Simple, phosphine free, reusable Pd(II)-2,2 `-dihydroxybenzophenone-SBA-15 catalyst for arylation and hydrogenation reactions of alkenes - Lazar, Anish; Vinod, Chathakudath P.; Singh, Anand Pal (New Journal of Chemistry, 2016)
An efficient, simple, phosphine and co-catalyst free C-C coupling reaction heterogeneous catalyst via a post grafting method is developed and reported. A covalently anchored phosphine free Pd(II) based 2,2'-dihydroxybenzophenone (DHBP) complex over organofunctionalized SBA-15 has been synthesized by the reaction between aminofunctionalized SBA-15 (NH(2)SBA-15) and a 2,2'-dihydroxybenzophenone (DHBP) ligand, and further complexation with Pd(II)Cl-2 to get Pd(II)-DHBP@ SBA-15. The synthesized catalysts were characterized by elemental analysis, XRD, N-2 sorption analyses, TG, DTA, FT-IR, solid state C-13 and Si-29 NMR spectra, XPS, UV-Visible, SEM, EDAX and TEM. The synthesized catalysts were screened in arylation (Heck reactions) and hydrogenation reactions of alkenes, and the results show that Pd(II)-DHBP@ SBA-15 exhibits high conversion and selectivity towards arylation and hydrogenation reactions of alkenes with high stability. The anchored solid catalysts can be recycled effectively and reused several times without major loss in activity.

Single pot transfer hydrogenation and aldolization of furfural over metal oxide catalysts - Biradar, Narayan S.; Hengne, Amol M.; Sakate, S. S.; Swami, R. K.; Rode, Chandrashekhar V. (Catalysis Letters, 2016)
One pot catalytic transfer hydrogenation (CTH) of furfural to furfuryl alcohol (FAL) by using hydrogen producing alcohols and simultaneous aldolization of carbonyl compounds produced during CTH, with furfural was achieved over non-noble metal oxides with bifunctional sites. Basic sites of MgO responsible for abstraction of proton showed complete conversion of furfural to give FAL and C8 monomer in a ratio of 3:1, respectively, the later altered to 1:1 by incorporating Al into MgO. Catalyst stability was established by its four cycles study. [GRAPHICS]
Keywords: Aldol; furfural; Furfuryl alcohol; Metal oxides; transfer hydrogenation

Site-selective synthesis and characterization of BODIPY-acetylene copolymers and their transistor properties - Debnath, Sashi; Singh, Saumya; Bedi, Anjan; Krishnamoorthy, Kothandam; Zade, Sanjio S. (Journal of Polymer Science Part A-Polymer Chemistry, 2016)
To study the effect of site-selective copolymerization of borondipyrromethene (BODIPY) with acetylene on the structural and optoelectronic properties, three copolymers P1-P3 were synthesized by the Sonogashira cross-coupling of BODIPY units with diacetylene and bromine capping through all the possible linkages: alpha-alpha (P1), alpha-beta (P2), and beta-beta (P3). The optoelectronic properties of the polymers were investigated systematically to understand the effect of site-selective polymerization. The HOMO levels of the polymers were significantly tuned from P1 to P3 with negligible change in the LUMO levels. Broadening of absorption spectra from P3 to P1 was observed because of increase in the extent of conjugation. Additionally, the charge transport properties of these polymers in organic thin-film transistors (OTFTs) revealed that P1 and P3 exhibited only p-type mobility, whereas P2 exhibited electron mobility. Notably, the further investigations of the surface morphology of polymer films by atomic force microscopy (AFM) unveiled that comb like nanostructural arrangements in P3 was beneficial for the charge-carrier mobility over the circular arrangements in P1 and P2. (C) 2016 Wiley Periodicals, Inc.
Keywords: acetylene; BODIPY; DFT; low-band gap

Situ fabrication of highly crystalline CdS decorated Bi2S3 nanowires (nano-heterostructure) for visible light photocatalyst application - Panmand, Rajendra P.; Sethi, Yogesh A.; Deokar, Rajashree S.; Late, Dattatray J.; Gholap, Haribhau M.; Baeg, Jin-Ook; Kale, Bharat B. (RSC Advances, 2016)
In situ synthesis of the orthorhombic Bi2S3 nanowires decorated with hexagonal CdS nanoparticles (nano-heterostructure) has been demonstrated by a facile solvothermal method. The tiny 5-7 nm CdS spherical nanoparticles are decorated on the surfaces of 30-40 nm Bi2S3 nanowires, successfully. Structural, morphological and optical studies clearly show the existence of CdS on the nanowires. A possible sequential deposition growth mechanism is proposed on the basis of experimental results to reveal the formation of the nano heterostructure. The heterostructures have been used as a photocatalyst for hydrogen production as well as degradation of methylene blue under solar light. The maximum hydrogen evolution i.e. 4560 and 2340 mu mol h(-1) 0.5 g was obtained from H2S splitting and glycerol degradation for Bi2S3 NWs decorated with CdS nanoparticles (nano-heterostructure) which is higher than that of the Bi2S3 NWs (3000 and 1170 mu mol h(-1) 0.5 g, respectively). The enhanced photocatalytical hydrogen evolution efficiency of the heterostructures is mainly attributed to its nanostructure. In the nano heterostructure, the CdS nanoparticles control the charge carrier transition, recombination, and separation, while the Bi2S3 nanowire serves as a support for the CdS nanoparticles. The photogenerated electron's migration is faster than the holes from the inside of a CdS nanoparticle to its surface or to the phase interface, resulting in a relatively higher hole density inside the CdS nanoparticle leaving electron density at surface of the Bi2S3 NWs. This influences the photocatalytic activity under solar light. Such nano-heterostructures may have potential in other photocatalytic reactions.

Solution chemistry-based nano-structuring of copper dendrites for efficient use in catalysis and superhydrophobic surfaces - Bakthavatsalam, Rangarajan; Ghosh, Subrata; Biswas, Ratul Kumar; Saxena, Aayushi; Raja, Alagar; Thotiyl, Musthafa Ottakam; Wadhai, Sandip; Banpurkar, Arun G.; Kundu, Janardan (RSC Advances, 2016)
Despite their performance and economic advantages over Ag and Au, there have been no focused research efforts on the nano-structuring of Cu dendrites with respect to fine-tuning their structure/morphology towards the efficiency enhancement of suitable applications. Reported here is a simple, versatile, environmentally-friendly and galvanic replacement reaction-based solution chemistry methodology to synthesize highly nano-structured copper dendrites targeted towards the efficiency enhancement of desired applications. Herein, copper is deposited galvanically on an Al foil in the presence of NaCl/HCl, wherein the chloride anions augment an uninterrupted replacement reaction. The growth process of Cu dendrites has been probed in detail. The presence of acid, the type of Cu2+ precursor salt, the Cu2+ ion concentration, the surfactant concentration and the reaction temperature are all demonstrated to provide useful means of modulating the surface structure/morphology of the dendrites. Notably, dendrites formed in the presence of acid are found to be highly nano-structured. Moreover, it is also found that the morphology/structure of the obtained Cu deposit depends considerably upon the choice of the Cu2+ precursor salt, a parameter that has been completely overlooked in the past. The acid-induced nano-structuring of the dendrites is exploited for enhancing their efficiency in the catalytic reduction of para-nitrophenol and for fabricating self-cleaning superhydrophobic surfaces. These nano-structured dendrites are demonstrated to have the highest ever normalized rate constant for the catalytic reduction reaction. Superhydrophobic surfaces fabricated using these dendrites demonstrate excellent self-cleaning abilities, showing a high contact angle (159 degrees) with low contact angle hysteresis (2 degrees). This facile synthetic strategy for the fabrication of highly nano-structured Cu dendrites is expected to open up avenues for the production of Cu-based low-cost functional nano/micro-materials.

