic and neutral ligand on metal: a comprehensive strategy to mimic ditopic ligands in olefin polymerization - Mote, Nilesh R.; Patel, Ketan; Shinde, Dinesh R.; Gaikwad, Shahaji R.; Koshti, Vijay S.; Gonnade, Rajesh G.; Chikkali, Samir H. (Inorganic Chemistry, 2017)
Self-assembly of two neutral ligands on a metal to mimic bidentate ligand coordination has been frequently encountered in the recent past, but self-assembly of an anionic ligand on a metal template alongside a neutral ligand remains an elusive target. Such a self-assembly is hampered by additional complexity, wherein a highly negatively charged anion can form intermolecular hydrogen bonding with the supramolecular motif, leaving no scope for self-assembly with neutral ligand. Presented here is the self-association of anionic ligand 3-ureidobenzoic acid (2a) and neutral ligand 1-(3-(diphenylphosphanyl)phenyl)urea (1a) on a metal template to yield metal complex [{COOC6H4-NH(CO)NH2}{Ph2PC6H4NH(CO)NH2}PdMeDMSO] (4a). The identity of 4a was established by NMR and mass spectroscopy. Along the same lines, 3-(3-phenylureido)benzoic acid (2b) and 1-(3-(diphenylphosphanyl)phenyl)-3-phenylurea (1b) self-assemble on a metal template to produce palladium complex [{COOC6H4NH(CO)NHPh}{Ph2PC6H4NH(CO)NHPh}PdMePy] (5c). The existence of 5c was confirmed by Job plot, 1-2D NMR spectroscopy, deuterium labeling, IR spectroscopy, UV-vis spectroscopy, model complex synthesis, and DFT calculations. These solution and gas phase investigations authenticated the presence of intramolecular hydrogen bonding between hydrogen's of 1b and carbonyl oxygen of 2b. The generality of the supramolecular approach has been validated by preparing six complexes from four monodentate ligands, and their synthetic utility was demonstrated in ethylene polymerization. Complex 4a was found to be the most active, leading to the production of highly branched polyethylene with a molecular weight of 55700 g/mol and melting temperature of 112 degrees C.

Healable network polymers bearing flexible poly(Lauryl Methacrylate) chains via thermo-reversible furan-maleimide diels-alder reaction - Patil, Sachin S.; Torris, Arun; Wadgaonkar, Prakash P. (Journal of Polymer Science Part A-Polymer Chemistry, 2017)
A new ATRP initiator containing two furyl rings, namely, bis(furan-2-ylmethyl) 2-bromopentanedioate was synthesized starting from commercially available L-glutamic acid as a precursor. Well-defined bisfuryl-terminated poly(lauryl methacrylate) macromonomers with molecular weight and dispersity in the range 5000-12,000 g mol(-1) and 1.30-1.37, respectively, were synthesized employing the initiator by atom transfer radical polymerization (ATRP). Independently, 1,1',1"(nitrilotris(ethane-2,1-diyl)) tris(1H-pyrrole-2,5-dione) was synthesized as a tris-maleimide counterpart for furan-maleimide click reaction. Thermo-reversible network polymer bearing flexible poly(lauryl methacrylate; (PLMA) chains was obtained by furan-maleimide Diels-Alder click reaction of bisfurylterminated PLMA with 1,1',1"-(nitrilotris(ethane-2,1-diyl)) tris(1Hpyrrole-2,5-dione). The prepared network polymer showed retro-Diels-Alder reaction in the temperature range 110-170 degrees C as determined from DSC analysis. The presence of low Tg (-40 degrees C) PLMA chains induced chain mobility to the network structure which led to the complete scratch healing of the coating at 60 degrees C in five days due to furan-maleimide adduct formation. The storage modulus of the network polymer was found to be 3.7 x 10(4) Pa at the constant angular frequency of 5 rad/ sec and strain of 0.5%. The regular reversal of storage (G0) and loss modulus (G") was observed with repeated heating (40 to 110 degrees C) and cooling cycles (110 to 40 degrees C) at constant angular frequency and strain. (C) 2017 Wiley Periodicals, Inc.
Keywords: ethane; Monomers; polymerization

Heterogeneous route for transfer hydrogenation reactions of ketones using Ru(II)Cymene complex over modified benzene-organosilica (PMOB) - Lazar, Anish; Silpa, S.; Prabhakaran, Vinod C.; Singh, A. P. (Molecular Catalysis, 2017)
An inorganic-organic hybrid catalyst, Ru(II)Cym@PMOB, was synthesized by anchoring of [Ru(II)Cl-2(Pcymene)](2) complex which is derived from a reaction between hydrated ruthenium(III) trichloride and ocphellandrene over aminofunctionalized benzene-organosilica (PMOB). In the context of secondary alcohol synthesis from ketones, transfer hydrogenation (TH) reactions are convenient compared to conventional hydrogenation reactions owing to its lower activation energy and ambient pressure and mild temperature reaction" conditions. The synthesized catalysts were characterized by CHN analysis, XRD, ICP, N-2-sorption analysis, TG & DTA, FFIR,C-13 & 29Si solid NMR, UV-vis, TEM, SEM and XPS. The catalytic activities of neat [Ru(II)C-12(p-cymene)]2 complex and Ru(II)Cym@PMOB were evaluated in transfer hydrogenation (TH) of ketones (-97%) and compared with conventional hydrogenation reactions (-5%) where molecular H-2 was used. The results showed Ru(II)Cym@PMOB as highly active catalyst towards transfer hydrogenation (TH) reaction of acetophenones compared to neat [Ru(II)Cl-2(p-cymene)(12) complex. The heterogeneity of Ru(II)Cym@PMOB was confirmed by Sheldon's test. (C) 2017 Elsevier B.V. All rights reserved.
Keywords: Conventional Hydrogenation Reactions; Ru(II)Cym@PMOB; Transfer Hydrogenation Reaction; [Ru(II)Cl2(p-cymene)]2 complex

Highly active recyclable SBA-15-EDTA-Pd catalyst for Mizoroki-Heck, Stille and Kumada C-C coupling reactions - Rathod, Jayant; Sharma, Priti; Pandey, Punam; Singh, A. P.; Kumar, Pradeep (Journal of Porous Materials, 2017)
Highly efficient SBA-15-EDTA-Pd(11) heterogeneous catalyst was synthesized by covalent anchoring Pd-EDTA complex over organo-modified surface of SBA-15. SBA-15-EDTA-Pd(11) catalyst was found to exhibit excellent catalytic activity in appreciable yield for Heck, Stille and Kumada cross-coupling reactions. Catalytic system exhibited excellent activity for completion of reaction, isolation, Pd loading (0.87 mmol%) and yields of products as compared to earlier reported heterogeneous supported Pd catalysts. Covalently anchored heterogeneous SBA-15-EDTA-Pd(11) catalyst can be recycled for more than five times without noticeable loss in activity and selectivity.

High-Performance Sensing Behavior Using Electronic Ink of 2D SnSe2 Nanosheets. - Pawar, Mahendra; Kadam, Sunil; Late, Dattatray J. (Chemistry Select, 2017)
Most of the recent research work on layered chalcogenides is understandably focused on single atomic layers. However, it is uncertain if the single layer units are most ideal structures for enhanced gas-solid interactions. To probe this concern, we have synthesized few layer thick SnSe<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 nanosheets ink using liquid exfoliation method. The morphology, thickness / layering and elemental analysis of the sheets were characterized by using SEM, TEM, AFM, Raman spectroscopy and by XPS. The two dimensional (2D) SnSe<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 nanosheets sensor device with different thicknesses was assessed for the humidity and gas sensing performances with exposure to humidity in different conditions. The results show that compared to the bulk / thicker counterpart, sensor device of few SnSe<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 layers exhibit excellent sensitivity, recovery and ability to be tune the sensing performance with thickness and can be used in lab on chip devices.

Hyaluronic acid layered chimeric nanoparticles: targeting MAPK-P13K signaling hub in colon cancer cells - Palvai, Sandeep; Kuman, Meenu Mahesh; Sengupta, Poulonu; Basu, Sudipta (ACS Omega, 2017)
Colon cancer has emerged as one of the most devastating diseases in the whole world. Mitogen-activated protein kinase (MAPK)-phosphatidylinsitol-3-kinase (PI3K) signaling hub has gained lots of attention due to its deregulation in colon cancer cells. However, selective targeting of oncogenic MAPK-PI3K hub in colon cancer has remained highly challenging, hence it has mostly been unexplored. To address this, we have engineered a hyaluronic acid layered lipid-based chimeric nanoparticle (HA-CNP) consisting of AZD6244 (MAPK inhibitor), PI103 (PI3K inhibitor), and cisplatin (DNA impairing drug) ratiometrically in a single particle. Electron microscopy (field emission scanning electron microscopy and atomic force microscopy) and dynamic light scattering were utilized to characterize the size, shape, morphology, and surface charge of the HA-CNPs. Fluorescent confocal laser scanning microscopy and flow cytometry analysis confirmed that HA-CNPs were taken up by HCT-116 colon cancer cells by merging of clathrin and CD44 receptor-mediated endocytosis along with macropinocytosis to home into acidic organelles (lysosomes) within 1 h. A gel electrophoresis study evidently established that HA-CNPs simultaneously inhibited MAPK-PI3K signaling hub with DNA damage in HCT-116 cells. These HA-CNPs stalled the cell cycle into G0/G1 phase, leading to induction of apoptosis (early and late) in colon cancer cells. Finally, these HA-CNPs exerted remarkable cytotoxicity in HCT-116 colon cancer cells at 24 h compared to that of the free triple drug cocktail as well as HA-coated dual drug-loaded nanoparticles without showing any cell death in healthy L929 fibroblast cells. These HA-coated CNPs have potential to be translated into clinics as a novel platform to perturb various oncogenic signaling hubs concomitantly toward next-generation targeted colon cancer therapy.

Hybrids of thienopyrimidinones and thiouracils as anti-tubercular agents: SAR and docking studies - Pisal, Mahesh M.; Nawale, Laxman U.; Patil, Manoj; Bhansali, Sujit G.; Gajbhiye, Jayant M.; Sarkar, Dhiman; Chavan, Subhash P.; Borate, Hanumant B. (European Journal of Medicinal Chemistry, 2017)
A number of hybrid molecules containing thienopyrimidinones and thiouracil moieties were designed, synthesized and tested against Mycobacterium tuberculosis H37Ra wherein it was observed that the compounds 11-1514 exhibited antitubercular activity in vitro (MIC 7.6–19.1 μg/ml, 12–35 μM) against dormant stage while compound 15 exhibited antitubercular activity in vitro against dormant (MIC 23.4 μg/ml, 41 μM) as well as active (MIC 25.4 μg/ml, 45 μM) stage. Structural modifications of compound 15 were carried out to study the structure-activity relationship and it was observed that compound 18 exhibited antitubercular activity comparable to compound 15. Cytotoxicity studies revealed that these molecules were non-toxic. The docking study of compound 15 showed that there was binding with the active site of mycobacterial pantothenate synthetase. Further docking studies led to the synthesis of the compounds 16 and 17 and the antitubercular activity screening results showed that these compounds have significant antitubercular activity. The compounds 15-18 (MIC 11–29 μg/ml, 19–51 μM) can be used as starting points for further optimization. The synthetic strategies used in the present work have potential to prepare a large number of compounds for further refinement of structures and the present results will be very useful in the development of a new class of antimycobacterial agents.

Identification of biomolecules involved in the biosynthesis of gold nanoparticles from living peanut seedlings - Raju, D.; Siddiqui, Ejaz Ahmad; Prasanth, S.; Khan, Bashir M.; Mehta, Urmil J.; Ahmad, Absar (Journal of Nanoscience and Nanotechnology, 2017)
In present work, we have fabricated gold nanoparticles by treating an aqueous solution of 10(-4) M HAuCl4 with the proteins extracted from roots of in vitro raised peanut seedlings and purified them by FPLC at room temperature. These proteins which tested positive for the reduction of 10(-4) M HAuCl4 were identified as Mannose glucose binding lectin and Ara h 8 allergen isoforms by ESI MS/MS. It is a well known fact that aromatic amino acids possess delocalized pi electrons in their ring structures, rendering them as the best electron donors which can transfer electrons and reduce the acceptor. These results suggest that the aromatic amino acids present in the proteins from the peanut seedlings are the primary biomolecules involved in the reduction of Au (III) to Au (0). We isolated different protein of molecular weight 16.4, 28.3 and 30 kDa involved in the formation of nanoparticles. The protein with molecular weight 16.4 kDa (allergens) yielded NPs of 25-60 nm whereas, the proteins with molecular weight 28.3 kDa and 30 kDa (lectins) yielded highly monodispersed NPs of 5-20 nm in size. The results clearly indicate that the size of nanoparticles can be controlled by different proteins.

Identification of new anti-inflammatory agents based on nitrosporeusine natural products of marine origin - Philkhana, Satish Chandra; Verma, Abhishek Kumar; Jachak, Gorakhnath R.; Hazra, Bibhabasu; Basu, Anirban; Reddy, D. Srinivasa (European Journal of Medicinal Chemistry, 2017)
Nitrosporeusines A and B are two recently isolated marine natural products with novel skeleton and exceptional biological profile. Interesting antiviral activity of nitrosporeusines and promising potential in curing various diseases, evident from positive data from various animal models, led us to investigate their anti-inflammatory potential. Accordingly, we planned and synthesized nitrosporeusines A and B in racemic as well as enantiopure forms. The natural product synthesis was followed by preparation of several analogues, and all the synthesized compounds were evaluated for in vitro and in vivo anti-inflammatory potential. Among them, compounds 25, 29 and 40 significantly reduced levels of nitric oxide (NO), reactive oxygen species (ROS) and pro-inflammatory cytokines. In addition, these compounds suppressed several pro-inflammatory mediators including inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2), nuclear factor-kappa B (NF -kappa B), and thereby can be emerged as potent anti-inflammatory compounds. Furthermore, all possible isomers of lead compound 25 were synthesized, characterized and profiled in same set of assays and found that one of the enantiomer (-)-25a was superior among them. (C) 2017 Elsevier Masson SAS. All rights reserved.

In situ grown nickel nanoparticles in a calixarene nanoreactor on a graphene-MoS2 support for efficient water electrolysis - Waghmode, Babasaheb J.; Bhange, Siddheshwar N.; Unni, SreeKuttan M.; Patil, Kashinath R.; Malkhede, Dipalee D. (Sustainable Energy & Fuels, 2017)
Electrochemical production of hydrogen, facilitated in electrolysers, holds great promise for energy storage and solar fuel production. Catalysis of the oxygen evolution reaction (OER) is a bottleneck of this process. However, the sluggish OER kinetics and the utilization of precious metal catalysts are key obstacles in the broad deployment of this energy technology. We report the preparation and use of an inexpensive GrMoS(2)SC(8)Ni nanocomposite material as a highly effective OER catalyst in an alkaline electrolyte. Experimental investigations have shown that improvements can be realized in the catalytic performance of Ni metal if it is a component of the composite material. We propose an explanation for these enhancements based on a hydrogen acceptor concept. This concept comprises the stabilization of an *-OOH intermediate, which effectively lowers the potential needed for breaking bonds on the surface. Herein, an inexpensive immobilized SC8 layer was used as the nanoreactor to synthesize metallic Ni nanoparticles (NPs) through an in situ redox process. The process was applied to form immobilized NPs on flat and curved 2D surfaces. The outstanding OER performance of Ni NPs could be attributed to their large surface area, efficient mass and charge transport, and high structural stability arising from the unique SC8 cage structure, built on the GrMoS(2) substrate. The GrMoS(2)SC(8)Ni nanocomposite shows the highest activity, exhibiting a 214 mV overpotential at 10 mA cm(-2) (equivalent to 10% efficiency of solarto-fuel conversion) and a Tafel slope of 31 mV dec(-1) in 1 M KOH solution. It further demonstrates high stability as there is no apparent OER activity loss (based on a chronoamperometry test) or particle aggregation (based on SEM image observation) after a 10 h anodization test. The facile preparation method and high efficiency and durability enable this electrocatalyst to be a promising candidate for future large-scale applications in water splitting. Thus, this work opens a new avenue toward the development of highly efficient, inexpensive OER catalysts.

Influence of carbon based supports on selectivity behavior of diols and propanol in Ru catalyzed glycerol hydrogenolysis - Mane, Rasika B.; Patil, S.; Shirai, Masayuki; Rayalu, Sadhana S.; Rode, Chandrashekhar V. (Applied Catalysis B: Environmental, 2017)
Activated carbon (AC) and three graphite materials were studied as supports for Ru catalyzed glycerol hydrogenolysis to propanediols and 1-propanol. Structural characteristics of AC and graphite materials were found to greatly affect the reducibility and particle size of supported Ru and hence, the activity and product distribution in glycerol hydrogenolysis. XRD of graphite materials showed distinctly (002) plane having highly organized layered structure and the peak intensity decreased in the order of Ru/KS150 > Ru/HSAG100 > Ru/KS6 due to decrease in the graphite sheet thickness. In Raman, the intense D band in HSAG100 compared to that in KS6 and KS150 samples indicated its highly amorphous nature or mixed carbon hybridization. Glycerol conversion for Ru on AC was higher than that on graphite and among different graphites, it showed a descending activity order of Ru/KS6 > Ru/HSAG100 > Ru/KS150. The product distribution for AC and HSAG100 supported Ru was similar, giving 1-propanol (45%) alongwith 1,2-propanediol (1,2-PDO) (37%) and 1,3-propanediol (1,3-PDO) (9–11%). For graphite supports, availability of Ru although bigger in size (4–5 nm), would be higher on the surface than in case of AC which formed deep hydrogenolysis products like 1-, 2- propanol, ethanol etc.
Keywords: activated carbon; Amorphous carbon; catalysis; Glycerol; Glycerol conversions; Glycerol hydrogenolysis; graphite composites; Graphite supports; Hydrogenolysis; Hydrolysis; layered structures; Particle size; Product distributions; Propanediols; Propanol; Selectivity behavior; Structural characteristics; Structural effect; Structural effects

Insertion or ziegler-natta polymerization of olefins: science and technology - Chikkali, S. H.; Patel, K.,; Netalkar, S. (Metal-catalyzed polymerization: fundamentals to applications, 2017)
One of the most disruptive discoveries of twentieth century has been metal-catalyzed polymerization of ethylene to polyethylene by Prof. Karl Ziegler from the Max Plank Institut Fuer Kohlenforschung, Mulheim, Germany. This discovery marked the beginning of an era, which revolutionized the field of chemistry, in particular, the field of polymer chemistry in many aspects and saw an avalanche of patents and publications. Unlike typical academic discoveries, this invention did not stop at the academic labs, but led to the development of a large-scale process that produces about 180 million tons of polyolefins (annually) today. 1 But the very obvious question that comes to our mind is what prompted Prof. Ziegler to react ethylene with the two components (that we will discuss later in this chapter)? It was not an overnight realization, but instead, it was rational analysis of a serendipitous observation and systematic experimentation by Prof. Ziegler.

Interfacial-active polymer nanoparticles, their assemblies, and SERS application - Visaveliya, Nikunjkumar R.; Li, Xiang; Knauer, Andrea; Prasad, Bhagavatula L. V.; Kohler, Johann Michael (Macromolecular Chemistry and Physics, 2017)
In this work, surface-active polymer nanoparticles as well as polymer-polymer and polymer-metal nanoassembly particles are synthesized, and different parameters such as their size, morphologies, and assembling strength are studied. Nanoassembly particles are attractive because of the coupled properties with a large surface to volume ratio. A key challenge is to produce the core-shell polymer nanoparticles via single-step processes. To address this concern, here, microfluidics approach and precise interfacial reaction strategies are used, and hence different types of surface layered polymer nanoparticles are obtained in one-step processes. An inner core material is hydrophobic, whereas a hydrophilic surface layer (in situ formed during the polymerization process) swells in the aqueous environment. Moreover, three different reaction setups (batch, flow, and in situ) are applied in order to architect the nanoassembling hierarchical structures via layer-by-layer strategy. On the other side, polymer-metal nanoassembly particles as well as metal catalyzed metal deposited four layered nanoassembly particles of tuned size and compositions are produced. It is shown that these particles can be used as nanosensor particles for surface-enhanced Raman spectroscopy.

Interplay between pi-bridges and positions of branched alkyl groups of unsymmetrical D-A-D-pi-A squaraines in dye-sensitized solar cells: mode of dye anchoring and the charge transfer process at the TiO2/Dye/electrolyte interface - Punitharasu, Vellimalai; Kavungathodi, Munavvar Fairoos Mele; Nithyanandhan, Jayaraj (ACS Applied Materials & Interfaces, 2017)
Far-red-absorbing squaraines possessing high molar absorptivity (>10(5) M-1 cm(-1)) are being attracted as high-efficiency chromophores in dye-sensitized solar cells (DSSCs). A series of donor acceptor -donor-pi spacer-acceptor (D-A-D-pi-A) unsymmetrical squaraines, PSQ1-5, with indoline donor and squaric/cyanoacetic acid acceptor units, were designed for sensitized solar cells. For extending the absorption toward the near-infrared region (NIR) and controlling the orientation on the TiO2 surface, benzene (PSQ1 and PSQ2) and thiophene (PSQ3-5) 7r-spacers and out-of-plane branched alkyl groups at the indoline that are away (PSQ1, PSQ3, and PSQS) or near (PSQ2 and PSQ4) the anchoring group, respectively, were introduced. Dynamic aggregation tendency of PSQ1 and PSQ3 than that of their isomers systematically modulates the orientation on the TiO2 surface, which in turn enhances photovoltaic performance. Absorptance on a thin transparent TiO2 film shows a visible-to-NIR response with an onset around 800 nm for PSQ3-5. Although there is resemblance in electrochemical redox levels, their high injection efficiency and recombination resistance differentiated impact on the way of anchoring and the dihedral angle between D-A-D units and g-spacers. DSSCs sensitized with PSQS achieved a PCE of 8.15% under simulated AM 1.5G illumination (100 mW cm(-2)), with the current density (j) and open-circuit voltage (Voc) of 19.73 mA cm(-2) and 630 mV, respectively. A clear comparison of the incident-photon-to-current conversion efficiency versus the light-harvesting efficiency correlates the structure-property relationship with J obtained for PSQ dyes. Electrochemical impedance spectroscopy was carried out to examine the TiO2/dye/electrolyte interface for further confirmation of the enhanced PCE of top-se-alkylated PSQS over that of other dyes.
Keywords: D-A-D-pi-A framework; dye-sensitized solar cell; H- and J-type aggregation; orientation of dyes; static/dynamic aggregates; unsymmetrical squaraine

Intramolecular ipso-arylative cyclization of aryl-alkynoates and N-arylpropiolamides with aryldiazonium salts through merged gold/visible light photoredox catalysis - Bansode, Avinash H.; Shaikh, Samir R.; Gonnade, Rajesh G.; Patil, Nitin T. (Chemical Communications, 2017)
A visible-light-promoted merged gold/photoredox catalyzed ipsoarylative cyclization has been reported. For instance, the reaction of aryl-alkynoates and N-arylpropiolamides with aryldiazonium salts in the presence of catalytic amounts of [(4-OCH3)C6H4](3)PAuCl and Ru(bpy)(3)(PF6)(2) under irradiation using a 32WCFL bulb gave arylated spirocarbocycles in moderate to good yields.