Spectroscopy and catalytic activity study of gold supported on barium titanate nanotubes for styrene epoxidation - Nepak, Devadutta; Srinivas, Darbha (Applied Catalysis A-General, 2016)
Gold (0.5-5 wt.%) supported on barium titanate nanotubes (Au/BaTNT) were prepared, characterized and for the first time, investigated as catalysts for selective oxidation of styrene with oxygen (O-2 or H-2 + O-2) and peroxides (H2O2 or TBHP). Conversion of styrene enhanced when H-2 was co-added to O-2 in the reactions. Au/BaTNT activated O-2 and H-2 and produced H2O2 in situ for use in oxidations. Peroxides were found better oxidants than O-2. At optimized conditions, styrene oxide selectivity of 80.1 wt.% at styrene conversion of 60.5 wt.% was achieved over Au(1 wt.%)/BaTNT using TBHP. Au particles (5.0-7.4 nm) were dispersed and decorated on the walls of BaTNT. They exhibited superior performance to the known Au catalysts in styrene oxidation. Reactive oxygen species formed during oxidation reactions were followed with in situ spectral characterizations (diffuse reflectance UV-vis and FT -Raman). Au/BaTNT was reusable in four recycles with little loss in catalytic activity. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Au Nanoparticles; reactive oxygen species; spectroscopy; Styrene Oxidation; Titanate nanotubes

State-of-the-art catechol porphyrin COF catalyst for chemical fixation of carbon dioxide via cyclic carbonates and oxazolidinones - Saptal, Vitthal; Shinde, Digambar Balaji; Banerjee, Rahul; Bhanage, Bhalchandra M. (Catalysis Science & Technology, 2016)
A highly porous, crystalline catechol porphyrin COF was synthesized and applied as an organocatalyst for the chemical fixation of carbon dioxide to synthesize value-added chemicals such as cyclic carbonates and oxazolidinones under solvent-free and transition-metal-free conditions. The high surface area and the functionalities of the COF catalyst act synergistically to activate the starting material. The 2,3-DhaTph shows excellent activity towards cyclic carbonates at the atmospheric pressure of carbon dioxide. Additionally, this catalytic system is recyclable in nature and provides a higher turnover number than previously reported organocatalysts.

Stereoselective quenching of cedryl carbocation in epicedrol biosynthesis - Shinde, Sandip S.; Navale, Govinda R.; Said, Madhukar S.; Thulasiram, Hirekodathakallu V. (Tetrahedron Letters, 2016)
Epicedrol synthase catalyzes the cyclization of achiral diphosphate substrate, (E,E)-farnesyldiphosphate (FPP) into epicedrol. GC-MS analysis of assay extracts obtained by incubating FPP with epicedrol synthase in 21.6 at % H2(18)O buffer showed the molecular ion of 224 for epicedrol. The labeled oxygen study presented here unambiguously demonstrates that the hydroxyl group of the epicedrol synthase enzymatic product, epicedrol, is derived from a water molecule, not from the phosphate moiety of the FPP. (C) 2016 Elsevier Ltd. All rights reserved.

Strategic Preparation of Efficient and Durable NiCo Alloy Supported N-Doped Porous Graphene as an Oxygen Evolution Electrocatalyst: A Theoretical and Experimental Investigation - Singh, Santosh K.; Kumar, Deepak; Dhavale, Vishal M.; Pal, Sourav; Kurungot, Sreekumar (Advanced Materials Interfaces, 2016)
Development of an efficient and durable water splitting electrocatalyst holds a great commitment for the future energy devices. The real application of oxygen evolution reaction (OER) catalysts mainly suffers from sluggish kinetics and high overpotential except for the Ir and Ru-based systems. However, the high cost and vulnerability of the Ir and Ru metals are the main hostiles to use them for marketization. Herein, a high-performance OER electrocatalyst consisting of NiCo alloy nanoparticles supported on high surface area N-doped porous graphene (NiCo/pNGr(75: 25)) is reported. The importance of the doped-N for achieving the uniform dispersion-cum-effective interaction of the size controlled NiCo alloy nanoparticles has been explicitly investigated by transmission electron microscopy, X-ray diffraction, X-ray photo electron spectroscopy, Raman, density functional theory (DFT) calculations, etc. The electrochemical analysis of NiCo/pNGr(75: 25) shows an overpotential of approximate to 260 mV at 10 mA cm(-2) with a smaller Tafel slope of approximate to 87 mV dec(-1) and long catalytic durability. DFT calculations are done to check the interaction between the NiCo alloy nanoparticles and the defective sites of pNGr and also with the doped-N, which could be attained for maintaining long catalytic durability. Furthermore, NiCo/pNGr(75: 25) is used as an OER catalyst to fabricate an electrolyzer, which works at very low potential of 1.5 V in 1 M KOH.

Streptomyces lonarensis sp nov., isolated from lonar lake, a meteorite salt water lake in India - Sharma, Trupti K.; Mawlankar, Rahul R.; Sonalkar, Vidya V.; Shinde, Vidhya K.; Zhan, Jing; Li, Wen-Jun; Rele, Meenakshi V.; Dastager, Syed Gulam; Kumar, Lalitha Sunil (Antonie Van Leeuwenhoek International Journal of General and Molecular Microbiology, 2016)
A novel alkaliphilic actinomycete, strain NCL716(T), was isolated from a soil sample collected from the vicinity of Lonar Lake, an alkaline salt water meteorite lake in Buldhana district of Maharashtra State in India. The strain was characterised using a polyphasic taxonomic approach which confirmed that it belongs to the genus Streptomyces. Growth was observed over a pH range of 7-11 at 28 A degrees C. The cell wall was found to contain ll-diaminopimelic acid and traces of meso-diaminopimelic acid. The major fatty acid components were identified as iso-C-16:0 (46.8 %), C-17:1 (12.4 %), anteiso-C-15:0 (5.1 %) and anteiso-C-17:1 (4.8 %). The major polar lipids were identified as diphosphatidylglycerol, phosphatidylethanolamine, phosphatidylglycerol and phosphatidylinositol. The major menaquinones were determined to be MK-9 (H-6) (70.3 %), MK-9 (H-4) (15.5 %) and MK-9 (H-8) (7.2 %). The G+C content of the DNA of the type strain was determined to be 71.4 mol %. The 16S rRNA gene sequence has been deposited in GenBank with accession number FJ919811. Although the 16S rRNA gene sequence analysis revealed that strain NCL716(T) shares > 99 % similarity with that of Streptomyces bohaiensis strain 11A07(T), DNA-DNA hybridization revealed only 33.2 +/- A 3.0 % relatedness between them. Moreover, these two strains can be readily distinguished by some distinct phenotypic characteristics. Hence, on the basis of phenotypic and genetic analyses, it is proposed that strain NCL716(T) represents a novel species of the genus Streptomyces, for which the name Streptomyces lonarensis sp. nov., is proposed. The type strain is NCL 716(T) (=DSM 42084(T) = MTCC 11708(T) = KCTC 39684(T)).
Keywords: Alkaliphile; DDH analysis; Polyphasic taxonomy; Streptomyces lonarensis sp nov.

Structural analysis of a penicillin V acylase from pectobacterium atrosepticum confirms the importance of two Trp residues for activity and specificity - Avinash, Vellore Sunder; Panigrahi, Priyabrata; Chand, Deepak; Pundle, Archana; Suresh, Cheravakattu Gopalan; Ramasamy, Sureshkumar (Journal of Structural Biology, 2016)
Penicillin V acylases (PVA) catalyze the deacylation of the beta-lactam antibiotic phenoxymethylpenicillin (Pen V). They are members of the Ntn hydrolase family and possess an N-terminal cysteine as the main catalytic nucleophile residue. They form the evolutionarily related cholylglycine hydrolase (CGH) group which includes bile salt hydrolases (BSH) responsible for bile deconjugation. Even though a few PVA and BSH structures have been reported, no structure of a functional PVA from Gram-negative bacteria is available. Here, we report the crystal structure of a highly active PVA from Gram-negative Pectobacterium atrosepticum (PaPVA) at 2.5 angstrom resolution. Structural comparison with PVAs from Gram-positive bacteria revealed that PaPVA had a distinctive tetrameric structure and active site organization. In addition, mutagenesis of key active site residues and biochemical characterization of the resultant variants elucidated the role of these residues in substrate binding and catalysis. The importance of residue Trp23 and Trp87 side chains in binding and correct positioning of Pen V by PVAs was confirmed using mutagenesis and substrate docking with a 15 ns molecular dynamics simulation. These results establish the unique nature of Gram-negative CGHs and necessitate further research about their substrate spectrum. (C) 2015 Elsevier Inc. All rights reserved.
Keywords: Aromatic stacking; Cholylglycine hydrolase; molecular dynamics; Mutagenesis; Oligomeric interactions

Structural insight of NICD-MAML interactions: virtual screening, docking and molecular dynamics study for the identification of potential inhibitor - Sinha, Noopur; Chowdhury, Saikat; Sarkar, Ram Rup (Letters in Drug Design & Discovery, 2016)
Activation of Notch signalling pathway is triggered by binding of NICD to transcription factor CSL and transcriptional co-activator MAML, which involves in various biological functions as well as progression of diseases. Recent prediction shows suppression of cancer causing genes of this pathway through inhibition of NICD-MAML interaction. Through virtual screening against ``NCI Diversity 3'' of Zinc database, we identified a potential inhibitor ``ZINC01690699'' (1-N,4-N-bis[3-(1H-benzimidazol-2-yl)phenyl]benzene-1,4-dicarboxamide; 1-N, 4-dicarboxamide) possessing highest binding affinity to block the two distinct Binding Sites of NICD to inhibit NICD-MAML interaction and also found the most imperative and essential Binding Site (Site I). Inhibition of this interaction caused by binding of ZINC01690699 is validated by protein-protein docking and the prolonged binding as well as stability of NICD-Inhibitor complex is supported by molecular dynamics simulation. The study not only identifies the best inhibitor but also proposes a potential drug for the treatment of cancers.
Keywords: free energy of binding; MAML; NICD; Notch signalling; potential inhibitor; ZINC01690699

Structural insights and functional implications of inter-individual variability in beta(2)-adrenergic receptor - Tandale, Aditi; Joshi, Manali; Sengupta, Durba (Scientific Reports, 2016)
The human beta(2)-adrenergic receptor (beta(2)AR) belongs to the G protein-coupled receptor (GPCR) family and due to its central role in bronchodilation, is an important drug target. The inter-individual variability in beta(2)AR has been implicated in disease susceptibility and differential drug response. In this work, we identified nine potentially deleterious non-synonymous single nucleotide polymorphisms (nsSNPs) using a consensus approach. The deleterious nsSNPs were found to cluster near the ligand binding site and towards the G-protein binding site. To assess their molecular level effects, we built structural models of these receptors and performed atomistic molecular dynamics simulations. Most notably, in the Phe290Ser variant we observed the rotameric flip of Trp286(6.48), a putative activation switch that has not been reported in beta(2)AR thus far. In contrast, the variant Met82Lys was found to be the most detrimental to epinephrine binding. Additionally, a few of the nsSNPs were seen to cause perturbations to the lipid bilayer, while a few lead to differences at the G-protein coupling site. We are thus able to classify the variants as ranging from activating to damaging, prioritising them for experimental studies.

Structural-functional insights and studies on saccharide binding of Sophora japonica seed lectin - Yadav, Priya; Shahane, Ganesh; Ramasamy, Sureshkumar; Sengupta, Durba; Gaikwad, Sushama (International Journal of Biological Macromolecules, 2016)
Functional and conformational transitions of the Sophora japonica seed lectin (SJL) were studied in detail using bioinformatics and biophysical tools. Homology model of the lectin displayed all the characteristics of the legume lectin monomer and the experimental observations correlated well with the structural information. In silico studies were performed by protein-ligand docking, calculating the respective binding energies and the residues involved in the interactions were derived from LigPlot(+) analysis. Fluorescence titrations showed three times higher affinity of T-antigen disaccharide than N-acetyl galactosamine (GaINAc) towards SJL indicating extended sugar binding site of the lectin. Thermodynamic parameters of T-antigen binding to SJL indicated the process to be endothermic and entropically driven while those of GaINAc showed biphasic process. SDS-PAGE showed post-translationally modified homotetrameric species of the lectin under native conditions. In presence of guanidine hydrochloride (0.5-5.0 M), the tetramer first dissociated into dimers followed by unfolding of the protein as indicated by size exclusion chromatography, fluorescence and CD spectroscopy. Different structural rearrangements were observed during thermal denaturation of SJL at physiological pH 7.2, native pH 8.5 and molten globule inducing pH 1.0. Topological information revealed by solute quenching studies at respective pH indicated differential hydrophobic environment and charge density around tryptophan residues. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Dissociation; docking; Homology model; Ligand binding; Sophora japonica seed lectin; Thermal transitions

Studies of synergy between metal-support interfaces and selective hydrogenation of HMF to DMF in water - Goyal, Reena; Sarkar, Bipul; Bag, Arijit; Siddiqui, Nazia; Dumbre, Deepa K.; Lucas, Nishita; Bhargava, Suresh Kumar; Bordoloi, Ankur (Journal of Catalysis, 2016)
Metal-support interfaces play a very important role in heterogeneous catalysis. The interfacial interactions not only are responsible for stabilizing the necessary oxidation state to facilitate the reaction but also enhance the stability of the catalyst system. Nano dispersion of Ni on mesoporous nitrogen-rich carbon material has been achieved using two different synthesis methods. It was observed that nickel (0) gets stabilized by strong interfacial interaction with the nitrogen atoms of the support material, and the material was found to be very economic and efficient for the conversion of HMF to DMF in aqueous medium. The material shows >= 99% conversion to 5-(hydroxymethyl) furfural (HMF) within 6 h of reaction with 98.7% DMF selectivity. A unique correlation between synthesis methods and particle sizes with catalytic performance has been observed for these newly developed materials. Furthermore, a DFT calculation has been performed to predict the reaction mechanism. (C) 2016 Elsevier Inc. All rights reserved.
Keywords: biofuels; Biomass; Hydrogenation; mesoporous carbon; Ni-CNx

Studies on the static and dynamic properties of different types of polyester industrial yarns - Samui, Barun Kumar; Dasgupta, Saikat; Mukhopadhyay, R.; Ramesh, C.; Chakrabarty, Debabrata (Journal of the Textile Institute, 2016)
Four major types of polyester industrial yarns, viz. high tenacity (HT), high modulus low shrinkage (HMLS), low shrinkage (LS) and super low shrinkage (SLS) polyester yarns, were studied for their static and dynamic properties. An attempt has been made to establish a linkage between static and dynamic properties of these yarns with its structure and with its end applications. HMLS and HT polyester yarns have lower tan delta and work loss, which are the desired characteristics required for its end applications which include tire and conveyer belt. Higher overall orientation and higher fraction of tie molecules helped to achieve these properties in HT and HMLS polyester yarns. LS and SLS polyester yarns are mostly used for static applications. Low thermal shrinkage is the key requirement for the downstream processes of these yarns. Lower amorphous orientation in these two yarns is primarily responsible for achieving very low thermal shrinkage. A good co-relation has been established between the peak temperature of work loss (in slow speed hysteresis test) and the peak temperature of tan delta (in high-speed dynamic test).
Keywords: creep; modulus; polyester; shrinkage; tan delta; work loss

Sunlight assisted degradation of dye molecules and reduction of toxic Cr(VI) in aqueous medium using magnetically recoverable Fe3O4/reduced graphene oxide nanocomposite - Boruah, Purna K.; Borthakur, Priyakshree; Darabdhara, Gitashree; Kamaja, Chaitanya Krishna; Karbhal, Indrapal; Shelke, Manjusha V.; Phukan, Pallabi; Saikia, Dulen; Das, Manash R. (RSC Advances, 2016)
In view of the significant impact of magnetically recoverable catalysts in photocatalytic applications, Fe3O4/reduced graphene oxide (rGO) nanocomposite photocatalyst was synthesized by adopting an eco-friendly solution chemistry approach and has been characterized by high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and photoluminescence (PL) spectroscopy. Fe3O4/rGO nanocomposite is efficiently utilized towards photocatalytic degradation of carcinogenic and mutagenic cationic as well as anionic dye molecules namely methyl green (MG), methyl blue (MB) and rhodamine B (RhB) under direct sunlight irradiation. The Fe3O4/rGO nanocomposite also demonstrated excellent photocatalytic reduction of aqueous Cr(VI) solution to nontoxic aqueous Cr(III) solution of more than 96% within 25 min under sunlight irradiation. Moreover, reusability of the magnetically recovered photocatalyst was studied efficiently up to 10 cycles in the degradation process. The catalyst was also characterized after the degradation of the dye molecule and the particle size of the Fe3O4 nanoparticles on the rGO sheets remained unchanged. The present investigation focuses on the importance of the use of Fe3O4/rGO nanocomposite towards photocatalytic degradation of waste water containing organic dye pollutants and toxic Cr(VI), as an easily recoverable and reusable photocatalyst with potential for many environmental remediation applications.