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''

Investigation of the biocompatibility and cytotoxicity associated with ROP initiator and its role in bulk polymerization of L-lactide - Parwe, Sharad P.; Warkad, Shrikant D.; Mane, Manoj V.; Shedage, Pranita S.; Garnaik, Baijayantimala (Polymer, 2017)
Poly (L-lactide) (PLLA) is one of the most attractive polymers for use in biomedical applications. In such applications it is necessary to reduce the use of toxic chemicals and catalysts used in PLLA synthesis, to minimize any adverse effects. In view of this, we have performed ring opening polymerization (ROP) of Llactide (LA) using biocompatible initiator, namely, Zinc L-Proline (ZnP) in bulk. High molecular weight PLLA (Mw up to 1.45 x 10(5) Da) was obtained using the ZnP complex. The ZnP complex is safe, easy to prepare, store and handle. H-1 and C-13 NMR spectra of PLLA were used to determine the extent of monomer conversion and stereo sequence respectively. Differential Scanning Calorimetry (DSC) and Size Exclusion Chromatography (SEC) were used to determine thermal properties, Mn, Mw and polydispersity index respectively. The mechanism of ROP of LA in the presence of ZnP was studied using Density Functional Theory (DFf) which was in good agreement with results from H-1 NMR and Matrix-Assisted Laser Desorption/Ionization Spectrometry (MALDI-TOF). Biocompatibility/non toxicity of PLLA prepared using ZnP was studied in-vitro using MTT assay by examining the proliferation rate of mouse myoblast C2C12 cell line. Escherichia coli and Staphylococcus aureus were used for the study of antibacterial activity of PLLA. (C) 2017 Elsevier Ltd. All rights reserved.

Ionic strength-dependent changes in tentacular ion exchangers with variable ligand density. II. functional properties - Shambure, Rahul; Angelo, James M.; Gillespie, Christopher M.; Phillips, Michael; Graalfs, Heiner; Lenhoff, Abraham M. (Journal of Chromatography A, 2017)
The effect of ligand density was studied on protein adsorption and transport behavior in tentacular cation-exchange sorbents at different ionic strengths. Results were obtained for lysozyme, lactoferrin and a monoclonal antibody (mAb) in order to examine the effects of protein size and charge. The combination of ligand density and ionic strength results in extensive variability of the static and dynamic binding capacities, transport rate and binding affinity of the proteins. Uptake and elution experiments were performed to quantify the transport behavior of selected proteins, specifically to estimate intraparticle protein diffusivities. The observed trend of decreasing uptake diffusivities with an increase in ligand density was correlated to structural properties of the ligand-density variants, particularly the accessible porosity. Increasing the ionic strength of the equilibration buffer led to enhanced mass transfer during uptake, independent of the transport model used, and specifically for larger proteins like lactoferrin and mAb, the most significant effects were evident in the sorbent of the highest ligand density. For lysozyme, higher ligand density leads to higher static and dynamic binding capacities whereas for lactoferrin and the mAb, the binding capacity is a complex function of accessible porosity due to ionic strength-dependent changes. Ligand density has a less pronounced effect on the elution rate, presumably due to ionic strength dependent changes in the pore architecture of the sorbents. (C) 2017 Elsevier B.V. All rights reserved.

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.

Isomerizing hydroformylation of cashew nut shell liquid - Pandey, Swechchha; Shinde, Dinesh R.; Chikkali, Samir H. (ChemCatChem, 2017)
A small library of bisphosphorus ligands was evaluated in the rhodium-catalyzed isomerizing hydroformylation (I-HF) of cashew nut shell liquid (CNSL). The rhodium complex of 1,2-bis((di-tert-butylphosphanyl)methyl)benzene (BDTBPMB; L4) outperformed the other bisphosphite and bisphosphine ligands and unveiled a moderate selectivity of 28% and 50% in the I-HF of CNSL monoene and methoxy-protected monoene, respectively. The resultant aldehyde 16-(3-methoxyphenyl)hexadecanal P1 was isolated and its identity was fully established. Application of bis-phosphine ligand L4 in the I-HF of highly challenging CNSL cardanol (S3) and methoxy-protected CNSL cardanol yielded a linear selectivity of 74%, although with reduced conversion. To demonstrate the synthetic utility of our strategy, the obtained aldehyde (derived from S3) was subjected to hydrogenation and the resultant 3-(16-hydroxyhexadecyl) phenol (P8) was isolated in 89% isolated yield. High-pressure NMR investigation revealed selective formation of a bis-equatorial BDTBPMB-rhodium complex, which might be responsible for the excellent linear selectivity.

Kinetics and thermodynamics of transpeptidation catalysed by Bacillus subtilis gamma glutamyl transferase - Balakrishna, Sharath; Prabhune, Asmita A. (Indian Journal of Biochemistry and Biophysics, 2017)
Gamma glutamyl transferases (GGT) catalyse the removal (deglutamylation) of the terminal gamma-glutamate residue from compounds such as glutathione and poly-gamma-glutamic acid and its transfer either to a water molecule (hydrolysis) or to a peptide/amino acid (transpeptidation). We analysed the kinetics of Bacillus subtilis GGT (BsGGT) catalysed transpeptidation using gamma-glutamyl-(3-carboxyl)-4-nitroaniline as the gamma-glutamate-donor and glycylglycine (Gly-Gly) as the gamma-glutamate acceptor. Addition of Gly-Gly improved the affinity (Km) of the enzyme for gamma-glutamyl-(3-carboxyl)-4-nitroaniline by nearly 25 times with negligible impact on the rate of deglutamylation (V-max). The asymmetric changes in the kinetic parameters improved the specificity constant (K-cat/K-m.) by about 43 times. BsGGT catalysed transpeptidation was pronounced in conditions that are unfavorable for hydrolysis. Maximum transpeptidation occurred near neutral pH and when the concentration of the gamma-glutamate-donor substrate is lower. The effect of Gly-Gly on the kinetics of BsGGT is contrastingly different from that observed for eukaryotic GGTs. In the case of mammalian GGTs, the addition of Gly-Gly increases both Km and k(cat); and, the specificity constant (K-cat/K-m) remains unaltered

Lewis acid catalyzed cascade annulation of alkynols with alpha-ketoesters: a facile access to gamma-spiroketal-gamma-lactones - Kambale, Digambar A.; Thorat, Sagar S.; Pratapure, Madhukar S.; Gonnade, Rajesh G.; Kontham, Ravindar (Chemical Communications, 2017)
A novel Lewis acid catalyzed intermolecular cascade annulation of alkynols with alpha-ketoesters has been developed. This simple and efficient cascade annulation proceeds through a 5-exo-dig cyclization of alkynols followed by annulation with alpha-ketoester to provide a wide variety of unsaturated gamma-spiroketal-gamma-lactones (1,6-dioxaspiro[4.4]non-3-en-2-ones) related to many natural products.

Ln(8) (Ln = Gd, Ho, Er, Yb) Butterfly core-exhibiting magnetocaloric effect and field-induced SMM behavior for Er analouge - Bala, Sukhen; Adhikary, Amit; Bhattacharya, Sudeshna; Sen Bishwas, Mousumi; Poddar, Pankaj; Mondal, Raju (ChemistrySelect, 2017)
In this article, we report four pyridyl-pyrazolyl based poly-nuclear cluster complexes with Ln(8) {Ln = [Gd-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](DMF)(2)(MeOH)(1), [Ho-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](2), [Er-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](DMF)(MeOH)(H2O)(3), [Yb-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](DMF)(MeOH)(4) [DEA = Diethanolamine] cores. The impetus for this study was to explore the magnetic behaviour of lanthanide ions which are often ignored or overlooked. X-ray crystal analysis show that these complexes are isostructural and exhibit an interesting butterfly like topology. The semi-rigidity and asymmetric nature of the ligand led to different coordination environment around the metal centres. The lanthanide ions adopt two types of geometry, a bicapped trigonal prism and a distorted square antiprismatic geometry around the metal center. Such dissimilar coordination environments around the lanthanide centre can have profound effects on their magnetic behaviour. Indeed, the magnetic measurements revealed significant magnetocaloric effect for octanuclear gadolinium complex 1 with magnetic entropy change (-Delta S-m ) of 31.4 J kg(-1) K-1 for Delta H = 9 T at T = 3 K whereas Er analogue complex 3 displayed SMM behavior.

Low-dimensional hybrid perovskites as high performance anodes for alkali-ion batteries - Tathavadekar, Mukta; Krishnamurthy, Shrreya; Banerjee, Aparna; Nagane, Satyawan; Gawli, Yogesh; Suryawanshi, Anil; Bhat, Suresh; Puthusseri, Dhanya; Mohite, Aditya D.; Ogale, Satishchandra (Journal of Materials Chemistry A, 2017)
State-of-the-art Li (or Na) ion batteries work by insertion/extraction of the alkali metal ions into a porous electrode material, where the overall capacity is strongly dependent on the accessibility of the host material interior to the ions. On the other hand, the performance stability depends on various factors governed by the specific constitution of the electrode. Here we show that molecularly engineered low-dimensional hybrid perovskites can work as excellent anode materials for alkali-ion batteries. We measure a high reversible capacity of 646 mA h g(-1) at 100 mA g(-1) with good stability tested up to 250 cycles for the benzidine mediated lead iodide based 1D system. An ex situ analysis of the electrodes reveals that the storage primarily occurs via the Li-x(or Na-x)Pb alloying/de-alloying process. We anticipate that these results open a new direction for the use of low-dimensional hybrid perovskites for energy storage applications.
Keywords: Generation; Inorganic-Organic Hybrid; Lead Iodide; lithiation-intramolecular electrophilic reaction; Na-Air Battery; Negative Electrodes; Organometal Halide perovskites; PB; Sequential Deposition; Solar-cells

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

Mechanistic investigation of the carbon-iodine bond activation on the niobium-carbon cluster - Sengupta, Turbasu; Khan, Muntazir S.; Pal, Sourav (ACS Omega, 2017)
The activation process of carbon-iodine (C-I) bond on neutral and cationic niobium metcars (Nb8C12) is investigated using density functional theory and related computational techniques. Metallocarbohedrenes or metcars are a class of stable metal-carbide clusters of specific stoichiometry and of great interest to cluster chemists since their first discovery. The detailed reaction mechanism along with the overall energy profile of the C-I dissociation reaction on niobium metcar and its cations is presented in this paper. The tunneling-corrected rate constants and their related reaction parameters such as the pre-exponential factor are also included alongside. The major differences between the reaction mechanism of the neutral and cationic metcars are also highlighted as well. Despite the available experimental results, the C-I bond dissociation on metcars has remained an unexplored problem in the theoretical and computational domains. Thus, the present investigation can fill in the gap and may also provide new insights provoking further developments in cluster and materials chemistry in future.

Mechanochemical synthesis of N-salicylideneaniline: thermosalient effect of polymorphic crystals - Mittapalli, Sudhir; Perumalla, D. Sravanakumar; Nangia, Ashwini (IUCRJ, 2017)
Polymorphs of the dichloro derivative of N-salicylideneaniline exhibit mechanical responses such as jumping (Forms I and III) and exploding (Form II) in its three polymorphs. The molecules are connected via the amide N-H center dot center dot center dot O dimer synthon and C-Cl center dot center dot center dot O halogen bond in the three crystal structures. A fourth high-temperature Form IV was confirmed by variable-temperature single-crystal X-ray diffraction at 180 degrees C. The behaviour of jumping exhibited by the polymorphic crystals of Forms I and III is due to the layered sheet morphology and the transmission of thermal stress in a single direction, compared with the corrugated sheet structure of Form II such that heat dissipation is more isotropic causing blasting. The role of weak C-Cl center dot center dot center dot O interactions in the thermal response of molecular crystals is discussed.
Keywords: crystal design; crystal engineering; Halogen bonding; hydrogen bonding; intermolecular interactions; materials science; mechanochemistry; polymorphism

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.

Microwave assisted batch and continuous flow synthesis of palladium supported on magnetic nickel nanocrystals and their evaluation as reusable catalyst - Nikam, Arun V.; Kulkarni, Amol A.; Prasad, Bhagavatula L. V. (Crystal Growth & Design, 2017)
Palladium nanocrystals (NCs) supported on nickel NCs (Pd/Ni) were synthesized in a continuous flow manner by the microwave-assisted method in the presence and absence of oleylamine. Parameters optimized for batch experiments were considered while performing continuous flow synthesis. The Pd/Ni NCs synthesized in the presence of oleylamine displayed good catalytic activity for hydrogenation of aromatic nitro compounds, and those bearing alkene, and alkyne moieties. The ferromagnetic character of the supporting nickel NCs allowed the recovery of the catalyst and these recovered catalysts could be reused several times.

Microwave-assisted synthesis of 5-substituted 1H-tetrazoles via [3+2] cycloaddition over a heterogeneous Cu-based catalyst: application to the preparation of N-13-labelled tetrazoles - Joshi, Sameer M.; Mane, Rasika B.; Pulagam, Krishna R.; Gomez-Vallejo, Vanessa; Llop, Jordi; Rode, Chandrashekhar (New Journal of Chemistry, 2017)
The [3+2] cycloaddition between various nitriles and sodium azide proceeds smoothly in the presence of a new Cu-II catalyst in N-methyl-2-pyrrolidone (NMP) to give the corresponding 5-substituted 1H-tetrazoles. The desired tetrazoles were obtained in high yields within 3-30 min by employing controlled microwave heating. The reaction most probably proceeds through the activation of the nitrile groups by the Cu-II species, followed by a successive [3+2] cycloaddition with the sodium azide. The good performance of the catalyst enabled the preparation of selected tetrazoles labelled with the positron emitter nitrogen-13 even under conventional heating. The short reaction time, simple work-up procedure, and recyclability of the catalyst are advantages of the method reported here.

Modeling G-L-L-S reactor: a case of hydrogenation of nitrobenzene - Sharma, Deepankar V.; Patwardhan, Ashwin W.; Ranade, Vivek V. (Industrial & Engineering Chemistry Research, 2017)
Gas-liquid liquid solid (GLLS) reaction systems are often encountered in manufacturing of fine and specialty chemicals. More often than not, such reaction systems involve multiple reactions, and selectivity toward the desired component always poses challenges. An adequate understanding of various parameters affecting GLLS reactor performance is essential to develop strategies for realizing desired selectivity. In this work, a comprehensive reaction engineering model for simulating four phase hydrogenation reactions has been developed. A generalized mixing cell based framework for a reaction system with four interacting phases (gas [G], aqueous [L], organic [L], and solid catalyst [S]) was developed. The model is written in a general way so as to specify one of the liquid phases as a continuous phase, and the other three phases are dispersed into it. In each cell, vapor space is included. The model includes the possibility of evaporation of solvent and internal condensation (in vapor space). The model can also be applied for a dead end (from a perspective of reacting gas) reactor. Model equations were solved using MATLAB. The equations and solution methodology were verified by comparing numerical solutions with available solutions of various limiting cases. A case of four phase hydrogenation of nitrobenzene to para amino phenol and aniline was considered to illustrate the application of the developed model. Key findings from the model were validated by comparing with laboratory scale experimental data. The model was then used to develop insights and guidelines for enhancing selectivity toward desired product. The developed model and presented results will be useful to develop general guidelines for design and optimization of GLLS reactors.

Molecular features of bile salt hydrolases and relevance in human health - Chand, D.; Avinash, V. S.; Yadav, Y.; Pundle, A. V.; Suresh, C. G.; Ramasamy, S. (Biochimica et Biophysica Acta - General Subjects, 2017)
Background: Bile salt hydrolase (BSH) enzyme is responsible for the de-conjugation of bile salts by commensal bacteria, thus playing a vital role in their colonization and survival in the mammalian intestine and determination of their probiotic potential. Further, bile deconjugation also leads to lowering of cholesterol and alterations in energy homeostasis, thus making BSH a clinically important enzyme. Scope of the review: Many recent observations have indicated that BSH may be involved in a multifaceted array of roles, directly or indirectly in the host and microbial physiology. BSH paralogues have now been found to occur in different microbes including free-living and pathogenic bacteria and Archaea. BSHs from various sources also show differential activity and substrate spectrum. Certain bacteria are known to possess multiple genes for BSH enzymes. BSHs have been reported to influence different metabolic phenomena, including bacterial pathogenesis and the maintenance of lipid and glucose homeostasis in the host. These observations necessitate an intense study into the biochemical, structural and regulatory features of BSH enzymes to better understand their role in regulating bacterial and host metabolism. Major conclusions: In this review, the available information on the characteristics of BSH enzymes have been organized in order to understand their interactions with a wide range of substrates and their myriad physiological roles, from bile resistance to signalling mechanisms. General significance: A detailed exploration of BSH architecture and regulation could provide insights into its evolution and a deeper appreciation of the multiple functions of this enzyme relevant to healthcare.

Molecular level control of the capacitance of two-dimensional covalent organic frameworks: role of hydrogen bonding in energy storage materials - Chandra, S.; Chowdhury, D.R; Addicoat, M.; Heine, T.; Paul, A.; Banerjee, R. (Chemistry of Materials, 2017)
Two-dimensional redox-active covalent organic frameworks (COFs) are ideal materials for energy storage applications due to their high surface area, extended pi conjugated structure, tunable pore size, and adjustable functionalities. Herein, we report the synthesis and super capacitor application of two redox active COFs [TpPa-(OH)(2) and TpBD-(OH)(2)] along with the role of their redox active functional groups for the enrichment of specific capacitance. Of these COFs, TpPa-(OH)2 exhibited the highest specific capacitance of 416 F g(-1) at 0.5 A g(-1) current density in three electrode configuration while the highest specific capacitance was 214 F g(-1) at 0.2 A g(-1) current density in two electrode configuration. Superior specific capacitance was due to emergence of excellent pseudocapacitance by virtue of precise molecular level control over redox functionalities present in the COF backbone. This COF also demonstrated 66% capacitance retention after 10 000 cycles along with 43% accessibility of the redox-active hydroquinone (H2Q) moieties in three electrode configuration while the capacitance retention was 88% after 10 000 cycles in two electrode configuration. Exceptionally high specific capacitance of TpPa-(OH)(2) was due to the reversible proton-coupled electron transfer (2H(+)/2(e-)) of hydroquinone/benzoquinone (H(2)Q/Q) moieties wherein H(2)Q and Qhad comparable chemical stabilities during redox cycling that originated from H-bonding, which was supported by calculated structures.

Molecular tools for controlling nanoparticle size/morphologies - Sahu, P.; Shimpi, J.; Prasad, B.L.V. (Molecular materials: preparation, characterization, and applications, 2017)
The preparation of nanoparticles (especially those of noble metals) predates the coinage of the term nano itself by several centuries. The earliest example of the preparation of nanoparticles has been linked to Roman artisans who created colored glass by probably mixing gold chloride and other salts of noble metals while making glass. Many artistic marvels such as the Lycurgus cup and the glass panels in many European cathedrals were created by this simple procedure. Furthermore, many believe that medicinal preparation such as “aurum potabile” and formulations injected for treating rheumatic arthritis were made of colloidal gold. Several people such as the fourteenth-century Bolognese painters, the alchemists Paracelsus, Andreus Cassius, and Johannes Kunckel are all believed to have made the colloidal form of gold, which is the most studied form among the metallic nanoparticles. However, none of these methods of preparations or people were really interested to see in what form the metals existed in composite/solution or whether these existed 190as small (“nano”) particles. Actually, it was Michael Faraday who first conjectured that the ruby red color imparted to the glass/ceramics could be due to the reduction of gold salts to metallic state. 1 He in fact prepared a “sol” of gold by reacting a gold chloride solution with red phosphorous, thus causing the reduction of gold (III) ions to metallic gold. He was also the first person who inferred that the color imparted to the glass/ceramics could be due to the existence of gold in a “finely divided metallic state.” Several systematic studies by Richard Adolf Zsigmondy, Theodor Svedberg, and Gustav Mie 2-5 on gold nanoparticles followed. However, the preparations in all these studies have been mainly curiosity driven and practical applications, if any, have been rather limited. One of the causes for this limitation could be related to the difficult preparative procedures. This major hurdle has been crossed thanks to the pioneering works first by Turkevich et al. 6 and later by Frens 7, 8 that provided the first major breakthrough as far as the simplification of gold colloid preparation was concerned. Procedures developed by these people were also the first ones where an organic molecule, trisodium citrate, was used for nanoparticle synthesis

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

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.