Supramolecular metallogel that imparts self-healing properties to other gel networks - Feldner, Tobias; Haering, Marleen; Saha, Subhadeep; Esquena, Jordi; Banerjee, Rahul; Diaz, David Diaz (Chemistry of Materials, 2016)
A unique proton conductive and moldable supramolecular metallogel (CuA-Ox-gel) made upon mixing at room temperature well-defined stock solutions of Cu(OAc)(2). H2O and oxalic acid dehydrate was found to have self-healing properties. Remarkably, the system also displayed an unprecedented ability to impart self-healing properties to other gel networks lacking this capacity. A self-healed CuA-Ox metallogel was found to have essentially the same nanofibrillar morphology, thermal stability, rheological properties, and conductivity as the freshly prepared sample. The discovery also allowed the fabrication of self-healing conductive composites containing conductive carbonaceous materials. Overall, this work serves as a proof of concept for the transfer of self-healing properties between completely different gel networks.

Surface modification of aligned CdO nanosheets and their enhanced field emission properties - Bagal, Vivekanand S.; Patil, Girish P.; Deore, Amol B.; Suryawanshi, Sachin R.; Late, Dattatray J.; More, Mahendra A.; Chavan, Padmakar G. (RSC Advances, 2016)
Porous aligned CdO nanosheets were grown on a cadmium (Cd) substrate by the simple and cost effective method of thermal annealing. Further, decoration of gold (Au) nanoparticles on the porous aligned CdO nanosheets (specimen A) was achieved by coating with a Au thin film and subsequent annealing treatment. The average diameters of decorated Au nanoparticles were found to be 15 nm, 21 nm and 28 nm for the Au thin films with 20 s, 40 s and 60 s (specimens B, C, and D) coating times. Detailed characterizations, such as structural and morphological analysis of porous CdO nanosheets and Au/CdO nanocomposite (Au decorated porous CdO nanosheets), have been carried out using a Field Emission Scanning Electron Microscope (FESEM), X-ray diffraction (XRD) and a Transmission Electron Microscope (TEM). Field emission studies of specimens A, B, C and D were carried out in the planar diode configuration. Turn-on fields of 1.9 V mu m(-1), 1.1 V mu m(-1), 2.4 V mu m(-1) and 2.8 V mu m(-1) have been found for the emission current density of 10 RA cm(-2) for specimens A, B, C and D, respectively. The observed low turn -on field of specimen B (Au diameter of 15 nm) was found to be superior to other semiconducting nanostructures reported in the literature. The field emission current stability over a period of 3 h at the preset current density of 1 RA cm(-2) is found to be excellent for all specimens. To the best of our knowledge, field emission studies along with surface modification of porous aligned CdO nanosheets have not been reported in the literature. The simple synthesis route, facile surface modification and the superior field emission results make the present emitter very suitable for micro/nano electronic devices.

Switch-on NIR probe for specific detection of Hg2+ ion in aqueous medium and in mitochondria - Agarwalla, Hrideshg; Mahajan, Pankaj S.; Sahu, Debashis; Taye, Nandaraj; Ganguly, Bishwajit; Mhaske, Santosh B.; Chattopadhyay, Samit; Das, Amitava (Inorganic Chemistry, 2016)
A new 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based probe molecule (L) is synthesized for specific binding to Hg2+ ion in physiological condition with an associated luminescence ON response in the near-IR region of the spectrum. Appropriate functionalization in the 5-position of each of two pyrrole moieties with styryl functionality in a BODIPY core helped us in achieving the extended conjugation and a facile intramolecular charge transfer transition with a narrow energy gap for frontier orbitals. This accounted for a poor emission quantum yield for the probe molecule L. Binding to. Hg2+ helped in interrupting the facile intramolecular charge transfer (ICT) process that was initially operational for L. This resulted in a hypsochromic shift of absorption band and a turn-on luminescence response with lambda(Em)(max) of 650 nm on specific binding to Hg2+. Observed spectral changes are rationalized based on quantum chemical calculations. Interestingly, this reagent is found to be localized preferentially in the mitochondria of the live human colon cancer (Hct116) cells. Mitochondria is one of the major targets for localization of He2+, which actually decreases the mitochondrial membrane potential and modifies various proteins having sulfudryl functionality(ies) to cause cell apoptosis. Considering these, ability of the present reagent to specifically recognize Hg2+] in the mitochondrial region of the live Hct116 cells has significance.

Synthesis and antitubercular activity of new 1,3,4-oxadiazoles bearing pyridyl and thiazolyl scaffolds - Dhumal, Sambhaji T.; Deshmukh, Amarsinh R.; Bhosle, Manisha R.; Khedkar, Vijay M.; Nawale, Laxman U.; Sarkar, Dhiman; Mane, Ramrao A. (Bioorganic & Medicinal Chemistry Letters, 2016)
In search of more potent and safe new antitubercular agents, here new 2-pyridinyl substituted thiazolyl-5-aryl-1,3,4-oxadiazoles (6a-o), have been designed and synthesized using thionicotinamide as a starting, following novel multistep synthetic route. An intermediate, pyridinyl substituted thiazolyl acid hydrazide (4) when condensed with benzoic acids/nicotinic acids (5a-o) in the presence of silica supported POCl3 yielded better to excellent yields of the title compounds. All the synthesized compounds (6a-o) and intermediate acid hydrazide (4) have been screened for their in vitro antitubercular activity against Mycobacterium tuberculosis H37Ra (MTB) and Mycobacterium bovis BCG. Amongst them, 6f, 6j, 6l and 6o have revealed promising activity against M. bovis BCG at concentrations less than 3 mu g/mL. These compounds have shown low cytotoxicity (CC50: > 100 mu g/mL) towards four human cancer cell lines. Molecular docking study has also been performed against mycobacterial enoyl reductase (InhA) enzyme to gain an insight into the binding modes of these molecules and recorded good binding affinity. The ADME properties the title products have also been analyzed. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: 1; 3; 4-Oxadiazole; Antitubercular activity; Cytotoxicity; Molecular docking; Pyridine; Thiazole

Synthesis and antitubercular activity of new benzo[b]thiophenes - Mahajan, Pravin S.; Nikam, Mukesh D.; Nawale, Laxman U.; Khedkar, Vijay M.; Sarkar, Dhiman; Gill, Charansingh H. (ACS Medicinal Chemistry Letters, 2016)
In vitro and ex vivo efficacies of four series of benzo[b]thiophene-2-carboxylic acid derivatives were studied against Mycobacterium tuberculosis H37Ra (MTB). Benzo[b]thiophenes were also tested in vitro against multidrug resistant Mycobacterium tuberculosis H37Ra (MDR-MTB), and 7b was found to be highly active against A- and DMDR-MTB/MTB (MIC ranges 2.73-22.86 mu g/mL). The activity of all benzo[b]-thiophenes against M. bovis BCG (BCG) was also assessed grown under aerobic and under conditions of oxygen depletion. Compounds 8c and 8g showed significant activity with MICs of 0.60 and 0.61 mu g/mL against dormant BCG. The low cytotoxicity and high selectivity index data against human cancer cell lines, HeLa, Panc-1, and THP-1 indicate the potential importance of the development of benzo[b]thiophene-based 1,3-diketones and flavones as lead candidates to treat mycobacterial infections. Molecular docking studies into the active site of DprE1 (Decaprenylphosphoryl-beta-n-ribose-2'-epimerase) enzyme revealed a similar binding mode to native ligand in the crystal structure thereby helping to understand the ligand protein interactions and establish a structural basis for inhibition of MTB. In summary, its good activity in in vitro and ex vivo model, as well as its activity against multidrug-resistant M. tuberculosis H37Ra in a potentially latent state, makes 7b an attractive drug candidate for the therapy of tuberculosis.
Keywords: Benzo[b]thiophene; Cytotoxicity; M. Bovis BCG; MDR-MTB; Molecular docking