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.

Nanoparticle assembly: a perspective and some unanswered questions - Kumar, Sanat K.; Kumaraswamy, Guruswamy; Prasad, Bhagavatula L. V.; Bandyopadhyaya, Rajdip; Granick, Steve; Gang, Oleg; Manoharan, Vinothan N.; Frenkel, Daan; Kotov, Nicholas A. (Current Science, 2017)
In early 2016, the Royal Society of Chemistry arranged a meeting on the topic 'Nanoparticle Assemblies: from Fundamentals to Applications' which was hosted at IIT-Bombay, Mumbai. The meeting brought several leading nanoscience and nanotechnology researchers to India and is only the second Faraday Discussions meeting to have been held in the country. The papers presented at the meeting and the resulting active discussions have been summarized in a Faraday Discussion issue(1). The broad range of topics discussed at the meeting led to an understanding on where we stand in the field of nanoparticle assembly, and also enunciated some of the outstanding fundamental and practical issues that remain to be resolved before these ideas can be applied to practical situations. Driven by these ideas, here we focus on four topics/questions: (i) Can we achieve function-driven design of nanoparticle assemblies? (ii) What is the minimal information needed to build a desired assembly? (iii) How complex a structure can one build? How can one make it responsive? What are the relative roles of equilibrium versus dynamics in the assembly process, and are we at a point where we can now pursue active assembly as a viable mode for creating complex assemblies? (iv) What are the applications that are being targeted and what are the barriers to implementation? In this perspective, we do not present an exhaustive survey of the vast literature in this area, but indicate overarching themes/questions that require immediate attention, largely based on the discussions at the Mumbai meeting.

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.

Nickel-catalyzed C(sp(2))-H/C(sp(3))-H oxidative coupling of indoles with toluene derivatives - Soni, V.; Khake, S. M.; Punji, B. (ACS Catalysis, 2017)
Nickel-catalyzed oxidative C(sp(2))-H/C(sp(3))-H coupling of indoles with toluene derivatives is successfully achieved in the presence of 2-iodobutane as the oxidant. This method allows the selective C-2 benzylation of indoles with toluene derivatives over the alkylation with 2-iodobutane and permits the coupling of diversified indoles via the monochelation assistance. The reaction proceeded through a single-electron-transfer (SET) process, wherein both the C-H nickelation of indole and the C-H activation of toluene derivatives have a significant effect on the entire reaction rate. The synthetic utility of this nickel-catalyzed protocol is demonstrated by the facile removal of the directing group and by the convenient synthesis of the melatonin receptor antagonist Luzindole derivatives.

Nickel-catalyzed direct synthesis of dialkoxymethane ethers - Subaramanian, Murugan; Bera, Abhijit; Prasad, Bhagavatula L. V.; Balaraman, Ekambaram (Journal of Chemical Sciences, 2017)
A simple and efficient method for the preparation of dialkoxymethane ethers (oxymethylene ethers) from alcohols and paraformaldehyde in the presence of commercially available nickel(II) salt is described. The reaction proceeds readily under neutral, solvent-free conditions using paraformaldehyde as a C-1 source. The present strategy has a broad substrate scope including aliphatic (both primary and secondary) and aromatic alcohols and provides a benign method for the preparation of symmetrical dialkoxymethanes in good yields (up to 89%).

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.

Norepinephrine alkaloids as antiplasmodial agents: Synthesis of syncarpamide and insight into the structure-activity relationships of its analogues as antiplasmodial agents - Aratikatla, Eswar K.; Valkute, Tushar R.; Puri, Sunil K.; Srivastava, Kumkum; Bhattacharya, Asish K. (European Journal of Medicinal Chemistry, 2017)
Syncarpamide 1, a norepinephrine alkaloid isolated from the leaves of Zanthoxylum syncarpum (Rutaceae) exhibited promising antiplasmodial activities against Plasmodium falciparum with reported IC50 values of 2.04 mu M (D6 clone), 3.06 mu M (W2 clone) and observed by us 3.90 mu M (3D7 clone) and 2.56 mu M (K1 clone). In continuation of our work on naturally occurring antimalarial compounds, synthesis of syncarpamide 1 and its enantiomer, (R)-2 using Sharpless asymmetric dihydroxylation as a key step has been accomplished. In order to study structure-activity-relationship (SAR) in detail, a library of 55 compounds (3-57), which are analogues/homologues of syncarpamide 1 were synthesized by varying the substituents on the aromatic ring, by changing the stereocentre at the C-7 and/or by varying the acid groups in the ester and/or amide side chain based on the natural product lead molecule and further assayed in vitro against 3D7 and K1 strains of P. falciparum to evaluate their antiplasmodial activities. In order to study the effect of position of functional groups on antiplasmodial activity profile, a regioisomer (S)-58 of syncarpamide 1 was synthesized however, it turned out to be inactive against both the strains. Two compounds, (S)-41 and its enantiomer, (R)-42 having 3,4,5-trimethoxy cinnamoyl groups as side chains showed better antiplasmodial activity with IC50 values of 3.16, 2.28 mu M (3D7) and 1.78, 2.07 mu M (I(1), respectively than the natural product, syncarpamide 1. Three compounds (S)-13, (S)-17, (S)-21 exhibited antiplasmodial activities with IC50 values of 6.39, 6.82, 6.41 mu M against 3D7 strain, 4.27, 7.26, 2.71 mu M against K1 strain and with CC50 values of 147.72, 153.0, >200 mu M respectively. The in vitro antiplasmodial activity data of synthesized library suggests that the electron density and possibility of resonance in both the ester and amide side chains increases the antiplasmodial activity as compared to the parent natural product 1: The natural product syncarpamide 1 and four analogues/homologues out of the synthesized library of 55, (S)-41, (R)-42, (S)-55 and (S)-57 were assayed in vivo assay against chioroquine-resistant P. yoelii (N-67) strain of Plasmodium. However, none of the five molecules, 1, (S)-41, (R)-42, (S)-55 and (S)-57 exhibited any promising in vivo antimalarial activity against P. yoelii (N-67) strain. Compounds 4, 6, 7 and 11 showed high cytotoxicities with CC50 values of 5.87, 5.08, 6.44 and 14.04 mu M, respectively. Compound 6 was found to be the most cytotoxic as compared to the standard drug, podophyllotoxin whereas compounds 4 and 7 showed comparable cytotoxicities to podophyllotoxin. (C) 2017 Elsevier Masson SAS. All rights reserved.

Nutty carbon: morphology replicating hard carbon from walnut shell for na ion battery anode - Wahid, M.; Gawli, Y.; Puthusseri, D.; Kumar, A.; Shelke, M. V.; Ogale, S. (ACS Omega, 2017)
<div id="absImg" style="position: relative; margin: 0px; padding: 5px; border: 1px solid rgb(204, 204, 204); border-radius: 5px; background-image: initial; background-position: initial; background-size: initial; background-repeat: initial; background-attachment: initial; background-origin: initial; background-clip: initial; text-align: center; color: rgb(0, 0, 0); font-family: Helvetica, Arial, sans-serif; font-size: 14px;"><img alt="Abstract Image" src="http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/acsodf/2017/acsodf.2017.2.issue-7/acsomega.7b00633/20170713/images/medium/ao-2017-00633k_0006.gif" style="border: 0px; max-width: 100%;"> <p class="articleBody_abstractText" style="margin: 0px 0px 1.5em; line-height: 1.6em; padding: 0pt; width: 610px; word-wrap: break-word; color: rgb(0, 0, 0); font-family: Helvetica, Arial, sans-serif; font-size: 14px;">Efficient Na ion intercalation/deintercalation in the semigraphitic lattice of a hard carbon derived from the walnut shell is demonstrated. High-temperature (1000 °C) pyrolysis of walnut shells under an inert atmosphere yields a hard carbon with a low surface area (59 m2 g–1) and a large interplanar c axis separation of 0.39–0.36 nm as compared to 0.32 nm for graphite, suitable for Na ion intercalation/deintercalation. A stable reversible capacity of 257 mAh g–1 is observed at a current density of 50 mA g–1 for such nutshell-derived carbon (NDC) with an impressive rate performance. No loss of electrochemical performance is observed for high current cycling (100 mA g–1 → 2 A g–1 → 100 mA g–1). Additionally, the NDC shows remarkably stable electrochemical performance up to 300 charge–discharge cycles at 100 mA g–1 with a minimal drop in capacity.
Keywords: Batteries; Biological and Medicinal chemistry; Biological materials; diffraction; Electric Properties; Electrode-electrolyte interface; spectra; Surface structure; Thermal properties

OFET based H2S gas sensing among reducing and mining gases using green synthesis SnO2 - Surya, S. G.; Roy, S.; Ganne, B. S. P.; Pasam, D.; Sastry, A. B.; Bhagavatula L. V. Prasad (2016 3rd International Conference on Emerging Electronics, ICEE 2016, 2017)
In this paper we present detection of H2S gas using an organic field effect transistor (OFET) based sensor. A low-cost green synthesis process for SnO2 nanoparticles and bi-layer approach for device fabrication have been adopted to come up with the sensor. With the help of multiparameteric analysis, selectivity towards H2S gas was proved among other reducing and mining gases.

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.

Optimizing culture conditions for establishment of hairy root culture of semecarpus anacardium L. - Panda, Bhuban Mohan; Mehta, Urmil J.; Hazra, Sulekha (3 Biotech, 2017)
Semecarpus anacardium L. is a tree species which produces secondary metabolites of medicinal importance. Roots of the plant have been traditionally used in folk medicines. Different strains of Agrobacterium rhizogenes (A4, ATCC15834 and LBA 9402) were used for induction of hairy roots in in vitro grown tissues of the plant. Hairy root initiation was observed after 25-30 days of infection. Optimum transformation frequency of 61% was achieved on leaf explants with ATCC15834 strain. Infection time of 30 min resulted in greater transformation frequency compared to 10 and 20 min, respectively. The hairy roots cultured in growth regulator-free semi-solid woody plant medium differentiated into callus. Whole shoots infected with ATCC 15834 were found to produce more transformants upon co-cultivation for 4 (65%) and 5 (67%) days. Induction of hairy roots in stem explants infected with ATCC 15834 was lower (52%) compared to leaves (62%) after 4 days of co-cultivation. In A4 and LBA9402 strains transformation efficiency was 49 +/- 2.8% and 36 +/- 5.7% in shoots after 4 days of co-cultivation. Transformation frequency was higher in ATCC15834 strain, irrespective of explants. The hairy roots of S. anacardium elongated slowly upon transfer to half-strength liquid medium. After 3-4 passages in liquid medium slender hairy roots started differentiating which were separated from the original explants. Visible growth of the roots was observed in hormone-free liquid medium after 2-3 months of culturing. Polymerase chain reaction with gene-specific primers from rol A, B and C genes confirms the positive transformation events.
Keywords: Hairy root culture; In vitro culture; rol genes; Semecarpus anacardium; Transformation

Orthogonally functionalized donor/acceptor homo- and heterodimeric dyes for dye-sensitized solar cells: an approach to introduce panchromaticity and control the charge recombination - Sil, Manik Chandra; Sudhakar, Vediappan; Kavungathodi, Munavvar Fairoos Mele; Punitharasu, Vellimalai; Nithyanandhan, Jayaraj (ACS Applied Materials & Interfaces, 2017)
Organic dyes possessing conjugated pi-framework forms closely packed monolayers on photoanode in dye-sensitized solar cell (DSSC), because of the limitation to control the orientation and the extend of intermolecular pi-pi interaction, self-aggregation of dyes leads to reduced cell performance. In this report, a series of homodimeric (D-1-D-1, and D-2,-D-2) and heterodimeric (D-1-D-2 and D-2-D-4) donor/acceptor (D/A) dyes containing spiroBiProDOT pi-spacer were designed and synthesized by utilizing Pd-catalyzed direct arylation reaction and correlates the device performance with monomeric dyes (D-1 and D-2). Both the thiophenes (pi-spacer) of spiroBiProDOT were functionalized with same or different donor groups which led to homodimeric and heterodimeric chromophores in a single sensitizer. The homodimeric spirodye D-1-D-1 showed higher power conversion efficiency (PCE), of 7.6% with a V-oc and J(sc) of 0.672 V and 16.16 mA/cm(2), respectively. On the other hand, the monomeric D-1 exhibited a PCE of 3.2% (V-oc of 0.64 V and J(sc) of 7.2 mA/cm(2)); which is lower by 2.4 fold compared to dimeric analogue. The spiro-unit 20 provides flexibility between the incorporated chromophores to orient on TiO2 due to four sp(3)-centers, which arrest the molecular motions after chemisorption. This study shows a new molecular approach to incorporate two chromophores in the dimeric dye possessing complementary absorption characteristics toward panchromatic absorption. The attenuated charge recombination at TiO2/Dye/redox couple interface in case of D-1-D-1, owing to better passivation of TiO2 surface, was elucidated through impedance analysis. The FT-IR spectrum of D,-D, adsorbed on TiO2 film indicated both the carboxylic units were involved in chemisorption which makes strong coupling between dye and TiO2.

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.

Oxidative intramolecular 1,2-amino-oxygenation of alkynes under Au I /Au III catalysis: discovery of a pyridinium-oxazole dyad as an ionic fluorophore - Shaikh, Aslam C.; Ranade, Dnyanesh Sadanand; Rajamohanan, Pattuparambil R.; Kulkarni, Prasad Padmakar; Patil, Nitin T. (Angewandte Chemie‐International Edition, 2017)

Oxidative intramolecular 1,2-amino-oxygenation of alkynes under Au-I/Au-III catalysis: discovery of a pyridinium-oxazole dyad as an ionic fluorophore - Shaikh, Aslam C.; Ranade, Dnyanesh S.; Rajamohanan, Pattuparambil R.; Kulkarni, Prasad P.; Patil, Nitin T. (Angewandte Chemie-International Edition, 2017)
Oxidative intramolecular 1,2-amino-oxygenation reactions, combining gold(I)/gold(III) catalysis, is reported. The reaction provides efficient access to a structurally unique ionic pyridinium-oxazole dyad with tunable emission wavelengths. The application of these fluorophores as potential biomarkers has been investigated.

Palladacycles for directed and nondirected C H bond functionalization of (Hetero)arenes - Soni, Vineeta; Punji, Benudhar (Strategies for palladium-catalyzed non-directed and directed C-H bond functionalization, 2017)
Application of palladacycle complexes in catalytic organic transformation is rapidly expanding. This chapter is mainly focused on the use of palladacycle precatalysts in CH bond functionalizations, as well as an overview of palladacycle intermediates in directed CH bond functionalization reactions. The described palladacycle precatalysts are more efficient and more selective than the traditional palladium complexes for CH bond functionalization processes. The second part of the chapter summarizes the involvement of palladacycle intermediates in various directed CH bond functionalizations that are proposed with experimental evidence. Some of the palladacycle intermediates described are shown to be competent as catalyst precursors. It has been demonstrated that the formation of palladacycle (precatalyst or intermediate) makes the CH functionalization process more facile, because of the high stability associated with palladacycles.

PbS nanostar-like structures as field emitters - Pawar, Mahendra S.; Bankar, Prashant K.; More, Mahendra A.; Late, Dattatray J. (Chemistryselect, 2017)
The crystalline PbS nanostars were synthesized by thermal decomposition of thioacetamide (TAA) in aqueous solutions of lead acetate and acetic acid at 80 8 degrees C. The structure and morphology of the PbS nanostars have been characterized using X-Ray Diffraction (XRD), Raman Spectroscopy, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The optical properties of the PbS nanostars have been studied using UV-Visible absorption Spectroscopy (UVVis). The field emission investigations have been carried out on the as synthesized PbS nanostars at the base pressure of similar to 13 10(-8) mbar. The turn on field required to draw an emission current density of 1 mu A/cm(2) is found to be 1.8 V/mm. The emission current-time plots show good emission current stability of the PbS nanostar emitter over a period of 4 hrs. The results in terms of low turn-on field and long term emission current stability of the PbS nanostars emitter reveals that it can be used in field emission based vacuum microelectronics / nanoelectronic devices.

Penicillin V acylases from gram-negative bacteria degrade N-acylhomoserine lactones and attenuate virulence in Pseudomonas aeruginosa - Sunder, Avinash Vellore; Utari, Putri Dwi; Ramasamy, Sureshkumar; van Merkerk, Ronald; Quax, Wim; Pundle, Archana (Applied Microbiology and Biotechnology, 2017)
Virulence pathways in gram-negative pathogenic bacteria are regulated by quorum sensing mechanisms, through the production and sensing of N-acylhomoserine lactone (AHL) signal molecules. Enzymatic degradation of AHLs leading to attenuation of virulence (quorum quenching) could pave the way for the development of new antibacterials. Penicillin V acylases (PVAs) belong to the Ntn hydrolase superfamily, together with AHL acylases. PVAs are exploited widely in the pharmaceutical industry, but their role in the natural physiology of their native microbes is not clearly understood. This report details the characterization of AHL degradation activity by homotetrameric PVAs from two gram-negative plant pathogenic bacteria, Pectobacterium atrosepticum (PaPVA) and Agrobacterium tumefaciens (AtPVA). Both the PVAs exhibited substrate specificity for degrading long-chain AHLs. Exogenous addition of these enzymes into Pseudomonas aeruginosa greatly diminished the production of elastase and pyocyanin and biofilm formation and increased the survival rate in an insect model of acute infection. Subtle structural differences in the PVA active site that regulate specificity for acyl chain length have been characterized, which could reflect the evolution of AHL-degrading acylases in relation to the environment of the bacteria that produce them and also provide strategies for enzyme engineering. The potential for using these enzymes as therapeutic agents in clinical applications and a few ideas about their possible significance in microbial physiology have also been discussed.
Keywords: N-acylhomoserine lactone acylase; Ntn hydrolase; pathogenesis; Penicillin Vacylase; Quorum quenching

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.

Physical mechanism behind enhanced photoelectrochemical and photocatalytic properties of superhydrophilic assemblies of 3D-TiO2 microspheres with arrays of oriented, single-crystalline TiO2 nanowires as building blocks deposited on fluorine-doped tin oxid - Sadhu, Subha; Gupta, Preeti; Poddar, Pankaj (ACS Applied Materials & Interfaces, 2017)
In comparison to the one-dimensional (1D) semiconductor nanostructures, the hierarchical, three-dimensional (3D) microstructures, composed of the arrays of 1D nanostructures as building blocks, show quite unique physicochemical properties due to efficient photon capture and enhanced surface to volume ratio, which aid in advancing the performance of various optoelectronic devices. In this contribution, we report the fabrication of surfactant-free, radially assembled, 3D titania (rutile-phase) microsphere arrays (3D-TMSAs) composed of bundles of single-crystalline titania nanowires (NWs) directly on fluorine-doped conducting oxide (FTO) substrates with tunable architecture. The effects of growth parameters on the morphology of the 3D-TMSAs have been studied thoroughly. The 3D-TMSAs grown on the FTO-substrate showed superior photon-harvesting owing to the increase in light-scattering. The photocatalytic and photon to electron conversion efficiency of dye sensitized solar cells (DSSC), where the optimized 3D-TMSAs were used as an anode, showed around 44% increase in the photoconversion efficiency compared to that of Degussa P-25 as a result of the synergistic effect of higher surface area and enhanced photon scattering probability. The TMSA film showed superhydrophilicity without any prior UV irradiation. In addition, the presence of bundles of almost parallel NWs led to the formation of arrays of microcapacitors, which showed stable dielectric performance. The fabrication of single-crystalline, oriented, self-assembled TMSAs with bundles of titania nanowires as their building blocks deposited on transparent conducting oxide (TCO) substrates has vast potential in the area of photoelectrochemical research.

Pilot-scale pretreatments of sugarcane bagasse with steam explosion and mineral acid, organic acid, and mixed acids: synergies, enzymatic hydrolysis efficiencies, and structure-morphology correlations - Pal, Siddhartha; Joy, Shereena; Kumbhar, Pramod S.; Trimukhe, Kalpana D.; Gupta, Rishi; Kuhad, Ramesh Chander; Varma, Anjani J.; Shankar, Sasi (Biomass Conversion and Biorefinery, 2017)
In lignocellulosic (LC) ethanol processes, to facilitate enzymatic hydrolysis of cellulose, a physical chemical pretreatment is vital. In this study, we explored a single as well as a two-step physical-chemical pretreatment involving steam and mixed acid on unwashed sugarcane bagasse at pilot-scale level in a continuous horizontal reactor. To serve as a large-scale model, pretreatments were carried out at high solid levels of 18–20 % w/w. For the pretreatment, partial replacement of corrosive sulfuric acid with a milder acid-like oxalic acid was explored to derive possible advantages and synergies accruing by using a mixture of mineral acid and organic acid. The results of this work showed that first-step pretreatment carried out by the mixing of sulfuric acid (1.5 % w/w) and oxalic acid (1.5 % w/w) at 150 °C followed by a second-step steam explosion pretreatment at 180 °C gave significant synergies and advantages over other variants of pretreatments investigated, such as lower inhibitor levels and lower reaction severity. On post-pretreated bagasse, this study conducted comparative enzymatic hydrolysis study using a simple lab enzyme and a robust commercial enzyme. It was found that the addition of Tween 80 to the lab enzyme improved its performance to match the performance of the commercial enzyme. Scanning electron microscopy (SEM) studies were further carried out to correlate the morphology of pretreated samples with efficiency of enzyme hydrolysis. Besides morphological study, Fourier transform infrared (FTIR) studies of pretreated samples showed higher syringyl/guaiacyl ratio for all pretreatments, indicating lower levels of pseudo-lignins, which is beneficial for improved enzyme hydrolysis.