Synthesis and bioactivity of novel triazole incorporated benzothiazinone derivatives as antitubercular and antioxidant agent - Shaikh, Mubarak H.; Subhedar, Dnyaneshwar D.; Arkile, Manisha A.; Khedkar, Vijay M.; Jadhav, Nandadeep J.; Sarkar, Dhiman; Shingate, Bapurao B. (Bioorganic & Medicinal Chemistry Letters, 2016)
In search of new active molecules against Mycobacterium tuberculosis (MTB) H37Ra and M. bovis BCG, a small focused library of benzothiazinone based 1,2,3-triazoles has been efficiently prepared via click chemistry approach. Several derivatives were found to be promising inhibitors of MTB and M. bovis BCG characterized by lower MIC values (27.34-29.37 mu g/mL). Among all the synthesized compounds, 6c and 6e is the most active compound against MTB and M. bovis BCG. The compounds were further tested for anti-proliferative activity against HeLa, A549 and A431 cell lines using MTT assay and showed no significant cytotoxic activity at the maximum concentration evaluated. Further, the synthesized compounds were found to have potential antioxidant activity with IC50 range = 14.14-47.11 mu g/mL. Furthermore, to rationalize the observed biological activity data, the molecular docking study also been carried out against a potential target MTB DprE1, which revealed a significant correlation between the binding score and biological activity for these compounds. The results of the in vitro and in silico study suggest that the triazole incorporated benzothiazinone may possess the ideal structural requirements for further development of novel therapeutic agents. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: 1; 2; 3-Triazole; ADME prediction; Antioxidant; Antitubercular; Docking study

Synthesis and characterization of nanoporous silica SBA-15 diaminocyclohexane and its application in removal of Cu(II) and Ni(II) from aqueous solution - Sreenu, Bhogineni; Sharma, Priti; Seshaiah, Kalluru; Singh, A. P. (Desalination and Water Treatment, 2016)
A new nanoporous 1,2-diaminocyclohexane-functionalized SBA-15 (Dach@SBA-15) silica sorbent was prepared. The structure and physicochemical properties of the material were characterized by elemental analysis, X-ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy, FT-IR spectroscopy, nitrogen adsorption-desorption isotherms and thermogravimetric analysis. TEM image clearly showed the sheet-like structure of Dach@SBA-15. The organic functional groups were successfully grafted onto the SBA-15 surface and the ordering of the support was not affected by the chemical modification. The Dach@SBA-15was used as a sorbent for removal of Cu(II) and Ni(II) from aqueous solution. Experimental parameters like effect of pH, contact time and metal ion concentration were studied and optimized. The adsorption isotherm data fitted well to Langmuir isotherm model and the monolayer adsorption capacity values for Cu(II) was 90.09 and for Ni (II) was 84.03 mg/g at 303 K. The experimental kinetic data fitted very well to the pseudosecond- order model. The Dach@SBA-15 could be used as a sorbent for removal of Cu(II) and Ni(II) from aqueous medium.
Keywords: Adsorption; BET; FAAS; FT-IR; Heavy metals; Nanoporous silica

Synthesis and characterization of novel polymer-hybrid silver nanoparticles and its biomedical study - Verma, Suresh Kumar; Jha, Ealisha; Kiran, K. J.; Bhat, Suresh; Suar, Mrutyunjay; Mohanty, P. S. (Materials Today: Proceedings, 2016)
Hybrid polymer metal nanoparticles have advantages over conventional metal nanoparticles with respect to their stability, chemical resistance, antibacterial activity and drug delivery properties. In the current work, we have synthesized novel stimuli-responsive polymer hybrid silver nanoparticles using green synthesis method, where the plant extract is used as a reducing agent in the synthesis. Encapsulating metal nanoparticles with stimuli-responsive soft-polymeric system is novel and provides additional versatility whose functions and properties can be tailored by controlling any of the stimuli such as pH, temperature, ionic strength with respect to their antibacterial activity and physiological condition. Moreover, green synthesis methods have advantages over conventional methods involving chemical reducing agents that are often associated with environmental toxicity because of their enhanced antibacterial and other biological effects. The synthesized hybrid particles were characterized using Dynamic light scattering, UV-Visible spectroscopy and Small angle x-ray scattering. Further, we have investigated the antibacterial and cytotoxicity effect of these hybrid particles against different bacterial cells ( Salmonella) and mammalian cell lines (HCT116) respectively. These results are discussed in the light of previous studied work and these results suggest that our synthesized polymer hybrid nanoparticles are more antibacterial and less cytotoxic than the usual silver nanoparticles. (C) 2015Elsevier Ltd.All rights reserved.
Keywords: Antibacterial effect; Cytotoxicity; Polymeric hybrid particless; silver nanoparticles

Synthesis and characterization of simple cost-effective trans-A(2)BC porphyrins with various donor groups for dye-sensitized solar cells - Kumar, Ravi; Sankar, Muniappan; Sudhakar, Vediappan; Krishnamoorthy, Kothandam (New Journal of Chemistry, 2016)
We have designed and synthesized a series of simple cost-effective 'push-pull' Zn(II) porphyrin dyes containing various electron donors such as 2-thienyl, pyrenyl, phenyl, 4'-bromophenyl, 4'-tbutylphenyl and 4'-carboxyphenyl acceptor moieties in three steps. Their optical absorption spectra, electrochemical redox and photovoltaic properties have been investigated in detail. The overall power conversion efficiencies (Z) of DSSCs based on these dyes are in the range of 2.1 to 4.2% and highly depend on their donor moiety. The incorporation of trans-10,20-dimesityl groups is highly beneficial for preventing the p-p aggregation among the porphyrin moieties, thus favorably suppressing the charge recombination and intermolecular interaction. Among all, pyrenyl appended Zn(II) porphyrin has exhibited a higher power conversion efficiency of 4.2% under 1 sun illumination due to the extended p-conjugation and electron donating ability of the pyrenyl moiety.

Synthesis and characterization of well-defined random and block copolymers of epsilon-caprolactone with l-lactide as an additive for toughening polylactide: Influence of the molecular architecture - Deokar, Megha D.; Idage, Susheela B.; Idage, Bhaskar B.; Sivaram, Swaminathan (Journal of Applied Polymer Science, 2016)
Well-defined multiarmed star random and block copolymers of epsilon-caprolactone with l-lactide with controlled molecular weights, low polydispersities, and precise numbers of arms were synthesized by the ring-opening polymerization of respective cyclic ester monomers. The polymers were characterized by H-1-NMR and C-13-NMR to determine their chemical composition, molecular structure, degree of randomness, and proof of block copolymer formation. Gel permeation chromatography was used to establish the degree of branching. Star-branched random copolymers exhibited lower glass-transition temperatures (T-g's) compared to a linear random copolymer. When the star random copolymers were melt-blended with poly(l-lactic acid) (PLA), we observed that the elongation of the blend increased with the number of arms of the copolymer. Six-armed block copolymers, which exhibited higher T-g's, caused the maximum improvement in elongation. In all cases, improvements in the elongation were achieved with no loss of stiffness in the PLA blends. (c) 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43267.
Keywords: biodegradable; copolymers; differential scanning calorimetry; mechanical properties; ring-opening polymerization

Synthesis and docking studies of pyrazine-thiazolidinone hybrid scaffold targeting dormant tuberculosis - Chitre, T. S.; Asgaonkar, K. D.; Miniyar, P. B.; Dharme, A. B.; Arkile, Manisha A.; Yeware, A.; Sarkar, Dhiman; Khedkar, Vijay M.; Jha, Prakash C. (Bioorganic & Medicinal Chemistry Letters, 2016)
The persistence of Mycobacterium tuberculosis (MTB) in dormant stage assists the pathogen to develop resistance against current antimycobactrial drugs. To address this issue, we report herein the synthesis of N-(4-oxo-2 substituted thiazolidin-3yl) pyrazine-2-carbohydrazide derivatives designed by following the molecular hybridization approach using pyrazine and thiazolidenone scaffolds. The compounds were evaluated against MTB H37Ra and Mycobacterium bovis BCG in dormancy model. Most of the compounds had IC50 values in 0.3-1 mu g/ml range. The active compounds were further tested for anti-proliferative activity against THP-1, Panc-1, A549, and MCF-7 cell lines using MTT assay and exhibited no significant cytotoxicity. We also report molecular docking studies using active analogs and MTB Decaprenylphosphoryl-beta-D-ribose-2'-epimerase (DprE1) to rationalize the biological activity and to provide an insight into the probable mechanism of action and binding mode of hybridized structures. The results obtained validate the use of molecular hybridization approach and also suggest that reported compounds can provide a novel pharmacophore to synthesize lead compounds against dormat MTB. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: docking; Dormant; Hybrid design; Pyrazine; Thiazolidenone; tuberculosis