Pinched tube flow reactor: hydrodynamics and suitability for exothermic multiphase reactions - Sharma, Mrityunjay K.; Potdar, Shital B.; Kulkarni, Amol A. (AIChE Journal, 2017)
A novel tubular flow reactor where a straight tube is modified by pinching it periodically at a fixed pitch and at different angles is presented. Pinched tubes (straight tube as well as helical coils) with different pitch and angles between successive pinching are studied. This work reports a detailed hydrodynamic study involving single and two-phase flow. Mixing experiments showed that having an angle of 90° between successive pinchs achieves the shortest mixing length when compared to lower angles. Pressure recovery along with sequence of high and low shear zones and change of flow direction imposed better mixing. Residence time distribution studies showed that higher number of pinch sections decreases the extent of dispersion, yet it deviates from plug flow. The performance is evaluated by carrying a homogeneous and two-phase aromatic nitration and also liquid-liquid extraction. Pinched tube presents an economical option as a flow reactor for conducting exothermic reactions. © 2016 American Institute of Chemical Engineers AIChE J, 2016
Keywords: pinched tube flow reactor; pressure drop; residence time distribution; mass transfer; reactions

Plant cholesterol biosynthetic pathway overlaps with phytosterol metabolism - Sonawane, P. D.; Pollier, J.; Panda, S.; Szymanski, J.; Massalha, H.; Yona, M.; Unger, T.; Malitsky, S.; Arendt, P.; Pauwels, L.; Almekias-Siegl, E.; Rogachev, I.; et al. (Nature Plants, 2017)
The amount of cholesterol made by many plants is not negligible. Whereas cholesterogenesis in animals was elucidated decades ago, the plant pathway has remained enigmatic. Among other roles, cholesterol is a key precursor for thousands of bioactive plant metabolites, including the well-known Solanum steroidal glycoalkaloids. Integrating tomato transcript and protein co-expression data revealed candidate genes putatively associated with cholesterol biosynthesis. A combination of functional assays including gene silencing, examination of recombinant enzyme activity and yeast mutant complementation suggests the cholesterol pathway comprises 12 enzymes acting in 10 steps. It appears that half of the cholesterogenesis-specific enzymes evolved through gene duplication and divergence from phytosterol biosynthetic enzymes, whereas others act reciprocally in both cholesterol and phytosterol metabolism. Our findings provide a unique example of nature's capacity to exploit existing protein folds and catalytic machineries from primary metabolism to assemble a new, multi-step metabolic pathway. Finally, the engineering of a 'high-cholesterol' model plant underscores the future value of our gene toolbox to produce high-value steroidal compounds via synthetic biology.

Possibly scalable solar hydrogen generation with quasi-artificial leaf approach - Patra, Kshirodra Kumar; Bhuskute, Bela D.; Gopinath, Chinnakonda S. (Scientific Reports, 2017)
Any solar energy harvesting technology must provide a net positive energy balance, and artificial leaf concept provided a platform for solar water splitting (SWS) towards that. However, device stability, high photocurrent generation, and scalability are the major challenges. A wireless device based on quasi-artificial leaf concept (QuAL), comprising Au on porous TiO2 electrode sensitized by PbS and CdS quantum dots (QD), was demonstrated to show sustainable solar hydrogen (490 +/- 25 mu mol/h (corresponds to 12 ml H-2 h(-1)) from similar to 2mg of photoanode material coated over 1 cm(2) area with aqueous hole (S2-/SO32-) scavenger. A linear extrapolation of the above results could lead to hydrogen production of 6 L/h.g over an area of similar to 23 x 23 cm(2). Under one sun conditions, 4.3 mA/cm(2) photocurrent generation, 5.6% power conversion efficiency, and spontaneous H-2 generation were observed at no applied potential (see S1). A direct coupling of all components within themselves enhances the light absorption in the entire visible and NIR region and charge utilization. Thin film approach, as in DSSC, combined with porous titania enables networking of all the components of the device, and efficiently converts solar to chemical energy in a sustainable manner.

Predesigned metal-anchored building block for in situ generation of Pd nanoparticles in porous covalent organic framework: application in heterogeneous tandem catalysis - Bhadra, Mohitosh; Sasmal, Himadri Sekhar; Basu, Arghya; Midya, Siba P.; Kandambeth, Sharath; Pachfule, Pradip; Balaraman, Ekambaram; Banerjee, Rahul (ACS Applied Materials & Interfaces, 2017)
The development of nanoparticle-polymer-hybrid-based heterogeneous catalysts with high reactivity and good recyclability is highly desired for their applications in the chemical and pharmaceutical industries: Herein, we have developed a novel synthetic strategy by choosing a predesigned metal-anchored building block for in situ generation of metal (Pd) nanoparticles in the stable, porous, and crystalline covalent organic framework (COF), without using conventional reducing agents. In situ generation of Pd nanoparticles in the COF Skeleton is explicitly confirmed' from PXRD, XPS, TEM images, and N-15 NMR spectral analysis. This hybrid material is found to be an excellent reusable heterogeneous catalyst for the synthesis of biologically and pharmaceutically important 2-substituted benzofurans from 2-bromophencils and terminal alkynes via a tandem process with the turnover number up to 1101. The heterogeneity of the catalytic process is unambiguously verified by a mercury poisoning experiment and leaching test. This hybrid material shows superior catalytic performance compared to commercially available homogeneous as well as heterogeneous Pd catalysts.

Prediction of degrees API values of crude oils by use of saturates/aromatics/resins/ asphaltenes analysis: computational-intelligence-based models - Goel, Purva; Saurabh, Kumar; Patil-Shinde, Veena; Tambe, Sanjeev S. (SPE Journal, 2017)
The degrees API value is an important physicochemical characteristic of crude oils often used in determining their properties and quality. There exist models-predominantly linear ones-for predicting the degrees API magnitude from the molecular composition of a crude oil. This approach is tedious and time-consuming because it requires quantitative determination of numerous crude-oil components. Usually, the hydrocarbons present in a crude oil are grouped according to their molecular average structures into saturates, aromatics, resins, and asphaltenes (SARA) fractions. An degrees API-value prediction model dependent on these four fractions is relatively easier to develop, although this approach has been rarely used. A rigorous scrutiny suggests that some of the dependencies between the individual SARA fractions and the corresponding degrees API value could be nonlinear. Accordingly, in this study, SARA-fraction-based nonlinear models have been developed for the prediction of values using three computational-intelligence (CI) formalisms: genetic programming (GP), artificialneural networks (ANNs), and support-vector regression (SVR). The SARA analyses and degrees API values of 403 crude-oil samples covering wide ranges have been used in developing these models. A comparison of the CI-based models with an existing linear model indicates that all the former class of models possess a significantly better degrees API-value prediction and generalization performance than those exhibited by the linear model. Also, the SVR-based model has been found to be the most accurate degrees API-value predictor. Because of their better prediction accuracy, CI-based models can be gainfully used to predict degrees API values of crude oils.

Preparation of MgO supported platinum nanoparticle catalyst using toluene dispersed platinum sol - Seth, J.; Nepak, D.; Chaudhari, V. R.; Prasad, B.L.V. (Applied Surface Science, 2017)
An effective way of anchoring Pt nanoparticles on MgO using toluene dispersed platinum nanoparticles (Pt-NPs) as one of the ingredient is demonstrated. The usage of particles dispersed in toluene allows the retention of size and size distribution of preformed Pt-NPs even after deposition on MgO support with high active surface area, which is crucial for heterogeneous catalysis. The catalyst thus prepared, displayed selective hydrogenation of cinnamaldehyde to cinnamyl alcohol with high turn on frequency (TOF − 105 h−1) with respect to the total Pt content. We attribute this efficient catalytic performance to the uniform distribution and deposition of Pt on the active MgO support and its better accessible surface as evidenced by the cyclic-voltammetry results.
Keywords: catalysis; Catalysts; cyclic voltammetry; Deposition; Magnesia; Nanoparticles; sol-gel process

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.

p-Selective (sp(2))-C-H functionalization for an acylation/alkylation reaction using organic photoredox catalysis - Pandey, Ganesh; Tiwari, Sandip Kumar; Singh, Bhawana; Vanka, Kumar; Jain, Shailja (Chemical Communications, 2017)
p-Selective (sp(2))-C-H functionalization of electron rich arenes has been achieved for acylation and alkylation reactions, respectively, with acyl/alkylselenides by organic photoredox catalysis involving an interesting mechanistic pathway.

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.

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.

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.

Rigid peptide scaffold-incorporated structural analogs of the potent antidepressant peptide drug rapastinel (GLYX-13) - Nadimpally, Krishna Chaitanya; Chakrapani, Aswathi; Prabhu, Priyanka J.; Madica, Krishnaprasad; Sanjayan, Gangadhar J. (Chemistryselect, 2017)
Rapastinel (GLYX-13) is a natural amidated tetrapeptide (Thr-Pro-Pro-Thr-NH2)endowed with strong antidepressant property. Rapastinel shows considerable promise for treating drug-resistant major depressive disorder (MDD), and is under clinical phase III development. Herein, we report the synthesis of a novel class of analogues of the potent antidepressant peptide drug rapastinel featuring rigid dipeptide scaffolds comprising proline (L/D) and amino thiophene carboxylates (Atc). Amino thiophene carboxylate is a conformationally constrained aromatic beta-amino acid, known to rigidify peptide backbones thereby limiting the conformational flexibility of peptides and improving proteolytic stability.

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.

Scalable metabolite supplementation strategy against antibiotic resistant pathogen Chromobacterium violaceum induced by NAD(+)/NADH(+) imbalanceA scalable metabolite supplementation strategy against antibiotic resistant pathogen Chromobacterium violaceu - Banerjee, Deepanwita; Parmar, Dharmeshkumar; Bhattacharya, Nivedita; Ghanate, Avinash D.; Panchagnula, Venkateswarlu; Raghunathan, Anu (BMC Syst Biol., 2017)
BACKGROUND: The leading edge of the global problem of antibiotic resistance necessitates novel therapeutic strategies. This study develops a novel systems biology driven approach for killing antibiotic resistant pathogens using benign metabolites. RESULTS: Controlled laboratory evolutions established chloramphenicol and streptomycin resistant pathogens of Chromobacterium. These resistant pathogens showed higher growth rates and required higher lethal doses of antibiotic. Growth and viability testing identified malate, maleate, succinate, pyruvate and oxoadipate as resensitising agents for antibiotic therapy. Resistant genes were catalogued through whole genome sequencing. Intracellular metabolomic profiling identified violacein as a potential biomarker for resistance. The temporal variance of metabolites captured the linearized dynamics around the steady state and correlated to growth rate. A constraints-based flux balance model of the core metabolism was used to predict the metabolic basis of antibiotic susceptibility and resistance. CONCLUSIONS: The model predicts electron imbalance and skewed NAD/NADH ratios as a result of antibiotics - chloramphenicol and streptomycin. The resistant pathogen rewired its metabolic networks to compensate for disruption of redox homeostasis. We foresee the utility of such scalable workflows in identifying metabolites for clinical isolates as inevitable solutions to mitigate antibiotic resistance.
Keywords: Antibiotic resistance; Flux balance analysis; Flux variability analysis; Metabolism; Metabolomic; NAD; NADH; Redox homeostasis

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.

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-exfoliated guanidinium-based ionic covalent organic nanosheets (iCONs) - Mitra, Shouvik; Kandambeth, Sharath; Biswal, Bishnu P.; Khayum, Abdul M.; Choudhury, Chandan Kumar; Mehta, Mihir R.; Kaur, Gagandeep; Banerjee, Subhrashis; Prabhune, Asmita; Verma, Sandeep; Roy, Sudip; Kharul, Ulhas K.; et al. (Journal of the American Chemical Society, 2017)
Covalent organic nanosheets (CONs) have emerged as functional two-dimensional materials for versatile applications. Although pi-pi stacking between layers, hydrolytic instability, possible restacking prevents their exfoliation on to few thin layered CONs from crystalline porous polymers. We anticipated rational designing of a structure by intrinsic ionic linker could be the solution to produce self-exfoliated CONs without external stimuli. In an attempt to address this issue, we have synthesized three self-exfoliated guanidinium halide based ionic covalent organic nanosheets (iCONs) with antimicrobial property. Self-exfoliation phenomenon has been supported by molecular dynamics (MD) simulation as well. Intrinsic ionic guanidinium unit plays the pivotal role for both self-exfoliation and antibacterial property against both Gram-positive and Gram-negative bacteria. Using such iCONs, we have devised a Mixed matrix membrane which could be useful for antimicrobial coatings with plausible medical benefits.

Silk degumming and utilization of silk sericin by hydrolysis using alkaline protease from beauveria Sp. (MTCC 5184): a green approach - More, Snehal V.; Chavan, Sakalya; Prabhune, Asmita Ashutosh (Journal of Natural Fibers, 2017)
Conventionally, degumming is carried out at 90°C--110°C temperature by boiling the raw silk with Marseilles soap and sodium bicarbonate which eventually requires a lot of water and energy. In this study, degumming of Chinese bivoltine raw silk fibres with alkaline protease produced by Beauveria sp. (MTCC 5184) is studied. Complete degumming was obtained in 45 min with 75 units of enzyme per gram of silk. Degumming was found to be optimal at 50°C and pH 9.0. Scanning electron micrographs showed that the sericin deposits were removed and the obtained fibres were clean, separated, had smooth feel with shine as compared to untreated fibres. Sericin isolated from silk cocoon (by-product which goes waste) was hydrolyzed with the same alkaline protease obtained from Beauveria sp. to get small molecular weight peptides. These peptides can be utilized further for cosmetic, pharmaceutical, and various industrial applications.
Keywords: Alkaline Protease; bivoltine; degumming; Silk; weight loss

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

Solution processed cellulose/melanin films and fibres - Farsa, Ram; Pimpalkar, Nikhil; Shete, Abhijit P.; Shanmuganathan, Kadhiravan (Green Materials, 2017)
Melanins constitute a class of biomacromolecules that are abundant in nature. Although they exhibit a unique range of physical and chemical properties, their intractable nature has precluded their dissolution in common solvents and facile processing into functional materials. The authors found that commercially available 40 wt% tetrabutylammonium hydroxide (Tbah) solution could yield stable solutions of synthetic and natural melanins at ambient conditions and the dissolution rate could be accelerated by microwave radiation. Transmission electron microscopy images clearly show the disruption of the aggregated structure of melanins in Tbah. Scanning electron microscopy images of melanin/Tbah solutions precipitated in acetone revealed that melanins are dissolved and regenerated and not merely dispersed. To the best of the authors’ knowledge, this is the first report demonstrating a facile approach to solution processing melanins with other biopolymers, which allows leverage of many unique properties of melanins. As an illustrative example, the authors demonstrate here the successful fabrication of cellulose/melanin composite films and fibers and their significant dye absorption capacity (62% reduction) with methylene blue.

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.

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.

Structural phases, magnetic properties and Maxwell-Wagner type relaxation of CoFe2O4/Sr2Co2Fe12O22 ferrite composites - Patel, Chirag K.; Solanki, Neha P.; Singh, Charanjeet; Jotania, Rajshree B.; Chauhan, Chetna C.; Kulkarni, Shailja D.; Shirsath, Sagar E. (Materials Research Express, 2017)
CoFe2O4 (S:Y-1:0) and Sr2Co2Fe12O22 (S:Y-0:1) ferrites were synthesized separately by using chemical coprecipitation technique and calcined at 1000 degrees C for 5 h. The mixed ferrite composites (S:Y-3:7, 4:6, 5:5, 6:4 and 7:3) were prepared by physical mixing of individual ferrite powders in required weight proportions. The prepared composites were heated at 1150 degrees C for 5 h in a muffle furnace and then slowly cooled to room temperature. The prepared ferrites were characterized using various instrumental techniques like FTIR, XRD, SEM, VSM and dielectric measurements. The x-ray diffraction studies of pure Sr2Co2Fe12O22 ferrite sample show the presence of M and Y-type hexagonal phases, while the composites consist of spinel and Y-type phases. FTIR spectra of all samples show two bands of Fe-O stretching vibrations. VSM results of composites reveal that the values of the saturation magnetization (M-s) vary from 50.44 emu g(-1) to 31.21 emu g(-1), while remanent magnetization values found from 11.18 emu g(-1) to 3.70 emu g(-1). A higher value of coercivity (H-c = 562 emu g(-1)) is observed in the composite S:Y-3:7 but Mr/Ms ratio of pure and composites is found to be less than 0.5. The dielectric behavior is explained using Maxwell-Wegner type interfacial polarization and N. Rezlescu's model.

Study on doped heterojunctions in TiO2 nanotubes: an efficient photocatalyst for solar water splitting - Preethi, L. K.; Antony, Rajini P.; Mathews, Tom; Walczak, Lukasz; Gopinath, Chinnakonda S. (Scientific Reports, 2017)
The two important factors that affect sunlight assisted water splitting ability of TiO2 are its charge recombination and large band gap. We report the first demonstration of nitrogen doped triphase (anatase-rutile-brookite) TiO2 nanotubes as sun light active photocatalyst for water splitting with high quantum efficiency. Nitrogen doped triphase TiO2 nanotubes, corresponding to different nitrogen concentrations, are synthesized electrochemically. Increase in nitrogen concentration in triphase TiO2 nanotubes is found to induce brookite to anatase phase transformation. The variation in density of intra-band states (Ti3+ and N 2p states) with increase in nitrogen doping are found to be critical in tuning the photocatalytic activity of TiO2 nanotubes. The presence of bulk heterojunctions in single nanotube of different nitrogen doped TiO2 samples is confirmed from HRTEM analysis. The most active nitrogen doped triphase TiO2 nanotubes are found to be 12 times efficient compared to pristine triphase TiO2, for solar hydrogen generation. The band alignment and charge transfer pathways in nitrogen doped TiO2 with triphase heterojunctions are delineated. Bulk heterojunctions among the three phases present in the nanotubes with intra-band defect states is shown to enhance the photocatalytic activity tremendously. Our study also confirms the theory that three phase system is efficient in photocatalysis compared to two phase system.

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.

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.

Syntheses and single crystal X-ray diffraction studies of hydroxynicotinic acid based complexes involving supramolecular interactions - Singh, S.K. (Polyhedron, 2017)
Aqua-bridged coordination polymers of Cu(II) and Cd(II) and a mononuclear complex of Cu(II) were solvothermally synthesized with hydroxy-decorated ligands such as 2-hydroxynicotinic acid (2-OHNAH) and 6-hydroxynicotinic acid (6-OHNAH) in aqueous-nonaqueous mixed media. All these complexes were characterized by elemental analyses (C, H, N), FT-IR, thermogravimetric analysis (TGA), powder XRD and single crystal X-ray crystallography. They are formulated as [Cu(2-OHNA)2] 1, [Cu(6-OHNA)2(μ-H2O)2]n 2 and [Cd(6-OHNA)2(μ-H2O)2]n 3. Complex 1 is mononuclear 0D square planar complex which extends its dimensionality by weak supramolecular interactions such as π–π stacking interactions and intermolecular hydrogen bonding. Complexes 2 and 3 are polymeric aqua-bridged 1D infinite chain of Cu(II) and Cd(II), respectively. The central metal ions in these two complexes are in octahedral coordination environment. These two complexes are also assembled by π–π stacking interactions, inter- and intramolecular hydrogen bonding interactions.
Keywords: 2-Hydroxynicotinic Acid; 6-Hydroxynicotinic Acid; Coordination polymer; Polymeric Aqua-Bridged; X-ray diffraction

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 and cell imaging applications of fluorescent mono/di/tri-heterocycl- yl-2,6-dicyanoanilines - Pisal, Mahesh M.; Annadate, Ritesh A.; Athalye, Meghana C.; Kumar, Dipak; Chavan, Subhash P.; Sarkar, Dhiman; Borate, Hanumant B. (Bioorganic & Medicinal Chemistry Letters, 2017)
Synthesis of 3,4,5-triheterocyclyl-2,6-dicyanoanilines, starting from heterocyclic aldehydes and 1,2-diheterocycle-substituted ethanones, is described. 2,6-Dicyanoanilines with one or two heterocyclic substituents have also been synthesized. It was found that some of these molecules have selective cell-staining properties useful for cell imaging applications. The compounds 1g, 10f and 11 were found to stain cytoplasm of the cells in contact but not the nucleus while the compound 12 showed affinity to apoptotic cells resulting in blue fluorescence. The cell imaging results with compound 12 were similar to Annexin V-FITC, a known reagent containing recombinant Annexin V conjugated to green-fluorescent FITC dye, used for detection of apoptotic cells. These compounds were found to be non-cytotoxic and have potential application as cell imaging agents.

Synthesis and characterization of D-2PA-Pd(II)@SBA-15 catalyst via ``click chemistry'': highly active catalyst for Suzuki coupling reactions - Pathak, Aruna; Singh, A. P. (Journal of Porous Materials, 2017)
Copper catalysed cycloaddition reaction between azide and terminal alkyne, called as ``click reaction'', was found to be modular approach for the synthesis of facile, highly efficient and recoverable D-2PA-Pd(II)@SBA-15 catalyst. In efforts to synthesize the catalyst, the cycloaddition reaction between azido-functionalized mesoporous SBA-15 and N,N-dimethyl-2-propynylamine (D-2PA) has been carried out, followed by the complexation with PdCl2. To analyze physiochemical properties of synthesized materials, various characterization techniques such as CHN elemental analysis, X-ray diffraction, solid state C-13 and Si-29 NMR spectra, FT-IR, XPS, SEM, TEM and N-2 sorption analysis, TGA and DTA, UV-Vis spectroscopy have been carried out. The synthesized catalyst, D-2PA-Pd(II)@SBA-15, exhibited excellent catalytic activities with good product yield and high TON towards Suzuki coupling reaction of various aryl halides with phenylboronic acid. The effect of solvent, base and temperature on coupling reactions has also been described. The developed protocol offers recyclability of catalyst for multiple (four) times without any appreciable loss in stability and catalytic reactivity.
Keywords: Click reaction; Cycloaddition; mesoporous materials; SBA-15; Suzuki coupling

Synthesis and characterization of six-membered pincer nickelacycles and application in alkylation of benzothiazole - Pandiri, H.; Sharma, D.M.; Gonnade, R.G.; Punji, B. (Journal of Chemical Sciences, 2017)
Six-membered pincer nickelacycle complexes have been synthesized and employed for the catalytic C–H bond alkylation of benzothiazole. The pincer nickelacycle, {κP, κC, κP- (2 - iPr 2POCH 2-C 6H 3- 6 -CH 2OP iPr 2)} NiBr , [(iPr4-POCCCOP)NiBr(2)] was synthesized by the reaction of 1,3 - iPr 2POCH 2-C 6H 4-CH 2OP iPr 2[(iPr4-POCCCOP)-H(1)] with (CH3CN)2NiBr2 in the presence of Et 3N via the C(2)–H activation on ligand 1. Treatment of [(iPr4-POCCCOP)NiBr](2) with AgOAc afforded the complex [(iPr 4-POCCCOP) Ni (OAc)] (3) in good yield. Both the complexes 2 and 3 were characterized by 1H , 13C and 31P -NMR spectral analysis. Further, the molecular structures of complexes 2 and 3 were established by X-ray crystallography. The complex 2 was found to be an active catalyst for the C–H bond alkylation of benzothiazole with alkyl halides containing β–hydrogen atoms. Graphical abstract: Synopsis. Six-membered pincer nickelacycles have been synthesized and structurally characterized, which show catalytic activity for the C–H bond alkylation of benzothiazole with alkyl halides containing β–hydrogen atoms.[Figure not available: see fulltext.].
Keywords: Active catalyst; Alkyl halides; Alkylation; Atoms; Benzothiazole; Benzothiazoles; Catalyst activity; Chemical activation; Crystallography; C–H activation; Hydrogen atoms; Nickelacycles; Pincer complex; Pincer complexessix-membered nickelacycle; six-membered nickelacycle; Spectrum analysis; Synthesis (chemical); Synthesis and characterizations; X ray crystallography

Synthesis, characterization and electrochemical investigations of mixed-ligand copper(II)-organic supramolecular frameworks - Singh, Sandeep K.; Srivastava, Ashish Kumar; Srivastava, Krishna; Banerjee, Rahul; Prasad, Jagdish (Journal of Molecular Structure, 2017)
Two mixed-ligand copper(II)-organic coordination compounds with 5,5'-dimethyl-2,2'-bipyridine (5,5'-Me(2)bpy) as a primary ligand while aliphatic malonate (Hmal) and aromatic 2-hydroxynicotinate (2-OHNA) as secondary ligands, were synthesized. These complexes are formulated as: [Cu(Hmal)(5,5'-Me(2)bPY)(H2O)](ClO4) 1 and [Cu-2(2-OHNA)(2)(5,5'-Me(2)bpy)(2)(NO3)KNO3) 2. These two complexes were structurally characterized by single crystal X-ray diffraction analysis. Characterization was further supported by powder X-ray diffraction analysis, elemental analyses, FT-IR, FAB-MASS and TGA, DSC studies. Cyclic voltammetric and UV-visible spectral studies of these two complexes have also been done. The electrochemical studies of complex 1 in DMSO and DMF have shown that this complex undergoes quasi reversible diffusion-controlled one-electron transfer reaction without any chemical complication while complex 2 in DMSO undergoes quasi-reversible diffusion-controlled one electron transfer reaction, following EC mechanism. The electrochemical behaviour of complex 2 in DMF is complicated probably due to presence of more than one species in solution phase. (C) 2017 Elsevier B.V. All rights reserved.
Keywords: 2 '-bipyridine; 3; 5; 5 '-dimethyl-2; 5-Tricarboxylic acid; Benzene-1; classification; Co-ordination-Compounds; Crystal-structures; cyclic voltammetry; magnetic properties; metal organic framework; Mixed-ligand complex; pi-pi stacking interaction; Polymers; Secondery Building Unit; Structural data; Supramolecular framework; Ternare Komplexe; X-ray diffraction

Synthesis of annulated bis-indoles through Au(I)/brønsted acid-catalyzed reactions of (1H-indol-3-yl)(aryl)methanols with 2-(arylethynyl)-1H-indoles - Patil, Nitin T.; Inamdar, Suleman M.; Gonnade, Rajesh Ghanshyam (Organic & Biomolecular Chemistry, 2017)
A general method to access annulated bis-indoles from (1H-indol-3-yl)(aryl)methanols and 2-(arylethynyl)-1H-indoles under the catalysis of the Ph3PAuOTf/Brønsted acid binary catalyst system has been developed. The reaction was found to proceed in a highly efficient manner and benefit from easy-to-make starting materials, broad substrate scope and operational simplicity. The potential of this method has also been exemplified for the synthesis of pyrrole-annulated indoles using 2-(phenylethynyl)-1H-indoles and phenyl(1H-pyrrol-2-yl)methanols. Furthermore, the use of a ternary catalyst system, involving PdCl2/Brønsted acid/Ph3PAuOTf catalysts, has been realized for the synthesis of annulated bis-indoles starting directly from 2-(phenylbuta-1,3-diyn-1-yl)aniline and (1H-indol-3-yl)(aryl)methanol. Mechanistically, this reaction is very interesting since the overall process involves three different catalytic cycles catalyzed by three different catalysts in a relay fashion.

Synthesis of fluorinated heterocycles via multicomponent reactions - Shinde, S. S.; Thore, S. N.; Pawar, R. P.; Ameta, K. L.; Patil, S. N. (Multicomponent reactions: synthesis of bioactive heterocycles, 2017)
Fluorine is one of the most important elements in the periodic table because it is the most electronegative element, makes the strongest C-F bond, and is more polarized in organic synthesis. These unique and distinctive properties of fluorine make it very useful and widely applicable in the pharmaceutical and agrochemical industries. Hydrogen replaced with the fluorine of an organic compound can tune the pharmacokinetic and pharmacological properties of the molecule, which improve solubility, membrane permeability, 184metabolic stability, and receptor-binding properties compared with nonfluorinated analogs.1 Due to these unique properties of fluorine, organofluorine compounds are very applicative in medicinal, pharmaceutical, agrochemical, and material chemistry. This wide applicability of fluorine and organofluorine compounds attracts the attention of researchers and chemists. Labeled fluorine-18 is one of the most commonly used positron emitting radioisotopes in positron emission tomography (PET) imaging technology, which can detect presymptomatic biochemical changes in body tissues. In addition to its use in PET-CT, fluorine is used in preparation of chemically resistant polymer materials such as polytetrafluoroethylene (Teflon) or polarity to piezoelectric material such as polyvinylidene fluoride and organic liquid crystals for displays. Because of these many advantages of fluorine, organic chemists have developed various methods to introduce fluorine in organic molecules. During the last two decades, numerous organofluorine heterocyclics have been developed; in this chapter, we have summarized synthesis of multicomponent reactions (MCRs) in application of fluorine compound synthesis.

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 of water soluble CdS nanoparticles and study of their DNA damage activity - Prasad, K. S.; Amin, T.; Katuva, S.; Kumari, Madhu; Selvaraj, Kaliaperumal (Arabian Journal of Chemistry, 2017)
This study reports a novel method for preparation of water soluble CdS nanoparticles using leaf extract of a plant, Asparagus racemosus. The extract of the leaf tissue which worked as a stabilizing and capping agent, assisted the formation of nanoparticles. Nanoparticles were characterized using a UV–vis spectrophotometer, Photoluminescence, TEM, EDAX, XRD and FT-IR. Transmission electron microscopy followed by selected area electron diffraction pattern analysis indicated the formation of spherical, polydispersed, crystalline, CdS of diameter ranging from 2 to 8 nm. X-ray diffraction studies showed the formation of 1 1 1, 2 2 0 and 3 1 1 planes of face-centered cubic (fcc) CdS. EDAX analysis confirmed the presence of Cd and S in nanosphere. The cytotoxicity test using MTT assay as well as DNA damage analysis using comet assay revealed that synthesized nano CdS quantum dots (QDs) caused less DNA damage and cell death of lymphocytes than pure CdS nanoparticles.

Systematic comparison of the response properties of protein and RNA mediated gene regulatory motifs - Iyengar, Bharat Ravi; Pillai, Beena; Venkatesh, K. V.; Gadgil, Chetan J. (Molecular BioSystems, 2017)
We present a framework enabling the dissection of the effects of motif structure (feedback or feedforward), the nature of the controller (RNA or protein), and the regulation mode (transcriptional, post-transcriptional or translational) on the response to a step change in the input. We have used a common model framework for gene expression where both motif structures have an activating input and repressing regulator, with the same set of parameters, to enable a comparison of the responses. We studied the global sensitivity of the system properties, such as steady-state gain, overshoot, peak time, and peak duration, to parameters. We find that, in all motifs, overshoot correlated negatively whereas peak duration varied concavely with peak time. Differences in the other system properties were found to be mainly dependent on the nature of the controller rather than the motif structure. Protein mediated motifs showed a higher degree of adaptation i.e. a tendency to return to baseline levels; in particular, feedforward motifs exhibited perfect adaptation. RNA mediated motifs had a mild regulatory effect; they also exhibited a lower peaking tendency and mean overshoot. Protein mediated feedforward motifs showed higher overshoot and lower peak time compared to the corresponding feedback motifs.

Tandem synthesis of glycidol via transesterification of glycerol with DMC over Ba-mixed metal oxide catalysts - Kondawar, S. E.; Patil, C. R.; Rode, C. V. (ACS Sustainable Chemistry & Engineering, 2017)
Glycerol carbonate (GC) and glycidol (GD) are commercial products possible from glycerol transformation, which has become a subject of great importance. Among several basic catalysts screened in this work, BaO showed the highest glycerol conversion of 71% with almost complete selectivity to GC. A tandem synthesis of GD with a selectivity as high as 80% with 98% glycerol conversion could be achieved with mixed oxides of Ba and lanthanides (La and Ce) prepared by the coprecipitation method. Although BaO alone showed the highest basicity as measured by CO2 TPD, tuning of basicity by incorporation of CeO2 resulted in the formation of GD. Incorporation of Ba into the ceria matrix induced oxygen vacancies in the cerium oxide material. The presence of u"/v" doublets at 888.7 and 903.2 eV, respectively, in XPS of the Ba-Ce sample also confirmed the oxygen vacancies in the lattice. In this tandem approach to GD, the subsequent decarboxylation of initially formed GC was due to the presence of a CeO2 lattice with defects, which is known to be the best for CO2 adsorption. Increase in both catalyst loading and temperature showed a dramatic enhancement in GD selectivity. A plausible reaction pathway for the transesterification of glycerol with DMC to give GC followed by its decarboxylation to GD is also proposed based on the structural characterization and activity studies.

Targeting RNA G-Quadruplexes for potential therapeutic applications - Pandey,Satyaprakash; Agarwala, Prachi; Maiti,Souvik (Topics in Medicinal Chemistry, 2017)
RNA G-quadruplexes are non-canonical structures formed in G-rich regions of transcriptome. Considerable research points towards the potential role for these dynamic structures in various genes involved in multiple pathways. The ability of these structures to influence important biological processes has been demonstrated in few selected important genes and more recently in a global manner across the transcriptome. RNA G-quadruplexes are implicated in fundamental processes such as translational regulation, alternative splicing, mRNA transport and telomere homeostasis to name a few. The involvement of these structures in key biological processes makes them attractive targets for therapeutic interventions. Here we discuss the structural features of RNA G-quadruplex that make it more monomorphic to develop ligands unlike the polymorphic DNA G-quadruplexes. Furthermore, the role of RNA G-quadruplexes in important genes involved in diseases and disorders such as neurodegeneration, cancer and viral infections has been highlighted. A summary of ligands and their established roles in targeting RNA G-quadruplex structures has been discussed in context of important processes. Moreover, we highlight the need to develop ligands that are highly specific in targeting RNA G-quadruplexes, a new target to restore homeostasis in dysregulated conditions.

Temperature and pH dual stimuli responsive PCL- b -PNIPAAm block copolymer assemblies and the cargo release studies - Patil, Sachin S.; Wadgaonkar, Prakash (Journal of Polymer Science Part A Polymer Chemistry, 2017)
A new atom transfer radical polymerization (ATRP) initiator, namely, 2-(1-(2-azidoethoxy)ethoxy)ethyl 2-bromo-2-methylpropanoate containing both “cleavable” acetal linkage and “clickable” azido group was synthesized. Well-defined azido-terminated poly(N-isopropylacrylamide)s (PNIPAAm-N3)s with molecular weights and dispersity in the range 11,000–19,000 g mol−1 and 1.20–1.28, respectively, were synthesized employing the initiator by ATRP. Acetal containing PCL-b-PNIPAAm block copolymer was obtained by alkyne–azide click reaction of azido-terminated PNIPAAm-N3 with propargyl-terminated PCL. Critical aggregation concentration (CAC) of PCL-b-PNIPAAm copolymer in aqueous solution was found to be 8.99 × 10−6 M. Lower critical solution temperature (LCST) of PCL-b-PNIPAAm copolymer was found to be 32 °C which was lower than that of the precursor PNIPAAm-N3 (36.4 °C). The effect of dual stimuli viz. temperature and pH on size and morphology of the assemblies of PCL-b-PNIPAAm block copolymer revealed that the copolymer below LCST assembled in spherical micelles which subsequently transformed to unstable vesicles above the LCST. Heating these assemblies above 40 °C led to the precipitation of PCL-b-PNIPAAm block copolymer. Whereas, at decreased pH, micelles of PCL-b-PNIPAAm copolymer disintegrate due to the cleavage of acetal linkage and precipitation of hydrophobic hydroxyl-terminated PCL. The encapsulated pyrene release kinetics from the micelles of synthesized PCL-b-PNIPAAm copolymer was found to be faster at higher temperature and at lower pH. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017

Thermally conductive thin films derived from defect free graphene-natural rubber latex nanocomposite: preparation and properties - George, Gejo; Sisupal, Suja Bhargavan; Tomy, Teenu; Pottammal, Bincy Akkoli; Kumaran, Alaganandam; Suvekbala, Vemparthan; Gopimohan, Rajmohan; Sivaram, Swaminathan; Ragupathy, Lakshminarayanan (Carbon, 2017)
Commercially useful rubber products viz. gloves, condoms, tyres, and rubber hoses used in high temperature environments, etc., require efficient thermal conductivity, which increases the lifetime of these products. Graphene can fetch this property, if it is effectively incorporated into the rubber matrix. The great challenge in preparing graphene-rubber nanocomposites is formulating a scalable method to produce defect free graphene and its homogeneous dispersion into polymer matrices through an aqueous medium. Here, we used a simple method to produce defect free few layer (2-5) graphene, which can be easily dispersed into natural rubber (NR) latex without adversely affecting its colloidal stability. The resulting new composite showed large increase in thermal conductivity (480-980%) along with 40% increase in tensile properties and 60% improvement in electrical conductivity. This study provides a novel and generalized approach for the preparation of graphene based thermally conductive rubber nanocomposites. (C) 2017 The Authors. Published by Elsevier Ltd.

Thermomechanical effect in molecular crystals: the role of halogen-bonding interactions - Mittapalli, Sudhir; Perumalla, D. Sravanakumar; Nanubolu, Jagadeesh Babu; Nangia, Ashwini (IUCRJ, 2017)
The design and synthesis of mechanically responsive materials is interesting because they are potential candidates to convert thermal energy into mechanical work. Reported in this paper are thermosalient effects in a series of halogen derivatives of salinazids. The chloro derivative, with higher electronegativity and a weaker inter-halogen bond strength (Cl center dot center dot center dot Cl) exhibits an excellent thermal response, whereas the response is weaker in the iodo derivative with stronger I center dot center dot center dot I halogen bonding. 3,5-Dichlorosalinazid (Compound-A) exists in three polymorphic forms, two room-temperature polymorphs (Forms I and II) and one high-temperature modification (Form III). The transformation of Form I to Form III upon heating at 328-333 K is a reversible thermosalient transition, whereas the transformation of Form II to Form III is irreversible and nonthermosalient. 3,5-Dibromo- (Compound-B) and 3-bromo-5-chloro(Compound-C) salinazid are both dimorphic: the Form I to Form II transition in Compound-B is irreversible, whereas Compound-C shows a reversible thermosalient effect (362-365 K). In the case of 3,5-diiodosalinazid (CompoundD) and 3,5-difluorosalinazid (Compound-E), no phase transitions or thermal effects were observed. The thermosalient behaviour of these halosalinazid molecular crystals is understood from the anisotropy in the cell parameters (an increase in the a axis and a decrease in the b and c axes upon heating) and the sudden release of accumulated strain during the phase transition. The dihalogen salinazid derivatives (chlorine to iodine) show a decrease in thermal effects with an increase in halogen-bond strength. Interestingly, Compound-B shows solid-state photochromism in its polymorphs along with the thermosalient effect, wherein Form I is cyan and Form II is light orange.

Thermo-responsive PNIPAM-metal hybrids: an efficient nanocatalyst for the reduction of 4-nitrophenol - Satapathy, Smith Sagar; Bhol, Prachi; Chakkarambath, Aswathy; Mohanta, Jagdeep; Samantaray, Kunal; Bhat, Suresh K.; Panda, Subhendu K.; Mohanty, Priti S.; Si, Satyabrata (Applied Surface Science, 2017)
Micron size thermoresponsive cross-linked polymeric microgels of poly(N-isopropylacrylamide) (PNIPAM) are used as "microreactor" for embedding metal nanoparticles of different shapes. Using a simple and robust method, we have synthesized various polymer-metal hybrid nanostructures incorporated with Au nanorods (AuNR), Au nanospheres (AuNS) and Ag nanospheres (AgNS). These hybrid nanostructures have been characterized by transmission electron microscope (TEM), UV-vis spectroscopy, dynamic light scattering (DLS) and static light scattering (SLS) followed by their catalytic activity. TEM studies directly confirmed the mondispersity of synthesized hybrid microgels and stability of the embedded metal nanoparticles within the microgels. Optical studies confirmed the presence of respective absorption bands that correspond to AuNS, AgNS and AuNR respectively. Extensive DLS studies demonstrated that although these hybrid microgels preserve their thermoresponsive properties, i.e their hydrodynamic radius decreased with increasing temperature, their thermosensitivity were comparatively lesser than pure PNIPAM microgels. Combining with studies using static light scattering, we further found that AuNS and AgNS were inhomogeneously distributed within microgels where the majority of the nanoparticles present within the loosely cross-linked shell. On the other hand AuNR were distributed more homogeneously within the microgels. Catalytic performance of various nanostructures loaded onto PNIPAM microgel beads were evaluated by studying the catalytic reduction of 4-nitrophenol. Complete catalytic conversion using AgNS occurred in similar to 30 min with a first-order rate constant of 0.159 min(-1) having a 7 min induction period. On the other hand no induction period was observed for AuNS and AuNR and the reaction completed in 3-4 min with a first-order rate constant of 1.607 min(-1) and 1.627 min(-1) respectively. Further, PNIPAM-AuNS and PNIPAM-AuNR possess better catalytic activity as well as recyclability compared to that of PNIPAM-AgNS. (C) 2017 Elsevier B.V. All rights reserved.

Thermo-reversible sol-gel transition of aqueous solutions of patchy polymers - Parmar, Indravadan A.; Shedge, Aarti S.; Badiger, Manohar V.; Wadgaonkar, Prakash P.; Lele, Ashish K. (RSC Advances, 2017)
While aqueous solutions of several amphiphilic thermo-reversible polymers show gelation upon heating, there are fewer examples of polymer solutions that exhibit gelation when cooled. This paper reports an interesting phenomenon of abrupt thermoreversible gelation of aqueous solutions of a hydrophobically modified polymer upon cooling. A high molecular weight precursor copolymer (PCP, (M-w) over bar approximate to 5 x 10(6) g mol(-1)) of N, N-dimethylacrylamide (70 mol%) and acrylic acid (30 mol%) was modified by reacting 10 mol% of the acrylic acid groups with n-dodecyl amine to form a hydrophobically modified copolymer (HMCP). The composition of the copolymer was ascertained using NMR spectroscopy. Cooling the solution of PCP at a controlled rate resulted in a gradual increase in its low shear viscosity as dictated by the flow activation energy. In contrast, cooling the solution of HMCP under identical conditions resulted in an abrupt and large non-Arrhenius increase in viscosity at a specific transition temperature, which decreased with decrease in polymer concentration. Fluorescence measurements and dynamic light scattering data showed that abrupt gelation happened upon cooling, when polymer coils percolate accompanied with concomitant transition in chain conformation from compact micellar coils formed by intra-chain hydrophobic associations to swollen polymer coils connected by inter-chain hydrophobic interactions.

Total synthesis of (+/-)-allocolchicine and its analogues using Co-catalyzed alkyne [2 - Paymode, Dinesh J.; Ramana, Chepuri V. (ACS Omega, 2017)
The total synthesis of (+/-)-allocolchicine has been completed by employing cobalt-catalyzed alkyne [2 + 2 + 2]-cyclotrimerization as the key reaction. The essential diyne has been synthesized from easily available 3,4,5-trimethoxybenzaldehyde following simple chemical transformations. In general, the cycloaddition gave a mixture of C(9) and C(10) isomers thus allowing the synthesis of both allocolchicine and its C(10)-carboxylate. Because this cycloaddition was employed at the penultimate stage, it allowed the synthesis of various analogues having the diverse functionality at C(9) and/or C(10) of ring C.