Synthesis and evaluation of thieno[2,3-d]pyrimidin-4(3H)-ones as potential antitubercular agents (vol 6, pg 2209, 2015) - Borate, Hanumant B.; Annadate, Ritesh A.; Vagh, Sandip S.; Pisal, Mahesh M.; Deokate, Sagar B.; Arkile, Manisha A.; Jadhav, Nandadeep J.; Nawale, Laxman U.; Sarkar, Dhiman (Medchemcomm, 2016)

Synthesis and properties of poly(arylene ether)s based on 3-pentadecyl 4,4'-biphenol - Tawade, Bhausaheb V.; Shaligram, Sayali V.; Valsange, Nitin G.; Kharul, Ulhas K.; Wadgaonkar, Prakash P. (Polymer International, 2016)
A new biphenol, 3-pentadecyl 4,4-biphenol, was synthesized starting from 3-pentadecylphenol and was polycondensed with 4,4-difluorobenzophenone, 1,3-bis(4-fluorobenzoyl)benzene and bis(4-fluorophenyl)sulfone to obtain poly(arylene ether)s with biphenylene linkages in the backbone and pendent pentadecyl chains. Inherent viscosities and number-average molecular weights (M-n) of the poly(arylene ether)s were in the range 0.50 - 0.81 dL g(-1) and 2.2 x 10(4) - 8.3 x 10(4), respectively. Detailed NMR spectroscopic studies of the poly(arylene ether)s indicated the presence of constitutional isomerism which existed because of the non-symmetrical structure of 3-pentadecyl 4,4-biphenol. The poly(arylene ether)s readily dissolved in common organic solvents such as dichloromethane, chloroform and tetrahydrofuran and could be cast into tough, transparent and flexible films from their chloroform solutions. The poly(arylene ether)s exhibited T-g values in the range 35-60 degrees C which are lower than that of reference poly(arylene ether)s without pentadecyl chains. The 10% decomposition temperatures (T-10) of the poly(arylene ether)s were in the range 410-455 degrees C indicating their good thermal stability. A gas permeation study of poly(ether sulfone) containing pendent pentadecyl chains revealed a moderate increase in permeability for helium, hydrogen and oxygen. However, there was a large increase in permeability for carbon dioxide which could be attributed to the internal plasticization effect of pendent pentadecyl chains. (c) 2016 Society of Chemical Industry
Keywords: cashew nut shell liquid (CNSL); gas permeation study; pentadecyl; poly(arylene ether)s; thermal stability

Synthesis and study of calixarene-doped polypyrrole-TiO2/ZnO composites: antimicrobial activity and electrochemical sensors - Waghmode, Babasaheb J.; Husain, Zahid; Joshi, Meenal; Sathaye, Shivaram D.; Patil, Kashinath R.; Malkhede, Dipalee D. (Journal of Polymer Research, 2016)
The present communication describes the synthesis of an electroactive nanocomposite of calixarene- doped polypyrrole ( PPY) containing an oxide of Ti/ Zn. The additive TiO2/ ZnO serves as an oxidizing agent for the polymerization, thus avoiding the use of hazardous organic solvents while calixarene doping stabilizes the polymer. The materials synthesized herein were characterized by UV- visible spectroscopy, FT- IR spectroscopy, scanning electron microscopy ( SEM), transmission electron microscopy ( TEM), energy- dispersive X- ray spectroscopy ( EDX), X- ray photoelectron spectroscopy ( XPS), and cyclic voltammetry ( CV) of synthesized nanocomposites. It was revealed that the resulting calixarene- doped polypyrrole- TiO2/ ZnO nanocomposite has ( 1) long- time stability, ( 2) significant electrochemical activity for sensing formaldehyde, and ( 3) good antimicrobial activity.

Synthesis and tyrosinase inhibition activity of trans-stilbene derivatives - Ismail, Tabasum; Shafi, Syed; Srinivas, Jada; Sarkar, Dhiman; Qurishi, Yasrib; Khazir, Jabeena; Alam, Mohammad Sarwar; Kumar, Halmuthur Mahabalarao Sampath (Bioorganic Chemistry, 2016)
Synthesis of a focussed library of trans-stilbene compounds through Wittig and other base catalysed condensation reactions is presented. The synthesized stilbenes were screened for their inhibitory potential against murine tyrosinase activity to explore the structure activity relationship (SAR). Presence of electron withdrawing group (-CN) at the double bond and hydroxyl group or halogen atom especially at para-position on the aromatic rings was found to significantly elevate the inhibitory activity. Among all the compounds screened, compounds 2, 6, 8, 10, 11, 15 and 21 were found to exhibit appreciable inhibitory activity. Compound 21 ((E)-2,3-bis(4-Hydroxyphenyl) acryonitrile) was found to be the most active with an IC50 value of 5.06 mu M which is less than half of the value 10.78 mu M observed for resveratrol (common standard used in murine tyrosinase activity studies) under similar conditions. The results obtained from the present study reveal structural/functional group sensitivity for the tyrosinase inhibitory activity of stilbenoid moieties and are expected to be very helpful for the design and synthesis of novel, selective and effective tyrosinase inhibitors. (C) 2016 Elsevier Inc. All rights reserved.
Keywords: Electron withdrawing groups; Murine tyrosinase activity; Resveratrol; Stilbenoids; Tyrosinase inhibitors; Wittig reaction

Synthesis, biological evaluation and molecular docking of novel coumarin incorporated triazoles as antitubercular, antioxidant and antimicrobial agents - Shaikh, Mubarak H.; Subhedar, Dnyaneshwar D.; Shingate, Bapurao B.; Khan, Firoz A. Kalam; Sangshetti, Jaiprakash N.; Khedkar, Vijay M.; Nawale, Laxman; Sarkar, Dhiman; Navale, Govinda R.; Shinde, Sandip S. (Medicinal Chemistry Research, 2016)
A series of new coumarin-based 1,2,3-triazole derivatives were designed, synthesized and evaluated for their antitubercular activity in vitro against Mycobacterium tuberculosis H37Ra, antioxidant activity by DPPH radical scavenging assay, antimicrobial activity in vitro against three gram-positive bacteria (Staphylococcus aureus, Micrococcus luteus and Bacillus cereus) and three gram-negative bacteria (Escherichia coli, Pseudomonas fluorescens and Flavobacterium devorans as well as three fungi (Aspergillus niger, Penicillium chrysogenum and Curvularia lunata). The bioactive assay showed that some synthesized coumarin triazoles displayed comparable or even better antitubercular, antioxidant, antibacterial and antifungal efficacy in comparison with reference drugs. Furthermore, docking study has been performed against DprE1 enzyme of M. tuberculosis that showed good binding interactions. Moreover, the synthesized compounds were also analyzed for ADME properties and showed potential to build up as good oral drug candidates. New coumarin-based 1,2,3-triazole derivatives were designed, synthesized and evaluated for their antitubercular, antioxidant, antibacterial and antifungal activity. Some of the coumarin-based triazole derivatives displayed comparable or even better efficacy in comparison with reference drugs. Molecular docking study has been performed against DprE1 enzyme of Mycobacterium tuberculosis showed good binding interactions. [GRAPHICS] .
Keywords: 1; 2; 3-Triazole; ADME prediction; Antimicrobial; Antioxidant; Antitubercular; Click chemistry; Docking study

Synthesis, biological evaluation and molecular docking studies of N-acylheteroaryl hydrazone derivatives as antioxidant and anti-inflammatory agents - Mahajan, Pravin S.; Nikam, Mukesh D.; Khedkar, Vijay M.; Jha, Prakash C.; Sarkar, Dhiman; Gill, Charansingh H. (Research on Chemical Intermediates, 2016)
In search of new therapeutics with greater potency, three new series of 3-methyl-1-phenyl-1H-thieno[2,3-c]pyrazole-5-carbohydrazide derivatives have been synthesized and evaluated for their in vitro antioxidant and anti-inflammatory activities. The hydrazones bearing a core pyrazole, chromone and tetrazolo[1,5-a]quinoline scaffold showed promising activities. Interestingly, compounds 3a (EC50 = 06.00 +/- A 2.36) and 5c (EC50 = 07.21 +/- A 0.67) showed the most potent antioxidant activity, while compounds 3a (EC50 = 10.25 +/- A 1.08), 7b (EC50 = 10.50 +/- A 0.99) and 7c (EC50 = 11.18 +/- A 0.15) showed significant anti-inflammatory activity. Furthermore, molecular docking studies also revealed a significant correlation between the binding score and biological activity for these compounds to describe the molecular basis for the structure activity relationship (SAR) results. As these compounds are good cyclooxygenase inhibitors, isoenzyme inhibitory potency studies are warranted.
Keywords: Anti-inflammatory; Antioxidant; Docking study; N-Acylhydrazones; Structure-activity relationship