Total synthesis of natural fregenedadiol and its diacetate, rearranged labdanes with aromatized B ring - Philkhana, Satish Chandra; Reddy, D. Srinivasa (Tetrahedron Letters, 2017)
Labdane based natural products are most abundant and widely distributed in nature with many compounds exhibiting exceptional biological properties. Fregenedadiol is a bicyclic diterpene isolated from Halimium viscosum and represents a new carbon skeleton fregenedane with its B ring aromatized. Here, we report a total synthesis of this interesting natural product using one-pot Diels-Alder/aromatization sequence and selective hydrogenolysis as key steps. (C) 2017 Elsevier Ltd. All rights reserved.

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, azide, and oxidant-free homo- and heterocoupling of ambiphilic tosylhydrazones to the regioselective triazoles and pyrazoles - Panda, Subhankar; Maity, Pradip; Manna, Debasis (Organic Letters, 2017)
With N-tosylhydrazone as an ambiphilic reagent, an unprecedented cyclization reaction of two identical or different tosylhydrazones has been developed to access various 4,5-disubstituted-2H-triazoles under transition metal, azide, and oxidant-free conditions. A mechanistic.rationalization study led to the identification of several electronically diverse unsaturated systems for regioselective synthesis of 1- and 2-substituted 1,2,3-triazoles and pyrazoles.

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.

Unraveling structure sensitivity in phenol hydrogenaton on Pd nanostructures - Haider, M. Ali; Seshadri, Sreedhala; Gupta, Shelaka; Khan, Tuhin; Prabhakaran, Vinod (253rd National Meeting of the American-Chemical-Society (ACS) on Advanced Materials, Technologies, Systems, and Processes, 2017)

Valorization of pomegranate peels: a biorefinery approach - Pathak, P. D.; Mandavgane, S. A.; Kulkarni, B. D. (Waste and Biomass Valorization, 2017)
Recent studies have shown that pomegranate peels (PP) is a valuable source of valuable bioactive compounds, most of which can be converted into value-added products. We herein review this conversion process and provide an outline on the chemical composition of PP and the possible value-added products that can be produced from this commonly discarded agro-waste. We have also discussed its use as a substrate to produce medicinal compounds and bioactive phenolic compounds (e.g., phenolic acids, flavonoids, vitamin C, fertilizers, dietary fibers, and tannins) as well as its use in nanomaterial synthesis. Based on available evidence, it is obvious that PP has a wide variety of applications, and thus, developing an efficient system to utilize PP adequately will help to completely utilize its potential benefits. The biorefinery approach shows promising potential for efficient utilization of PP; however, additional studies should be conducted in this area. © 2016, Springer Science+Business Media Dordrecht.

Valorization of potato peel: a biorefinery approach - Pathak, P. D.; Mandavgane, S. A.; Puranik, N. M.; Jambhulkar, S. J; Kulkarni, B. D. (Critical Reviews in Biotechnology, 2017)
Potato is the fourth main crop consumed worldwide and is an important constituent in the human diet. Consequently, potato is widely used in food-processing industries. However, these industries generate massive amounts of potato peel (PP) as a by-product, which is usually considered a waste, and is discarded. Interestingly, recent research suggests that PP is a valuable source of bioactive compounds, which can be converted into value-added products. In this study, we review the physicochemical composition and valorization of PP. In addition to being used as a dietary fiber or medicine, the value-added products obtained by the fermentation of PP have multiple uses, including their use as adsorbents, biocomposites and packaging materials. These products can also be used in energy production, biopolymer film development, corrosion inhibition and the synthesis of cellulose nanocrystals. The biorefinery approach for PP will increase the value of this waste by producing an array of value-added products and reducing extensive waste generation.
Keywords: Bioactive compounds; Biorefinery; Potato peel; Valorization; Value-added products

Vapor-liquid equilibrium data for binary mixtures of acetic acid plus anisole, acetone plus anisole, and isopropanol plus anisole at pressure 96.15 kPa - Mali, Nilesh A.; Mali, Pawan K.; Patil, Asmita P.; Joshi, Sunil S. (Journal of Chemical and Engineering Data, 2017)
In this work, the vapor-liquid equilibrium (VLE) data have been generated at the local atmospheric pressure of 96.15 kPa for the binary systems acetic acid + anisole, acetone + anisole, and isopropanol + anisole. A circulation type apparatus was designed and developed with few modifications in one of the stills proposed in the literature. For the validation of the new apparatus, VLE data were generated for the known system of N,N-DMF + aniline and compared with the literature data. The VLE data, generated in Txy form for all pairs, were found to be consistent through the point-to-point consistency test. Activity coefficient models, Wilson, NRTL, and UNIQUAC, were fitted to these data using an objective function of minimizing the sum of deviation between experimental and calculated total pressures to estimate the binary interaction parameters. The model predictions with estimated parameters were compared with the experimental data and found appropriate.

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

VIMAL: A chemoinformatics toolkit for design of novel antiviral agents through textmining of scientific literature - Karthikeyan, Muthukumarasamy; Pahujani, Rakhi; Vyas, Renu (253rd National Meeting of the American-Chemical-Society (ACS) on Advanced Materials, Technologies, Systems, and Processes, 2017)

Vitro study of novel microparticle based silk fibroin scaffold with osteoblast-like cells for load-bearing osteo-regenerative applications - Parekh, Nimisha Anant; Hushye, Chandni; Warunkar, Saniya; Gupta, Sayam Sen; Nisal, Anuya (RSC Advances, 2017)
Silk Fibroin (SF) is today considered to be one of the most favorable materials for bone tissue engineering. We have prepared novel SF microparticle based 3D scaffolds, with appropriate pore size, pore interconnectivity and porosity, excellent mechanical properties and tunable bioresorption, while retaining the inherent biocompatibility of SF. These properties make them ideal candidates for osteoregenerative applications. Here, we report the in vitro cell viability, cell adhesion and proliferation with osetoblastic differentiation of MG 63 osteoblast-like cell line on these scaffolds. In addition, we have also modified the surface of these scaffolds using collagen type I and chitosan biopolymers. Our results show that although the SF scaffold does support in vitro cell attachment, proliferation and differentiation, this performance can be further enhanced using the surface coating approach. Also, the ALP activity and bone mineralization was found to be particularly superior in the chitosan modified scaffolds.

2D layered transition metal dichalcogenides (MoS2): Synthesis, applications and theoretical aspects - Singh, A.K.; Kumar, P.; Late, D.J.; Kumar, A.; Patel, S.; Singh, J. (Applied Materials Today, 2018)
Recently, graphene and other two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been widely explored due to their unique optical, mechanical, electrical and sensing properties for versatile electronic and optoelectronic applications. The atomically thin layers of TMDC materials have shown potential to replace state-of-the-art silicon-based technology. Graphene has already revealed an excess of new physics and multifaceted applications in several areas. Similarly, mono-layers of TMDCs such as molybdenum disulfide (MoS2) have also shown excellent electrical and optical properties possessing a direct band-gap of ∼1.8 eV combined with high mechanical flexibility. In contrast to semi-metallic graphene, the semiconducting behavior of MoS2 allows it to overcome the deficiencies of zero-band-gap graphene. This review summarizes the synthesis of 2D MoS2 by several techniques, i.e., mechanical and chemical exfoliation, RF-sputtering, atomic layer deposition (ALD) and chemical vapor deposition (CVD), etc. Furthermore, extensive studies based on potential applications of MoS2 such as the sensor, solar cells, field emission and as an efficient catalyst for hydrogen generation has been included. Theoretical aspects combined with the experimental observations to provide more insights on the dielectric, optical and topological behavior of MoS2 was highlighted.

2D molecular precursor for a one-pot synthesis of semiconducting metal sulphide nanocrystals - Bera, Abhijit; Prasad, Bhagavatula L. V. (Bulletin of Materials Science, 2018)
2D molecular materials, namely, metal alkyl thiolates, have been used as a single-source precursor for the synthesis of semiconducting metal sulphide nanocrystals (NCs) by thermal decomposition. These 2D molecular precursors have all the ingredients required for metal sulphide synthesis (metal source, sulphur source and protecting ligand). In this study, we demonstrate a simple and general solvothermal decomposition' approach for the synthesis of high-quality , PbS, CdS, MnS and ZnS NCs. The size of the NC can also be controlled by changing the decomposition temperature. Furthermore, the optical properties of the NCs have also been studied.

Accelerated in vitro model for occlusion of biliary stents: investigating the role played by dietary fibre - Surwase, Sachin; Balakrishnan, Harishankar; Acharya, Subrat K.; Makharia, Govind K.; Kumaraswamy, Guruswamy; Bhagavatula L. V. Prasad (BMJ Innovations, 2018)
ackground To develop a new accelerated in vitro model that has implications for investigating the mechanism of biliary stent occlusion and help in the development of new materials that can alleviate this problem. Methods We employ a combination of reconstituted animal bile, bacteria and cellulose fibres optimised to reproducibly generate accelerated occlusion of stents, and produce occlusions that closely mimic those found in clinical studies. Results Our model affords repeatable, highly accelerated occlusion (within 2–3 days, compared with between about a week to 2 months in previous models). Our results highlight the role of dietary fibre in blockage of stents and demonstrate their importance in the onset of occlusion. Conclusions This accelerated model may have implications for developing biliary stents with enhanced patency.

Access to silicon(II)- and germanium(II)-indium compounds - Pahar, Sanjukta; Karak, Suvendu; Pait, Moumita; Raj, K. Vipin; Vanka, Kumar; Sen, Sakya S. (Organometallics, 2018)
Despite the remarkable ability of N-heterocyclic silylene to act as a Lewis base and form stable Lewis adducts with group 13 elements such as boron, aluminum, and gallium, there has been no such comparable investigation with indium and the realization of a stable silylene-indium complex has still remained elusive. Similarly, a germylene-indium complex is also presently unknown. We describe herein the reactions of [PhC(NtBu)(2)SiN-(SiMe3)(2)] (1) and [PhC(NtBu)(2)GeN(SiMe3)(2)] (4) with InCl3 and InBr3 that have resulted in the first silylene-indium complexes, [PhC(NtBu)(2)Si{N(SiMe3)(2)}-> InCl3] (2) and [PhC(NtBu)(2)Si{N(SiMe3)(2)}-> InBr3] (3), as well as the first germylene-indium complexes, [PhC(NtBu)(2)Ge{N(SiMe3)(2)}-> InCl3] (5) and [PhC(NtBu)(2)Ge{N(SiMe3)(2)}-> InBr3] (6). The solid-state structures of all species have been validated by single-crystal X-ray diffraction studies. Note that 5 and 6 are the first structurally characterized organometallic compounds that feature a Ge-In single bond (apart from the compounds in Zintl phases). Theoretical calculations reveal that the Si(II)-> In bonds in 2 and 3 and the Ge(II)-> In bonds in 5 and 6 are dative bonds.

Acid modified H-USY zeolite for efficient catalytic transformation of fructose to 5-hydroxymethyl furfural (biofuel precursor) in methyl isobutyl ketone-water biphasic system - Pande, Ashwini; Niphadkar, Prashant; Pandare, Kiran; Bokade, Vijay (Energy Fuels, 2018)
Sustainable process and efficient heterogeneous acid catalyst for the preparation of platform chemicals like 5-hydroxymethyl furfural (5-HMF) from renewable source is much in demand in the context of heterogeneous catalysis. Commercially available solid acid catalyst, H-USY zeolite was modified by treating with aqueous solution of H3PO4 and H2SO4 (10–30 wt %). Modified H-USY was completely characterized by XRD, NH3-TPD, energy dispersive analysis X-ray (EDAX), FT-IR, pyridine-IR, and NMR. Its catalytic performance was evaluated for the fructose conversion to 5-HMF in methyl isobutyl ketone (MIBK)–water system. Modified H-USY zeolite was identified to have potential in enhancement of 5-HMF yield up to 65% from 32% (parent H-USY) with minimum formation of furfural (8%). H-USY modified with 10 wt % H3PO4 (10P–Y) was found to be the best compared to other studied catalysts, namely, H-USY modified with 20 and 30 wt % H3PO4 (20 and 30P–Y) or 10–30 wt % H2SO4 (10- to 30S–Y). Best performance of 10P–Y is associated with the optimum combination of moderate acidity (both weak as well as strong), moderate dealumination of Al from extra-framework sites as well as from framework sites of H-USY, formation of new Al–O–P bonds between framework Al and elemental monomeric phosphorus, presence of Brønsted as well as Lewis acidity, and creation of mesopores. This gives new insight on a potential heterogeneous acid catalyst for the synthesis of 5-HMF.

Activation of HRI is mediated by Hsp90 during stress through modulation of the HRI-Hsp90 complex - Berwal, Sunil K.; Bhatia, Varsha; Bendre, Arneya; Suresh, C. G.; Chatterjee, Sangeeta; Pal, Jayanta K. (International Journal of Biological Macromolecules, 2018)
Heme Regulated Inhibitor (HRI) is known to get activated in various stresses such as heme deficiency, heat shock, heavy metal toxicity etc. Heat shock protein 90 (Hsp90), a ubiquitous cytoplasmic protein interacts with HRI in order to regulate protein synthesis. However, it still remains to establish this interaction of HRI and Hsp90 at cellular levels and how this modulation of HRI activity is mediated by Hsp90 during stress. In the present report, using co-immunoprecipitation analysis we show that HRI interacts with Hsp90 and this association is independent of other co-chaperones in in vitro conditions. Further, analysis using truncated domains of HRI revealed that the K1 subdomain is essential for HRI - Hsp90 complex formation. Our in silico protein - protein interaction studies also indicated interaction of Hsp90 with K1 subdomain of HRI. Mammalian two hybrid assay validated this HRI - Hsp90 interaction at cellular levels. When the in vitro kinase assay was carried out with the co-immunoprecipitated complex of HRI - Hsp90, an increase in the kinase activity was observed resulting elevated levels of eIF2 alpha phosphorylation upon heavy metal stress and heat shock. Thus, our results clearly indicate modulation of HRI kinase activity with simultaneous Hsp90 association under stress conditions. (C) 2018 Elsevier B.V. All rights reserved.

Bismuth(III)-catalyzed cycloisomerization and (hetero)arylation of alkynols: simple access to 2-(hetero)aryl tetrahydrofurans and tetrahydropyrans - Nakate, Ashwini K.; Pratapure, Madhukar S.; Kontham, Ravindar (Organic & Biomolecular Chemistry, 2018)
2-(Hetero)aryl tetrahydrofurans and tetrahydropyrans were successfully synthesized using Bi(OTf)(3)-catalyzed hydroalkoxylation (cycloisomerization) of alkynols (via 5 or 6 exo-dig cyclization) and intermolecular (hetero)arylation. This reaction involves a highly efficient cascade process, where initially the alkynol undergoes a cycloisomerization step via activation of the triple bond and generates the oxocarbenium ion, which subsequently participates in the (hetero)hydroarylation step with electron-rich arenes. Simple to complex suitably functionalized alkynols (4-pentyn-1-ols and 5-hexyn-1-ols) and electron-rich aromatic compounds were found to be reliable substrates in this cascade transformation and furnished a wide range of oxygen heterocycles. This practical tandem process provides a means to build libraries related to pharmacologically active molecules and natural product like scaffolds.

Bubble size prediction in gas-solid fluidized beds using genetic programming - Sonolikar, R. R.; Patil, M. P.; Mankar, R. B.; Tambe, S. S.; Kulkarni, B. D. (Current Science, 2018)
The hydrodynamics of a gas-solid fluidized bed (FB) is affected by the bubble diameter, which in turn strongly influences the performance of a fluidized bed reactor (FBR). Thus, determining the bubble diameter accurately is of crucial importance in the design and operation of an FBR. Various equations are available for calculating the bubble diameter in an FBR. It has been found in this study that these models show a large variation while predicting the experimentally measured bubble diameters. Accordingly, the present study proposes a new equation for computing the bubble diameter in a fluidized bed. This equation has been developed using an efficient, yet infrequently employed computational intelligence (CI)-based data-driven modelling method termed genetic programming (GP). The prediction and generalization performance of the GP-based equation has been compared with that of a number of currently available equations for computing the bubble diameter in a fluidized bed and the results obtained show a good performance by the newly developed equation.

Calixarene intercalated NiCo layered double hydroxide for enhanced oxygen evolution catalysis - Waghmode, Babasaheb J.; Gaikwad, Aarti P.; Rode, V, Chandrashekhar; Sathaye, Shivaram D.; Patil, Kashinath R.; Malkhede, Dipalee D. (ACS Sustainable Chemistry & Engineering, 2018)
Water splitting provides a promising, sustainable way to resolve problems arising due to depleting fossil fuels. The success needs development of low-cost and high-performance electrode materials. The oxygen evolution reaction (OER) is a crucial reaction in water splitting. The combined Ni and Co oxide developed nanostructures having a small overpotential and fast kinetics of OER. They have drawn considerable attention, because of their theoretically high efficiency, high abundance, low cost, and environmental benignity in comparison with precious metal oxides, such as RuO2 and IrO2. However, the desired efficiency needs the developments of enhanced specific active area and conductivity. In the present communication, we address these issues. Specifically, exfoliation of layer double hydroxide (LDH) is applied to enhance the active surface area. The study reveals that intercalation by calixarene in NiCo LDH affords a multifunctional interlayer to deliver a large active surface area and fast electron transport toward the carbon nano-onion (CNO) support. It favorably lowers the overpotentials in OER (290 mV) and attains Tafel slope of 31 mV/decade. Enhanced conductivity is achieved using CNO as a support for the calixarene intercalated NiCo LDH. These developments offer a synergistic effect in achieving superior electrocatalytic activity for OER. This work gives insight into designing binder-free electrodes in alkaline media with good stability for advanced OER activity.
Keywords: Calixarene; electrocatalyst; Exfoliation; NiCo LDH; Oxygen Evolution Reaction

Cascade dehydrative amination of glycerol to oxazoline - Pandya, R.; Mane, R.; Rode, C. V. (Catalysis Science & Technology, 2018)
Transformation of biomass into valuable nitrogen-containing compounds is highly desired, yet less explored. Here, we report a simple and efficient method for the direct conversion of bioglycerol to oxazoline involving glycerol dehydration to acetol followed by its amination using an aqueous solution of ammonia. For the two-step strategy a non-noble metal Cu-Zr catalyst was developed, giving a glycerol to acetol conversion of 78% followed by amination separately with 95% selectivity to oxazoline. Moreover, we have demonstrated a single-pot oxazoline synthesis using Ru/C as the most stable catalyst to achieve 95% selectivity to oxazoline without any leaching. XPS studies revealed the co-existence of multivalent Ru species in different percentages depending on the nature and structure of the support. These multivalent species (RuO2 and RuO3) have a synergistic effect on the activation of the carbonyl group, whereas Ru-0 is an active site for ammonia dissociation. NH3-TPD and Py-IR spectroscopy results also suggest that the presence of relatively moderate acid sites and a higher BrOnsted/Lewis acid ratio in the catalyst promote the selective production of oxazoline. The reaction pathway involves first glycerol dehydration to acetol. In the subsequent step, NH3 is dissociatively adsorbed on the catalyst surface and the imine thus formed is condensed with a second molecule of acetol to obtain oxazoline. The studied catalyst could be recycled successfully without any significant loss of catalytic activity.

Catalytic and efficient synthesis of optically active terminal epoxides and 1,2-diols using a new lanthanum triflate assisted C1-symmetric bimetallic chiral salen cobalt complex - Patel, D.; Thakur, S. S.; Shinde, S. S.; Kumar, P. (Letters in Organic Chemistry, 2018)
The catalytic asymmetric synthesis of terminal epoxides and 1,2-diols via a hydrolytic kinetic resolution of racemic terminal epoxides using a new bimetallic chiral salen CoIII complex incorporated with La(OTf)3 as a catalyst is reported. The new bimetallic chiral salen CoIII complex bearing La(OTf)3 was prepared in a one-pot procedure by activation and bimetallic complex formation from the inactive Jacobsen chiral salen CoII complex (salen = N, N′-bis(3,5-di-tert-butylsalicylidene)-1,2- cyclohexane-diamine). We observed that C1-symmetric chiral bimetallic Co-complex coordinated with La(OTf)3 works as a chiral catalyst and remarkably increased the reactivity and enantioselectivity in the hydrolytic kinetic resolution of terminal epoxides compared to its monometallic analogues. La(OTf)3 plays a crucial role as an achiral Lewis acid in this process, which is supported by the experimental observation presented. To explore the absolute configuration of glycidyl butyrate a vibrational circular dichroism (VCD) spectra was calculated using density functional theory.

Catalytic enantioselective 1,3-alkyl shift in alkyl aryl ethers: efficient synthesis of optically active 3,3 '-diaryloxindoles - Gade, Amol B.; Bagle, Pradip N.; Shinde, Popat S.; Bhardwaj, Vipin; Banerjee, Subhrashis; Chande, Ajit; Patil, Nitin T. (Angewandte Chemie-International Edition, 2018)
Reported is the first organocatalytic asymmetric 1,3-alkyl shift in alkyl aryl ethers for the synthesis of chiral 3,3'-diaryloxindoles using a chiral Bronsted acid catalyst. Preliminary results showed that each enantiomer of the 3,3'-diaryloxindole, and a racemic mixture, showed different antiproliferative activities against HeLa cell lines by using an MTT assay.

Chitosan-thiobarbituric acid: a superadsorbent for mercury - Bhatt, Rahul; Kushwaha, Shilpi; Bojja, Sreedhar; Padmaja, P. (ACS Omega, 2018)
In the present investigation, chitosan (CH) as supramolecularly cross-linked with thiobarbituric acid to form CT. CT was well characterized by UV, scanning electron microscopy-energy-dispersive X-ray analysis, Fourier trans form infrared, NMR, differential scanning calorimetry, thermogravimetric analysis, and X-ray difTraction analyses, and its adsorption potential for elemental mercury (Hg-0), inorganic mercury (Hg2+), and methyl mercury (CH3Hg+) was investigated. Adsorption experiments were conducted to optimize the parameters for removal of the mercury species under study, and the data were analyzed using Langmuir, Freundlich, an Temkin adsorption isotherm models. CT was found to have high adsorption capacities of 1357.69, 2504.86, and 2475.38 rng/g for Hg-0, Hg2+, and CH3Hg+, respectively. The adsorbent CT could be reused up elemental mercury using 0.01 N thiourea, inorganic mercury using 0.01 N perchloric acid, and methyl to three cycles by eluting mercury with 0.2 N NaCl.

Cloning and characterization of trehalase: a conserved glycosidase from oriental midge, Chironomus ramosus - Shukla, Ekta; Thorat, Leena; Bendre, Ameya D.; Jadhav, Santosh; Pal, Jayanta K.; Nath, Bimalendu B.; Gaikwad, Sushama M. (3 Biotech, 2018)
Insect trehalase is a multiferous enzyme, crucial for normal physiological functions as well as under stress conditions. In this report, we present a fundamental study of the trehalase gene segment (1587 bp) from Chironomus ramosus (CrTre) encoding for 529 amino acids, using appropriate bioinformatics tools. C. ramosus, a tropical midge is an emerging animal model to investigate the consequences of environmental stresses. We observed that CrTre belongs to GH family 37 in the CAZy database and possess 57-92% identity to dipteran trehalases. In silico characterization provided information regarding the structural, functional and evolutionary aspects of midge trehalase. In the phylogenetic tree, CrTre clustered with the soluble dipteran trehalases. Moreover, domain functional characterization of the deduced protein sequence by InterProScan (IPR001661), ProSite (PS00927 and PS00928) and Pfam (PF01204) indicated presence of highly conserved signature motifs which are important for the identification of trehalase superfamily. Furthermore, the instability index of CrTre was predicted to be < 40 suggesting its in vivo stability while, the high aliphatic index indicated towards its thermal stability (index value 71-81). The modelled 3D tertiary structure of CrTre depicts a (alpha/alpha)(6) barrel toroidal core. The catalytic domain of the enzyme comprised Glu424 and Asp226 as the putative active site residues. Interestingly, the conserved motifs were observed to be formed by the flexible loopy regions in the tertiary structure. This study revealed essential sequence features of the midge trehalase and offers better insights into the structural aspects of this enzyme which can be correlated with its function.
Keywords: Conserved motifs; Homology modelling; Midges; Secondary structure; trehalose

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.

Composite thin film of simultaneously formed carbon and SnO2 QDs for supercapacitance application - Jadhav, Aarti; Patil, Sagar; Patil, Kashinath Rangu; Sathaye, Shivaram Dattatray; Rode, Chandrashekhar Vasant (New Journal of Chemistry, 2018)
Composite material with uniform size and structure is a critical asset that decides its properties like charge transfer, thermal, photoluminescence, mechanical, etc. and consequently the applications. Here for the first time, we report the concept of flame/combustion at liquid-liquid interface to synthesize in situ, thin film formation of composite consisting of two or more quantum dots. Synthesis of thin films of a composite containing C and SnO2 QDs having particle sizes below 3 nm was successfully done. As compared to a single quantum dots system, the formed composite showed significantly improved specific capacitance due to the synergistic effect arising from strong interaction between C and SnO2 QDs. This was confirmed by XPS, UV visible spectroscopy and photoluminescence spectra. Moreover, it was confirmed that even after 1000 charge/discharge cycles, the interaction between C and Sn remained unaltered; indicating significant stability of capacitance. Some of the advantages of this method include one step, eco-friendly process at ambient conditions. The generality of the method was established by synthesizing C-ZnO and C-TiO2 composite thin film. This new approach can be extended to form many other valuable composite thin films for various applications.

Controlled release nanocomposite microcapsules for agricultural applications - Shanmuganathan, Kadhiravan; Shukla, Parshuram; Jagtap, Siddheshwar; Patil, Vishal; Sapre, Aditya (256th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nanoscience, Nanotechnology and Beyond, 2018)

Controlled surface/interface structure and spin enabled superior properties and biocompatibility of cobalt ferrite nanoparticles - Ansari, Sumayya M.; Sinha, Bhavesh B.; Pai, Kalpana R.; Bhat, Suresh K.; Ma, Yuan-Ron; Sen, Debasis; Kolekar, Yesh D.; Ramana, C., V. (Allied Surface Science, 2018)
High quality, crystalline, well-dispersed, and stable magnetic oxide nanoparticles (NPs) of inverse spinel cobalt ferrite (CoFe2O4; CFO) were prepared by a facile, reproducible, and simple hydrothermal route. The transmission electron microscopy, small-angle scattering and X-ray diffraction analyses demonstrate the structural quality of CFO NPs with a controlled size of similar to 12 nm. Small-angle scattering experiments demonstrate that the pristine CFO NPs have the individual size similar to 8.5 nm and spherical shape. The Raman and infrared spectroscopic measurements further confirm their high chemical quality and cubic symmetry. CFO NPs exhibit a remarkable, maximum coercivity (H-c) value of 18.92 kOe, which is the highest value achieved to date. Surface spins and spins canting along with a weak dipolar interaction accounts for the giant H-c and large effective anisotropy (11.45 x 10(6) erg/cm(3)) of these CFO NPs. The magnetic grain size of NPs reveals that the canted surface spins exist around the magnetic particles. Reorientation of surface spins and interparticle interaction causes the jumping behaviour in M-H hysteresis loops at H = 0. The cell viability of CFO NPs against the cancer (cisplatin resistant ovarian cancer - A2780/CP70) was evaluated to determine their potential application in biomedicine and health science. The mild response of CFO NPs in terms of their anti-proliferative nature against cancer cells and negligible cytotoxicity suggests their human-safe-and-friendly nature which makes them suitable for biomedical/health-related applications. Assessment of toxicity toward human red blood cells (RBC) revealed that hemolysis is less than 5% compared to the positive control confirming the potential applications of CFO NPs targeting human cells and making relevant for adopting them in biomedicine.

Copper- and phosphine-free nickel(II)-catalyzed method for C-H bond alkynylation of benzothiazoles and related azoles - Patel, Ulhas N.; Punji, Benudhar (Asian Journal of Organic Chemistry, 2018)
A phosphine-free nickel(II)-catalyzed method for the C(2)-H bond alkynylation of (benzo)thiazoles, (benz)imidazoles, and oxazoles is described. Well-defined and air-stable (Phen)NiCl2 catalyst efficiently catalyzes the coupling of diverse azoles with alkynyl bromides without the use of a copper co-catalyst, and the method tolerates synthetically important functional groups. Preliminary mechanistic studies on this Ni-II-catalyzed alkynylation emphasize the homogeneous nature of the catalyst, and rule out a radical manifold for the reaction. The synthetic utility of this Ni-catalyzed method is demonstrated by further functionalizing the alkynylated benzothiazoles to 3-methyl-2-(alkynyl)benzo[d]thiazolium salts that are known DNA cleaving agents.
Keywords: alkynylation; azoles; C-H activation; heterocycles; Nickel

Correlation trends in the magnetic hyperfine structure of atoms: a relativistic coupled-cluster case study - Talukdar, Kaushik; Sasmal, Sudip; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Physical Review A, 2018)
The role of electron correlation in the hyperfine structure of alkali metals and alkaline earth metal monopositive ions in their ground electronic configuration is investigated using the Z-vector method in a relativistic coupled-cluster regime within the singles and doubles approximation. The systematic effects of core-correlating functions, polarization of core electrons, and high-lying virtual functions on core electrons correlation are studied. The study reveals that the core-correlating function plays a significant role in core polarization and thus is very important for precise calculation of the wave function near the nuclear region. The inner-core electrons (1s-2p) require very high virtual energy functions for proper correlation. Therefore, the all-electron correlation treatment and the inclusion of higher-energy virtual functions are the key factors for precise calculation of the hyperfine structure constant of atoms. Our calculated values are in excellent agreement with the available experimental values, which also implies that the wave function produced by the Z-vector method is accurate enough for further calculation of the parity- and time-reversal symmetry-violating properties in atoms and molecules.

De novo transcriptome analysis of the egg parasitoid Trichogramma chilonis Ishii (Hymenoptera: Trichogrammatidae): a biological control agent - Kerima, O.Z.; Niranjana, P.; Vinay Kumar, B.S.; Ramachandrappa, R.; Puttappa, S.; Lalitha, Y.; Jalali, S.K.; Ballal, C.R.; H. V. Thulasiram (Gene Reports, 2018)
Trichogramma chilonis Ishii is an endoparasitic wasp widely used as a biological control agent of economically important pests. However, absence of genetic information on T. chilonis hampers further research, especially at the molecular level. Here, we performed the first RNA-Seq of the adult T. chilonis. A total of 18,372,639 high-quality reads were generated using Illumina pair-ended sequencing platform. De novo assembly resulted into 24,488 transcripts, with mean length and N50 values of 1444.2 bp and 2667 bp, respectively. Of the transcripts, 14,643 exhibited putative homology with class Insecta proteins from UniPROT database. To understand the contig functions, gene descriptions, gene ontology and cluster of orthologous group annotations were analyzed. Following functional annotation, a number of transcripts encoding detoxification, target receptor action and olfaction- related proteins were identified and analyzed. In addition, 4520 transcripts containing simple sequence repeats, ranging from dinucleotide to hexanucleotide repeats were discovered, with trinucleotide being the most enriched repeats. This new sequence resource will shed light on various molecular mechanisms in T. chilonis and related species.

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.

Design, synthesis and biological screening of novel 1,3,4-oxadiazoles as antitubercular agents - Tambe, Macchindra S.; Choudhari, Amit; Sarkar, Dhiman; Sangshetti, Jaiprakash; Patil, Rajesh; Gholap, Somnath S. (Chemistryselect, 2018)
A series of novel 2,5-disubstitued 1,3,4-oxadiazole derivatives bearing 2,2-dimethyl-2,3-dihydrobenzofuran scaffold has been synthesized and screened for antitubercular activity. All the synthesized compounds were characterized by IR, H-1 NMR, C-13-NMR and Mass spectral study. The in vitro antitubercular activity of the synthesized compounds was evaluated against Mycobacterium tuberculosis H37Ra(ATCC 25177) strain. Among the synthesized compounds, four compound displayed good antitubercular activity IC50 values in low micro-gram range (<10 mu g/mL). The antitubercular data suggested that growth inhibition MTB can be imparted by the introduction of a 4- trifluoromethyl phenyl acetylene substituent. Specificity of these compounds was checked by screening them for their anti-bacterial activity against four bacterial strains (Gram-negative strains: E. coli, S. aureus; Gram-positive strains: P. aeruginosa and B. subtilis). None of the compound displayed antibacterial activity against any of the seleted strain. Molecular docking studies were carried out on InhA (FabI/ENR) which shows that the synthesized compounds bind at the catalytic site in a most favourable manner suggesting their potential as anti-mycobacterial agents. The research presented here was found to be adventitious for the development of new therapeutic agents against Mycobacterium infection.

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.

Development of enhanced hypericin yielding transgenic plants and somaclones: high throughput direct organogenesis from leaf and callus explants of Hypericum perforatum - Khan, Shamshad A.; Verma, Priyanka; Arbat, Akshata; Gaikwad, Sushma; Parasharami, Varsha A. (Industrial Crops and Products, 2018)
Hypericum perforatum is well known for its anti-depressent properties due to the presence of hypericins and hyperforins. The direct regeneration protocol from leaf explants and Agrobacterium tumefaciens mediated genetic transformation is a prerequisite for gene transfer studies in this valuable plant system as H. perforatum has shown its recalcitrance to these studies previously. The aim of generating transgenic shoots or somaclones in the present study is to select high hypericine yielding H. perforatum plants. High throughput direct bud organogenesis from leaf explants has been achieved for the first time in this plant system on media combination of MS + 5.0 mg/l BAP + 1.0 mg/l. This medium interestingly also worked as the indirect regeneration media for generation of somaclones from callus cultures. Thus far optimized single media can be used for direct and indirect regeneration in H. perforatum. The direct regeneration frequency of plantlets from leaf explants was found to be 80% while 100% was the regeneration frequency noted for indirect plantlet regeneration from callus cultures. The optimized direct regeneration protocol from leaf explants was utilized for A. tumefaciens (harbouring pCAMBIA 1301) mediated genetic transformation studies with the aim of establishing transgenic lines of H. perforatum. The resultant study successfully gave rise to kanamycin resistant GUS positive shoots with transformation efficiency of 3136 +/- 3.6. A total of four transgenic H. perforatum clones namely T2, T3, T5 and T8 with different growth parameters were established, where highest of fivefold increase in hypericin content was recorded by T5 (276.8 +/- 9.2 mu g/g dry wt.) in comparison to control non transformed plants (35.6 +/- 2.7 mu g/g dry wt.). Interestingly the presence of serotonin and melatonin was also detected in transgenic plants on TLC basis. The transgenic nature of the plants was confirmed by PCR with amplification of uidA gene. Apart from it, from indirect regeneration from callus, total of ten somaclones were generated. The ISSR profiling of somaclones scored a total of 156 bands, among which 118 were polymorphic in nature. The glasshouse established soma clones showed up to twofold increase in hypericin content on HPLC analysis.
Keywords: Direct regeneration; Hypericin; Hypericum perforation; Indirect regeneration; ISSR; Somaclones; Transgenic plants

Differential responses of CHO cells adapted to limitation of inorganic phosphate, glucose or glutamine - Maralingannavar, Vishwanathgouda; Parmar, Dharmeshkumar; Pant, Tejal; Gadgil, Chetan; Panchagnula, Venkateswarlu; Gadgil, Mugdha (255th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nexus of Food, Energy, and Water, 2018)

Direct access to N-alkylated amines and imines via acceptorless dehydrogenative coupling catalyzed by a cobalt(ii)-NNN pincer complex - Midya, Siba P.; Pitchaimani, Jayaraman; Landge, Vinod G.; Madhu, Vedichi; Balaraman, Ekambaram (Catalysis Science & Technology, 2018)
A simple, phosphine-free Co(ii)-NNN pincer complex catalyzed direct N-alkylation of anilines with alcohols via hydrogen auto-transfer (HA) and selective acceptorless dehydrogenative coupling (ADC) of benzylamines with alcohols affording imines with the liberation of molecular hydrogen and water is reported.

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.

Dissociative chemisorption of hydrogen molecules on defective graphene-supported aluminium clusters: a computational study - Kumar, Deepak; Govindaraja, Thillai; Krishnamurty, Sailaja; Kaliaperumal, Selvaraj; Pal, Sourav (Physical Chemistry Chemical Physics, 2018)
Using periodic density functional theory-based calculations, in the present study, we address the chemical bonding between aluminium clusters (Al-n, n = 4-8 and 13) and monovacant defective graphene. The adsorption strength of the above-mentioned aluminium clusters is fivefold (approximate to 3 to 5 eV) higher on defective graphene as compared to the earlier reported values on non-defective graphene and BN-doped graphene. The Bader charge analysis and different charge densities reveal that this adsorption is driven by significant charge transfer from the Al clusters to defective graphene. Thus, chemisorbed Al clusters demonstrate high activity towards dissociative adsorption of molecular hydrogen.

Divergent synthesis of oxindolylidene acetates and spirooxindolopyrrolidones from arynes - Pandya, Virat G.; Mhaske, Santosh B. (Organic Letters, 2018)
A novel process for the preparation of various (E)-oxindolylidene acetates using arynes and carbamoylpropiolates has been developed. The utility of this protocol is also further extended to the one-pot synthesis of complex spirooxindolopyrrolidones. This method provides a milder and transition-metal-free access to both of the target scaffolds in moderate to good yields.

Effect of membrane composition on receptor association: implications of cancer lipidomics on ErbB receptors - Pawar, Aiswarya; Sengupta, Durba (Journal of Membrane Biology, 2018)
The association of single transmembrane receptors, such as the ErbB receptors is a key event in initiating cell signaling networks. The interactions between these receptors have been well characterized for both ligand-driven and pre-formed dimers. However, the role of the membrane in modulating association is less well understood and assumes greater importance in light of altered membrane composition in diseased states. Here, we discuss how membrane composition has been observed to induce both structural and dynamic differences in receptor association. Computational studies, especially those using coarse-grain simulations have been successful in predicting the role of the membrane and calculating the related free energy landscapes. Membrane perturbations and differences in lipid chain order, related to the lipophobic effect, have been shown to play a large role in driving membrane protein association. Further, we review lipid compositions reported in diseased conditions and its effect on transmembrane receptor association, focusing on the ErbB growth factor receptor dimers in cancer. Understanding the role of the membrane in receptor association will provide general design principles driving receptor organization, as well as help to identify novel therapeutic strategies.

Effect of turbulent dispersion on hydrodynamic characteristics in a liquid jet ejector - Sharma, Deepankar; Patwardhan, Ashwin; Ranade, Vivek (Energy, 2018)
Gas induction using a liquid jet is an extensively studied phenomenon. Many studies have been published detailing various hydrodynamic and mass transport aspects of gas induction in ejectors. Conversely, multiple studies have been published detailing jet dynamics, jet break up, nozzle geometry, effects of turbulence etc. In the modelling of the jet ejector systems CFD framework is used as the flow of gas is coupled with the liquid flow and the flow parameters like volume fraction, pressure drop/profile and velocity profiles both local and average are highly interdependent. Hence, it becomes important to capture all the flow physics in the simulations in order to understand the hydrodynamics. In the previous models the effect of turbulent dispersion was not included which led to incorrect calculation of phase profile, and other related parametric values. In the present work, the turbulence effects and its impact on the jet dynamics and gas induction rate in an ejector have been studied. Capturing the correct phase as well as velocity profile is imperative for the extension of the model to mass transfer and reactions. Lastly, other hydrodynamic properties like pressure drop, phase hold up and pressure profile help better the design correlations for jet ejectors.

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.

Enantioselective N-heterocyclic carbene-catalyzed cascade reaction for the synthesis of pyrroloquinolines via N-H functionalization of indoles - Mukherjee, Subrata; Shee, Sayan; Poisson, Thomas; Besset, Tatiana; Biju, Akkattu T. (Organic letters, 2018)
Functionalization of the indole N-H bond for enantioselective synthesis of biologically important pyrroloquinoline derivatives has been reported under oxidative N-heterocyclic carbene catalysis conditions. The interception of catalytically generated chiral alpha,beta-unsaturated acylazoliums with the indole derivatives proceeds in an aza-Michael/Michael/lactonization sequence to deliver the pyrroloquinoline derivatives in good yields, diastereoselectivities, and enantioselectivities. The simultaneous enhancement of reactivity and selectivity observed in polar aprotic solvents is noteworthy.

Enhanced activity of Withania somnifera family-1 glycosyltransferase (UGT73A16) via mutagenesis - Singh, Somesh; Patel, Krunal A.; Sonawane, Prashant D.; Vishwakarma, Rishi K.; Khan, Bashir M. (World Journal Of Microbiology & Biotechnology, 2018)
This work used an approach of enzyme engineering towards the improved production of baicalin as well as alteration of acceptor and donor substrate preferences in UGT73A16. The 3D model of Withania somnifera family-1 glycosyltransferase (UGT73A16) was constructed based on the known crystal structures of plant UGTs. Structural and functional properties of UGT73A16 were investigated using docking and mutagenesis. The docking studies were performed to understand the key residues involved in substrate recognition. In the molecular model of UGT73A16, substrates binding pockets are located between N- and C-terminal domains. Modeled UGT73A16 was docked with UDP-glucose, UDP-glucuronic acid (UDPGA), kaempferol, isorhamnetin, 3-hydroxy flavones, naringenin, genistein and baicalein. The protein-ligand interactions showed that His 16, Asp 246, Lys 255, Ala 337, Gln 339, Val 340, Asn 358 and Glu 362 amino acid residues may be important for catalytic activity. The kinetic parameters indicated that mutants A337C and Q339A exhibited 2-3 fold and 6-7 fold more catalytic efficiency, respectively than wild type, and shifted the sugar donor specificity from UDP-glucose to UDPGA. The mutant Q379H displayed large loss of activity with UDP-glucose and UDPGA strongly suggested that last amino acid residue of PSPG box is important for glucuronosylation and glucosylation and highly specific to sugar binding sites. The information obtained from docking and mutational studies could be beneficial in future to engineer this biocatalyst for development of better ones.

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.