Synthesis, biological evaluation and molecular docking study of some novel indole and pyridine based 1,3,4-oxadiazole derivatives as potential antitubercular agents - Desai, N. C.; Somani, Hardik; Trivedi, Amit; Bhatt, Kandarp; Nawale, Laxman; Khedkar, Vijay M.; Jha, Prakash C.; Sarkar, Dhiman (Bioorganic & Medicinal Chemistry Letters, 2016)
A series of indole and pyridine based 1,3,4-oxadiazole derivatives 5a-t were synthesized and evaluated for their in vitro antitubercular activity against Mycobacterium tuberculosis H37Ra (MTB) and Mycobacterium bovis BCG both in active and dormant state. Compounds 5b, 5e, 5g and 5q exhibited very good antitubercular activity. All the newly synthesized compounds 5a-t were further evaluated for antiproliferative activity against HeLa, A549 and PANC-1 cell lines using modified MTT assay and found to be noncytotoxic. On the basis of cytotoxicity and MIC values against Mycobacterium bovis BCG, selectivity index (SI) of most active compounds 5b, 5e, 5g and 5q was calculated (SI = GI(50)/MIC) in active and dormant state. Compounds 5b, 5e and 5g demonstrated SI values >= 10 against all three cell lines and were found to safe for advance screening. Compounds 5a-t were further screened for their antibacterial activity against four bacteria strains to assess their selectivity towards MTB. In addition, the molecular docking studies revealed the binding modes of these compounds in active site of enoyl reductase (InhA), which in turn helped to establish a structural basis of inhibition of mycobacteria. The potency, low cytotoxicity and selectivity of these compounds make them valid lead compounds for further optimization. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: 1; 3; 4-Oxadiazole; Antitubercular activity; Cytotoxicity; Indole; Molecular docking; Pyridine

Synthesis, microstructure, optical and field emission studies of iron vanadium oxide nanosheets - Badadhe, Satish S.; Suryawanshi, Sachin R.; Naphade, Rounak A.; Chaudhary, Minakshi V.; More, Mahendra A.; Shelke, Manjusha V.; Ogale, Satishchandra B. (Journal of Physics D-Applied Physics, 2016)
We report a single step growth of thin graphene-like, densely packed FeV3O8 (FVO) nanosheets on silicon substrates via facile hydrothermal synthesis. These nanosheets have dimensions of a few microns with thin edges, offering very high aspect ratio. These FVO nanosheets exhibit excellent field emission behaviour with low turn on and threshold voltages of 1.3 V mu m(-1) and 1.7 V mu m(-1), respectively. The corresponding emitter delivers high emission current density of (similar to 1.650 mA cm(-2)) at fairly low applied field (similar to 4.00 V mu m(-1)).
Keywords: FeV3O8; field emission; nanosheets

Synthesis of Au@Ni bimetallic core shell nanoparticle and nanochains in soyabean oil and their catalytic hydrogenation reactions - Bharathan, Vysakh A.; Yadukiran, V.; Lazar, Anish; Singh, Anand. P.; Vinod, Chathakudath P. (ChemistrySelect, 2016)
Synthesis of Au@Ni bimetallic core shell nanostructures using commercially available soya bean oil as the solvent through a sequential reduction strategy is reported. The energy efficiency and economic viability comes from the much milder temperatures and replacement of expensive and environmentally hazardous solvents like long chain organic amines and acids previously reported for synthesis. Thus, core shell nanoparticles having size regime of 10-15 nm with an excellent control over the nickel shell thickness (2 nm) over the gold core (8-10 nm) and Au@Ni nanochains is achieved. The synthesized materials are demonstrated to synergistically catalyze hydrogenation of nitro and C-C multiple bonds with much better efficiency as compared to individual nanoparticle counterparts.
Keywords: Bimetallic nanoparticles; Gold catalysis; hydrogenation reactions; synergistic effects

Synthesis of new hybrid sorbent 2-mercaptobenzaldehyde SBA-15 and its application in solid phase extraction of Cd(II) from water and food samples - Sreenu, B.; Imran, K.; Seshaiah, K.; Sharma, Priti; Singh, A. P. (Analytical Methods, 2016)
In this paper, a new mesoporous hybrid material was fabricated by anchoring 2-mercaptobenzaldehyde (2MB) onto the surface of SBA-15. The adsorbent (2MB-SBA-15) was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherm measurements and thermogravimetric analysis (TGA) and applied as a sorbent in the preconcentration of Cd(II) in water samples and food samples. The effect of various analytical parameters such as pH, dose of sorbent, amount of eluent, sample flow rate and interfering ions was investigated. The preconcentration capacity of the prepared material under optimized conditions for Cd(II) was 0.94 +/- 0.01 mmol g(-1). The Cd collected onto the sorbent was eluted out with 10 mL of 1 M HNO3 and determined by AAS. The LOD, LOQ and preconcentration factor of the present method were found to be 6.93 x 10(-6), 1.21 x 10(-5) mM and 100, respectively. The relative standard deviation for four preconcentration experiments was found to be <= 5%.

Synthesis of Ni-doped ZnO nanostructures by low-temperature wet chemical method and their enhanced field emission properties - Rana, Amit Kumar; Bankar, Prashant; Kumar, Yogendra; More, Mahendra A.; Late, Dattatray J.; Shirage, Parasharam M. (RSC Advances, 2016)
In this study, we report an enhancement in the field emission (FE) properties of ZnO nanostructures obtained by doping with Ni at a base pressure of similar to 1 x 10(-8) mbar, which were grown by a simple wet chemical process. The ZnO nanostructures exhibited a single-crystalline wurtzite structure up to a Ni doping level of 10%. FESEM showed a change in the morphology of the nanostructures from thick nanoneedles to nanoflakes via thin nanorods with an increase in the Ni doping level in ZnO. The turn-on field required to generate a field emission (FE) current density of 1 mu A cm(-2) was found to be 2.5, 2.3, 1.8 and 1.7 V mu mcm(-2) for ZnO (Ni0%), ZnO (Ni5%), ZnO (Ni7.5%) and ZnO (Ni10%), respectively. A maximum current density of similar to 872 mu A cm(-2) was achievable, which was generated at an applied field of 3.1 V mu m cm(-2) for a Ni doping level of 10% in ZnO. Long-term operational current stability was recorded at a preset value of 5 mA for a duration of 3 h and was found to be very high. The experimental results indicate that Ni-doped ZnO-based field emitters can open up many opportunities for their potential use as an electron source in flat panel displays, transmission electron microscopy, and the generation of X-rays. Thus, the simple low-temperature (similar to 80 degrees C) wet chemical synthesis approach and the robust nature of the ZnO nanostructure field emitter can provide prospects for the future development of cost-effective electron sources.