Excited state intramolecular proton transfer in 1,8-Dihydroxy-9,10-anthraquinone dye: Revealing microstructures in [C(n)mIm][NTf2] and [C(n)mIm][BF4] series of ionic liquid solvents - Beniwal, Vijay; Kumar, Anil; Pal, Haridas (Journal of Photochemistry and Photobiology A-Chemistry, 2018)
Excited state intramolecular proton transfer (ESIPT) in 18-dihydroxy-9,10-anthraquinone (18DHAQ) dye has been investigated in two series of 1-alkyl-3-methylimidazolium ([C(n)mIm](+)) based ionic liquid (IL) solvents, [C(n)mlm][NTf2] and [C(n)mlm][BF4], with n = 2, 4, 6, 8 and 10, using steady-state (SS) and time resolved (TR) fluorescence studies. In both the IL series, fluorescence intensity for tautomer (T*) form gradually decreases relative to normal (N*) form with increasing n value for [C(n)mlm](+) cations. Observed results suggest microstructure formation and its consequent effect on the ESIPT process of the dye in these IL solvents. Since more extensive microstructures are likely with larger n values of [C(n)mIm](+) cations, the dye is expectedly solubilized more in the polar microdomains of the solvent microstructures, resulting better stabilization for the more dipolar N* state and hence a higher emission intensity from this state. This proposition is clearly supported by ultrafast (sub-picosecond) fluorescence kinetics for both N* and T* states, though sub-nanosecond TR results indicate very similar fluoresce decays for both N* and T*, suggesting an eventual kinetic equilibrium between two states subsequent to the initial ultrafast and fast forward and backward ESIPT processes. Small differences between the results in the [C(n)mIm][NTf2] and [C(n)mIm][BE4] series of ILs are attributed to dissimilar size, shape and basicity of [NTf2]- and [BF4]- anions, responsible for some characteristic changes in the microstructures formed in the respective solvent series. To the best of our knowledge, present study is the only report demonstrating modulations in the ESIPT process through microstructure formations in neat [C(n)mIm](+) based IL solvents. (C) 2017 Elsevier B.V. All rights reserved.
Keywords: 1; 1-Alkyl-3-methylimidazolium ionic liquids; 8-Dihydroxyanthraquinone; Emission modulations of tautomeric forms; ESIPT process; Microstructure formation

Excited-state prototropism of 7-hydroxy-4-methylcoumarin in [C(n)mim][BF4] series of ionic liquid-water mixtures: insights on reverse micelle-like water nanocluster formation - Beniwal, Vijay; Kumar, Anil; Pal, Haridas; Choudhury, Sharmistha Dutta (Photochemical & Photobiological Sciences, 2018)
This study explores the excited state prototropic behavior of the fluorophore, 7-hydroxy-4-methylcoumarin (7H4MC), in the [C(n)mim][BF4] (n = 2, 4, 6, 8, 10) series of ionic liquid (IL)-water mixtures at low water contents. In pure IL media, 7H4MC exists in the neutral form in both ground and excited states. However, on addition of water to the ILs, the excited neutral form of the dye is gradually converted to the anionic and the tautomeric species, leading to characteristic changes in the emission spectra. The similarity in the spectral features of 7H4MC in the IL-water system with that in a conventional reverse micelle system rather than with organic solvent-water mixtures, suggests that in the presence of water, the ILs are organized into reverse micelle-like structures with the consequent formation of confined water pockets. The results further suggest that formation of water nanoclusters and the ensuing changes in excited state prototropic behavior of the dye, is facilitated by increase in the alkyl chain length of the IL cation. These propositions are supported by time-resolved fluorescence studies. To the best of our knowledge this is the first report on proton transfer reaction in IL-water mixtures at low water contents. Considering that ILs are useful as solvents and surfactants, and IL-water mixtures in particular have applications in chemical extractions and biocatalysis, an understanding of the structural organization and water pool formation in these systems is quite important. The insights obtained from the prototropic transformations of 7H4MC are significant not only for fundamental self-assembly studies, but also for the development of ILs as chemical reaction media.

Exploring GPCR lipid interactions by molecular dynamics simulations: excitements, challenges, and the way forward - Sengupta, Durba; Prasanna, Xavier; Mohole, Madhura; Chattopadhyay, Amitabha (Journal of Physical Chemistry B, 2018)
Gprotein-coupled receptors (GPCRs) are seven transmembrane receptors that mediate a large number of cellular responses and are important drug targets. One of the current challenges in GPCR biology is to analyze the molecular signatures of receptor-lipid interactions and their subsequent effects on GPCR structure, organization, and function. Molecular dynamics simulation studies have been successful in predicting molecular determinants of receptor-lipid interactions. In particular, predicted cholesterol interaction sites appear to correspond well with experimentally determined binding sites and estimated time scales of association. In spite of several success stories, the methodologies in molecular dynamics simulations are still emerging. In this Feature Article, we provide a comprehensive overview of coarse-grain and atomistic molecular dynamics simulations of GPCR-lipid interaction in the context of experimental observations. In addition, we discuss the effect of secondary and tertiary structural constraints in coarse-grain simulations in the context of functional dynamics and structural plasticity of GPCRs. We envision that this comprehensive overview will help resolve differences in computational studies and provide a way forward.

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.

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.

First total synthesis of (+/-)-rhodoconferimide - Pandhade, Kailas R.; N. P. Argade (Synthesis-Stuttgart, 2018)
Starting from vanillin and dimethyl maleate, a concise and efficient racemic total synthesis of the potent antioxidant marine natural product (+/-)-rhodoconferimide has been carried out via the Wittig reaction, catalytic hydrogenation, selective brominations, and imide formation. An appropriate regioselective double bromination of the aromatic ring was a key step in the synthesis.
Keywords: (+/-)-rhodoconferimide; Antioxidants; Bromination; Natural products; Total synthesis; Vanillin

Flexible composite mechanical energy harvester from a ferroelectric organoamino phosphonium salt - Vijayakanth, Thangavel; Srivastava, Anant Kumar; Ram, Farsa; Kulkarni, Priyangi; Shanmuganathan, Kadhiravan; Praveenkumar, Balu; Boomishankar, Ramamoorthy (Angewandte Chemie-International Edition, 2018)
A new binary organic salt diphenyl diisopropylamino phosphonium hexaflurophosphate (DPDPPF6) was shown to exhibit a good ferroelectric response and employed for mechanical energy harvesting application. The phosphonium salt crystallizes in the monoclinic noncentrosymmetric space group Cc and exhibits an H-bonded 1D chain structure due to N-HF interactions. Ferroelectric measurements on the single crystals of DPDPPF6 gave a well-saturated rectangular hysteresis loop with a remnant (P-r) polarization value of 6Ccm(-2). Further, composite devices based on polydimethylsiloxane (PDMS) films for various weight percentages (3, 5, 7, 10 and 20wt%) of DPDPPF6 were prepared and examined for power generation by using an impact test setup. A maximum output peak-to-peak voltage (V-PP) of 8.5V and an output peak-to-peak current (I-PP) of 0.5A was obtained for the non-poled composite film with 10wt% of DPDPPF6. These results show the efficacy of organic ferroelectric substances as potential micropower generators.
Keywords: binary phosphonium salts; energy conversion; ferroelectricity; hydrogen bonding; polymer composites

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.

Four-step total synthesis of (+)-yaoshanenolides A and B - Thorat, Sagar S.; Palange, Megha N.; Kontham, Ravindar (ACS Omega, 2018)
A highly concise bioinspired four-step total synthesis of yaoshanenolides A and B possessing tricyclic spirolactone with an unusual 5'H-spiro-[bicyclo[2.2.2]-oct[2] ene-7,2'-furan]-5'-one scaffold is reported. This synthesis features high-yielding aldol-type addition of gamma-butyrolactone on to the aldehyde, exocyclic olefination of lactone derivative using Eschenmoser's salt, and highly facial-and endo-selective [4 + 2]-cycloaddition of fully functionalized 5-methylene-2(5H)-furanone with natural R-(-)-alpha-phellandrene. The approach allows access to yaoshanenolides A and B in four linear steps in 11 and 13% overall yield.

Functionalized carbon nanotube reinforced polymer nanocomposite microcapsules with enhanced stiffness - Jagtap, Siddheshwar B.; Patil, Vishal D.; Suresh, Karthika; Ram, Farsa; Mohan, Muthu Subramanian; Rajput, Shatruhan S.; Patil, Shivprasad; Shukla, Parshuram G.; Shanmuganathan, Kadhiravan (Colloids and Surfaces A-Physicochemical and Engineering Aspects, 2018)
Microcapsules with tunable mechanical properties are highly desirable in pressure sensitive applications. We report here a facile approach to prepare polyurea/multiwall carbon nanotube (MWCNTs) nanocomposite microcapsules (MICs) with enhanced stiffness. A model compound dimethyl phthalate (DMP) was used as core material. MWCNTs were modified with reactive functional groups namely carboxyl (-COOH), amines (-NH2), and isocyanates (-NCO) to ensure a stronger interface between polymer wall and MWCNTs. Functionalization of MWCNTs was corroborated by Fourier transformed infrared spectroscopy (FTIR). Scanning electron microscopy (SEM) was employed to study the surface morphology of MICs. The presence of MWCNTs in the microcapsule wall was confirmed by transmission electron microscopy (TEM). MICs with functionalized MWCNTs show almost 100% increase in stiffness with respect to pristine capsules. All MICs show 92-97 +/- 1% encapsulation efficiency. The approach used in this paper can be broadly utilized to tune the mechanical properties of the microcapsules.

Generic and scalable method for the preparation of monodispersed metal sulfide nanocrystals with tunable optical properties - Bera, Abhijit; Mandal, Debranjan; Goswami, Prasenjit N.; Rath, Arup K.; Bhagavatula L. V. Prasad (Langmuir, 2018)
A rational synthetic method that produces monodisperse and air-stable metal sulfide colloidal quantum dots (CQDs) in organic nonpolar solvents using octyl dithiocarbamic acid (C(8)DTCA) as a sulfur source, is reported. The fast decomposition of metal-C(8)DTCA complexes in presence of primary amines is exploited to achieve this purpose. This novel technique is generic and can be applied to prepare diverse CQDs, like CdS, MnS, ZnS, SnS, and In2S3, including more useful and in-demand PbS CQDs and plasmonic nanocrystals of Cu2S. Based on several control reactions, it is postulated that the reaction involves the in situ formation of a metal-C(8)DTCA complex, which then reacts in situ with oleylamine at slightly elevated temperature to decompose into metal sulfide CQDs at a controlled rate, leading to the formation of the materials with good optical characteristics. Controlled sulfur precursor's reactivity and stoichiometric reaction between C(8)DTCA and metal salts affords high conversion yield and large-scale production of monodisperse CQDs. Tunable and desired crystal size could be achieved by controlling the precursor reactivity by changing the reaction temperature and reagent ratios. Finally, the photovoltaic devices fabricated from PbS CQDs displayed a power conversion efficiency of 4.64% that is comparable with the reported values of devices prepared with PbS CQDs synthesized by the standard methods.

Genetic and phytochemical investigations for understanding population variability of the medicinally important tree Saraca asoca to help develop conservation strategies - Hegde, Satisha; Pai, Sandeep Ramchandra; Bhagwat, Rasika M.; Saini, Archana; Rathore, Poonam Kanwar; Jalalpure, Sunil Satyappa; Hegde, Harsha Vasudev; Sugunan, Attayoor Purushottaman; Gupta, Vidya S.; Kholkute, Sanjiva D.; Roy, Subarna (Phytochemistry, 2018)
Saraca asoca (Roxb.) De Wilde (Caesalpiniaceae) is a highly traded IUCN red listed tree species used in Ayurvedic medicines for the treatment of various disorders, especially gynaecological problems. However, information about the genetic variations between populations and corresponding variation in specialized metabolites of S. asoca remains unclear. To address this issue, we analysed 11 populations of S. asoca with 106 accessions collected from Western Ghats of India using ISSR markers along with selected phytocompounds using RP-HPLC. Twenty primers were screened, out of which seven were selected for further analysis based on generation of clear polymorphic banding patterns. These seven ISSR primers produced 74 polymorphic loci. AMOVA showed 43% genetic variation within populations and 57% among the populations of S. asoca. To estimate the genetic relationships among S. asoca populations, UPGMA and Bayesian Models were constructed, which revealed two clusters of similar grouping patterns. However, excluding minor deviations, UPGMA and dissimilarity analysis showed close association of genotypes according to their geographical locations. Catechin (CAT), epicatechin (EPI) and gallic acid (GA) were quantified from bark and leaf samples of corresponding genotypes collected from 106 accessions. ROC plots depicted the sensitivity and specificity of the concentrations of tested phytocompounds at various cut-off points. Although, multiple logistic regression analysis predicted some association between few loci with GA, EPI and CAT, but PCA for phytochemical data failed to distinguish the populations. Overall, there were no significant trends observed to distinguish the populations based on these phytocompounds. Furthermore, the study advocates the delineate provenance regions of S. asoca genotypes/chemotype snapshots for in-situ conservation and ex-situ cultivation.

Genetic programming based models for prediction of vapor-liquid equilibrium - Patil-Shinde, Veena; Tambe, Sanjeev S. (Calphad-Computer Coupling of Phase Diagrams and Thermochemistry, 2018)
The design, operation, and control of chemical separation processes heavily rely on the knowledge of the vapor liquid equilibrium (VLE). Often, conducting experiments to gain an insight into the separation behavior becomes tedious and expensive. Thus, standard thermodynamic models are used in the VLE prediction. Sometimes, exclusively data-driven models are also used in VLE prediction although this method too possesses drawbacks such as a trial and error approach in specifying the data-fitting function. For overcoming these difficulties, this paper employs a machine learning (ML) formalism namely "genetic programming (GP)" possessing certain attractive features for the VLE prediction. Specifically, three case studies have been performed wherein GP-based models have been developed using experimental data, for predicting the vapor phase composition of a ternary, and a group of non ideal binary systems. The inputs to models consists of three pure component attributes (acentric factor, critical temperature, and critical pressure), and as many intensive thermodynamic parameters (liquid phase composition, pressure, and temperature). A comparison of the VLE prediction and generalization performance of the GP-based models with the corresponding standard thermodynamic models reveals that the former class of models possess either superior or closely comparable performance vis-a-vis thermodynamic models. Noteworthy features of this study are: (i) a single GP-based model can predict VLE of a group of binary systems, and (ii) applicability of a GP-based model trained on an alcohol-acetate series data for its higher homolog. The VLE modeling approach exemplified here can be gainfully extended to other ternary and non-ideal binary systems, and for designing corresponding experiments in different pressure and temperature ranges.

Genomic roadmaps for augmenting salinity stress tolerance in crop plants - Suprasanna, P.; Ghuge, S. A.; Patade, V. Y.; Mirajkar, S. J.; Nikalje, G. C. (Salinity Responses and Tolerance in Plants, 2018)
Serious antagonistic impacts of saline environment on plant growth, development, and yield are well established. In this regard, researchers and breeders have been utilizing many conventional as well as modern approaches to aid the pro- cess of developing salt-tolerant crops. Biotechnological tools have made the task of engineering salinity tolerance in plants easier. Currently, two major annexes are effectively employed to develop salt-tolerant crops, first, investigation of genetic variation via marker-assisted selection (MAS) and second the transgenic technology. Sustenance of plants under dynamically growth-limiting saline environment depends on alterations and/or switching between multiple biochemical pathways involved in response. A number of key regulatory genes have been successfully identified and characterized in this context which can be explored to serve the purpose of alleviation in salt-tolerant nature of plants. Several genomics-abetted approaches have been reported aiming toward improvement in growth and yield of crops under saline envi- ronment. Present chapter focuses on genomic roadmaps for augmentation of crop salt tolerance by various methods including MAS, transgenic breeding, manipulations in small non-coding RNAs, and genome editing. These approaches utilize key players involved in salinity-mediated plant defense mechanisms, such as ion transporters, osmolytes, antioxidants, transcription factors, signaling proteins, and microRNA. The chapter attempts to summarize the effective targets and exploration of these key entities to raise salt-tolerant plants through various genomics-related tools.

Gold(I)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes - Akram, Manjur O.; Shinde, Popat S.; Chintawar, Chetan C.; Patil, Nitin T. (Organic & Biomolecular Chemistry, 2018)
Gold(I)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes are described. This redox neutral strategy offers an efficient approach to diverse biaryls, vinyl arenes and arylacetylenes. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the in situ formation of Ph3PAuIR (R = aryl, vinyl and alkynyl) species which is crucial for the activation of aryldiazonium salts.

Graphene quantum dots-driven multiform morphologies of β-NaYF4:Gd3+/Tb3+ phosphors: the underlying mechanism and their optical properties - Malik, M.; Padhye, P.; Poddar, P. (ACS omega, 2018)
Dimension and shape tunable architectures of inorganic crystals are of extreme interest because of morphology-dependent modulation of the properties of the materials. Herein, for the first time, we present a novel impurity-driven strategy where we studied the influence of in situ incorporation of graphene quantum dots (GQDs) on the growth of β-NaYF4:Gd3+/Tb3+ phosphor crystals via a hydrothermal route. The GQDs function as a nucleation site and by changing the concentration of GQDs, the morphology of β-NaYF4:Gd3+/Tb3+ phosphors was changed from rod to flowerlike structure to disklike structure, without phase transformation. The influence of size and functionalization of GQDs on the size and shape of phosphor crystals were also systematically studied and discussed. Plausible mechanisms of formation of multiform morphologies are proposed based on the heterogeneous nucleation and growth. Most interestingly, the experimental results indicate that the photoluminescence properties of β-NaYF4:Gd3+/Tb3+ phosphor crystals are strongly dependent on the crystallite size and morphology. This study would be suggestive for the precisely controlled growth of inorganic crystals; consequently, it will open new avenues and thus may possess potential applications in the field of materials and biological sciences.

Harnessing visible-light and limited near-IR photons through plasmon effect of gold nanorod with AgTiO2 - Patra, Kshirodra Kumar; Gopinath, Chinnakonda S. (Journal of Physical Chemistry C, 2018)
The utilization of the red-green-blue (RGB) and limited near-IR photons for solar hydrogen evolution (SHE) has been reported in a single plasmonic nanocomposite. Present study describes the use of AgTiO2 (AgT) decorated with Au nanorods (AgT-AuNR) to enhance the absorption of entire visible-light and limited near-IR wavelength range in the sunlight for SHE from photocatalytic water splitting reaction. It is demonstrated that the longitudinal plasmon resonance of AuNR in AgT-AuNR induces SHE between 550 and 800 nm, whereas TiO2-AuNR or AgT shows no activity in this wavelength range. The key aspect of achieving the high photocatalytic activity of AgT-AuNR in the solar spectrum is the electronic integration among metal NPs as well as with TiO2, and the heterojunctions among them. Presence of such heterojunctions has been supported by different characterization studies. However, gold nanorod exhibits field effect and further enhances light harvesting. Although the absolute amount of energy harvested only from near-IR photons is low, when combined with high-energy visible-light photons within one sun conditions, it shows a multiplier effect rather than a simple additive effect. Likely, this is the first report, where SHE has been achieved with significant amount of light absorption at lambda >= 550 nm with a plasmonic nanocomposite.

High and reversible lithium ion storage in self-exfoliated triazole-triformyl phloroglucinol-basedcovalent organic nanosheets - Haldar, Sattwick; Roy, Kingshuk; Nandi, Shyamapada; Chakraborty, Debanjan; Puthusseri, Dhanya; Gawli, Yogesh; Ogale, Satishchandra; Vaidhyanathan, Ramanathan (Advanced Energy Materials, 2018)
Covalent organic framework (COF) can grow into self-exfoliated nanosheets. Their graphene/graphite resembling microtexture and nanostructure suits electrochemical applications. Here, covalent organic nanosheets (CON) with nanopores lined with triazole and phloroglucinol units, neither of which binds lithium strongly, and its potential as an anode in Li-ion battery are presented. Their fibrous texture enables facile amalgamation as a coin-cell anode, which exhibits exceptionally high specific capacity of approximate to 720 mA h g(-1) (@100 mA g(-1)). Its capacity is retained even after 1000 cycles. Increasing the current density from 100 mA g(-1) to 1 A g(-1) causes the specific capacity to drop only by 20%, which is the lowest among all high-performing anodic COFs. The majority of the lithium insertion follows an ultrafast diffusion-controlled intercalation (diffusion coefficient, D-Li(+) = 5.48 x 10(-11) cm(2) s(-1)). The absence of strong Li-framework bonds in the density functional theory (DFT) optimized structure supports this reversible intercalation. The discrete monomer of the CON shows a specific capacity of only 140 mA h g(-1) @50 mA g(-1) and no sign of lithium intercalation reveals the crucial role played by the polymeric structure of the CON in this intercalation-assisted conductivity. The potentials mapped using DFT suggest a substantial electronic driving-force for the lithium intercalation. The findings underscore the potential of the designer CON as anode material for Li-ion batteries.

Highly diverged novel subunit composition of apicomplexan F-type ATP synthase identified from Toxoplasma gondii - Salunke, Rahul; Mourier, Tobias; Banerjee, Manidipa; Pain, Arnab; Shanmugam, Dhanasekaran (Plos Biology, 2018)
The mitochondrial F-type ATP synthase, a multisubunit nanomotor, is critical for maintaining cellular ATP levels. In T. gondii and other apicomplexan parasites, many subunit components necessary for proper assembly and functioning of this enzyme appear to be missing. Here, we report the identification of 20 novel subunits of T. gondii F-type ATP synthase from mass spectrometry analysis of partially purified monomeric (approximately 600 kDa) and dimeric (> 1 MDa) forms of the enzyme. Despite extreme sequence diversification, key F-O subunits a, b, and d can be identified from conserved structural features. Orthologs for these proteins are restricted to apicomplexan, chromerid, and dinoflagellate species. Interestingly, their absence in ciliates indicates a major diversion, with respect to subunit composition of this enzyme, within the alveolate clade. Discovery of these highly diversified novel components of the apicomplexan F-type ATP synthase complex could facilitate the development of novel antiparasitic agents. Structural and functional characterization of this unusual enzyme complex will advance our fundamental understanding of energy metabolism in apicomplexan species.

Highly efficient field emission properties of radially aligned carbon nanotubes - Tripathi, P.; Gupta, B.K.; Bhatnagar, A; Patel, C.R.P; Banker, P.K.; Late, D.J.; More, M.A.; Lalla, N.P.; Phase, D.M.,; Choudhary, R.J.; Shaz, M.A.; Ajayan, P.M.; et al. (Journal of Materials Chemistry C, 2018)
Here, we report extraordinary field emission properties from one pot synthesized aligned carbon nanotubes endowed with related Fe nanoparticles (NPs). The CNT configuration is in the form of a carbon hollow cylinder (CHC) with CNTs radially aligned towards the CHC axis. The structure generates electron field emission properties such as an ultralow turn on field (0.35 V μm−1 at 10 μA cm−2), a low threshold field (0.41 V μm−1 at 100 μA cm−2) and a high field emission current density (7.71 mA cm−2 at 0.78 V μm−1). It also exhibits multi-fold improvement in the field enhancement factor (1.34 × 104) with highly stable current emission at 100 μA measured for 14 h. No post synthesis treatment is required for enhanced field emission characteristics. The growth related Fe NPs assist in lowering the work function and hence enhancing the field emission properties. The possibility of assembling nano-structured field emitters into macroscale architectures suggests new prospects for next generation three dimensional electron sources.