Synthesis of novel Cu2S nanohusks as high performance counter electrode for CdS/CdSe sensitized solar cell - Kamaja, Chaitanya Krishna; Devarapalli, Rami Reddy; Dave, Yasha; Debgupta, Joyashish; Shelke, Manjusha V. (Journal of Power Sources, 2016)
An important component of quantum dot sensitized solar cells (QDSSC) is the counter electrode which mediates the regeneration of oxidized quantum dots by reducing the polysulphide electrolyte. However, design and synthesis of an efficient counter electrode material is a challenging task. Herein, we report the synthesis of a unique Cu2S nanohusks directly on FTO coated glass substrates by electrodeposition and used as a counter electrode in QDSSC. When these electrodes are used for the reduction of polysulfide electrolyte in QDSSC, they exhibit higher catalytic activity and photovoltaic performance as compared to the Platinum counter electrode. The power conversion efficiency of about 4.68% has been achieved by optimizing the deposition time of Cu2S. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: counter electrode; Cu2S electrodeposition; Cu2S nanohusks; Quantum dot-sensitized solar cell

Synthesis of ophiocerins A, B and C, botryolide E, decarestrictine O, stagonolide C and 9-epi-stagonolide C employing chiral hexane-1,2,3,5-tetraol derivatives as building blocks - Show, Krishanu; Kumar, Pradeep (European Journal of Organic Chemistry, 2016)
An organocatalytic approach to the synthesis of (2R,3S)-hexane-1,2,3,5-tetraol (11) derivatives (in the forms of different stereoisomers and bearing different protecting groups) has been developed. The key chiral intermediates 11 were prepared with complete stereocontrol through the proline-catalyzed intermolecular aldol reaction between acetone and d-glyceraldehyde acetonide. The synthetic utility of the intermediates was demonstrated by their transformation into the title hydroxylated pyrans and a variety of unsaturated lactones through standard synthetic protocols.

Synthesis of renewable copolyacetals with tunable degradation - Rajput, Bhausaheb S.; Chander, Umesh; Arole, Kailash; Stempfle, Florian; Menon, Shamal K.; Mecking, Stefan; Chikkali, Samir H. (Macromolecular Chemistry and Physics, 2016)
Acetal metathesis copolymerization (AMCP) of renewable isohexide diacetals and aliphatic long-chain diacetals is reported and access to a small family of copolyacetals has been established. Crucial 1-2D NMR and MALDI-ToF-MS findings unambiguously confirm the existence of a copolymeric structure. In a stark contrast to the earlier reported isohexide-polyacetals, the current copolyacetals reveal very slow degradation. Hydrolytic degradation of copolyacetal pellets is extremely slow at pH 7, whereas only 30% degradation over a period of 15 d is observed in 9 M hydrochloric acid solution. GPC investigations reveal that with increasing chain-length the rate of degradation reduces, whereas copolyacetals with short-chain aliphatic segments display a faster degradation profile. The reduced rate of degradation can be attributed to the hydrophobic nature of long-chain acetal segments. In situ NMR spectroscopy reveals the existence of formates, hemiacetals, and diols as degradation products. Thus, the rate of degradation can be tuned by the judicious choice of isohexide-diacetal and linear-diacetals in a copolyacetal.
Keywords: copolyacetals; degradable polymers; diacetals; isohexides; renewable polymers

Synthesis of silicon(II) compounds and their reactions - Sen, Sakya S.; Roesky, Herbert W. (Efficient methods for preparing silicon compounds, 2016)

Synthesis of Sn-containing anatase (TiO2) by sol-gel method and their performance in catalytic water splitting under visible light as a function of tin content - Tangale, N. P.; Niphadkar, P. S.; Samuel, V.; Deshpande, Suvarna S.; Joshi, P. N.; Awate, S. V. (Materials Letters, 2016)
Sol-gel route was employed to prepare a series of Sn-containing anatase with different molar (Ti/Sn) ratios ranging from 49 to 1. Samples were characterized by powder XRD, UV-vis, XPS, SEM, EDAX, low temperature N-2 sorption technique and Raman Spectroscopy. Except anatase phase, no other crystalline phase was observed when Ti/Sn molar ratio was varied from 49 to 9 and for Sn free sample. However, further decrease in the ratio lead to the appearance of additional SnO2 phase whose peak intensities were increased with the increase in the tin content. Irrespective of tin content, all samples showed red-shift in UV-vis spectra. Moreover, samples showed Raman shift to higher vibration side from 143 cm(-1) to 147 cm(-1) indicating the doping of Sn2+ into TiO2. By virtue of low band gap, anatase crystallite size and an absence of XRD visible SnO2, ST (19) has shown maximum photocatalytic activity upon 1 wt% Pt loading. It has exhibited the highest rate (0.1264 mmole/g/h) for visible light induced hydrogen evolution by water splitting. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Semiconductors; Sn2+ doped titania; SnO2/TiO2; Sol-gel preparation; visible light; water splitting

Synthesis of (+/-)-thia-calanolide A, its resolution and in vitro biological evaluation - Chopade, Anil U.; Chopade, Manojkumar U.; Chanda, Bhanu M.; Sawaikar, Dilip D.; Sonawane, Kiran B.; Gurjar, Mukund K. (Arabian Journal of Chemistry, 2016)
A synthesis of (+/-)-thia-calanolide A 3 has been successfully accomplished starting from 3,5-dimethoxythiophenol 4, in six steps in an overall yield of 4.5%. The key reaction involved Friedel-Crafts tigloylation of 5,7-dihydroxy-4-n-propyl thiocoumarin 6 employing an appropriate solvent of CS2-PhNO2 in a ratio of 7:3. In its biological evaluation for anti-HIV activity, (+/-)-thia-calanolide A 3 demonstrated comparatively less activity with calanolide A and its synthetic analogue aza-calanolide. Further, (+/-)-3 has been resolved by chiral HPLC to (+) and (-)-3. (C) 2012 Production and hosting by Elsevier B.V. on behalf of King Saud University.

Syringic acid: structural elucidation and co-crystallization - Thipparaboina, Rajesh; Mittapalli, Sudhir; Thatikonda, Sowjanya; Nangia, Ashwini; Naidu, V. G. M.; Shastri, Nalini R. (Crystal Growth & Design, 2016)
Syringic acid (SYRA) is a potential antioxidant used in traditional Chinese medicine and is an emerging nutraceutical. Current reports claim its potential anti-angiogenic, anti-glycating, anti-hyperglycaemic, neuroprotective, and memory-enhancing properties in various animal models. To date, SYRA crystal structure has not been elucidated, and no crystal engineering studies have been reported. This study reports the crystal structure of SYRA for the first time along with its nicotinamide (SNCT-E) and urea (SU-EA-M) co-crystals. All forms were successfully characterized using single crystal X-ray diffraction (XRD), powder XRD, and differential scanning calorimetry. Single crystal analysis revealed that SYRA crystallized in the C2/c space group, whereas SNCT-E (2:1) and SU-EA-M (1:2) crystallized in the P21/n and Cmca space group, respectively. Novel co-crystals have shown improved solubility, modified dissolution profiles, and improved flow and compressibility. Cytotoxic effects were explored in DU145 prostate cancer cell lines for the first time, and significant enhancement in cytotoxicity by the co-crystals was observed compared to plain components. A two-fold increase in % cytotoxicity of SNCT-E was observed when compared to the corresponding physical mixture. These studies shed light on potential utility of SYRA as a coformer for various pharmaceutical applications to design synergistic and organ-protective co-crystals.

Systematic evaluation of biophysical and functional characteristics of selenomethylene-locked nucleic acid-mediated inhibition of miR-21 - Nahar, Smita; Singh, Amrita; Morihiro, Kunihiko; Moai, Yoshihiro; Kodama, Tetsuya; Obika, Satoshi; Maiti, Souvik (Biochemistry, 2016)
miRNAs constitute an important layer of gene regulation mediated by sequence-specific targeting of mRNAs. Aberrant expression of miRNAs contributes to a host of pathological states. Promoting cancer, miR-21 is upregulated in variety of cancers and promotes tumor progresion by suppressing a network of tumor suppressor genes. Here we describe a novel class of bicyclic RNA analogues, selenomethylene-locked nucleic acid (SeLNA), that display high affinity, improved metabolic stability, and increased potency for miR-21 inhibition. The thermal stability (T-m) for duplexes was increased significantly with incorporation of SeLNA monomers as compared to that of the unmodified DNA RNA hybrid. A comprehensive thermodynamic profile obtained by isothermal titration calorimetry revealed a favorable increase in the enthalpy of hybridization for SeLNA containing DNA and target RNA heteroduplexes. SeLNA modifications displayed remarkable binding affinity for miR-21 target RNA with a K-a of <= 1.05 x 10(8) M-1. We also observed enhanced serum stability for SeLNA RNA duplexes with a half-life of <= 36 h. These in vitro results were well correlated with the antisense activity in cancer cells imparting up to similar to 91% inhibition of miR-21. The functional impact of SeLNA modifications on miR-21 inhibition was further gauged by investigating the migration and invasion characterisitics of cancer cells, which were drastically reduced to similar to 49 and similar to 55%, respectively, with SeLNA having four such modifications. Our findings demonstrate SeLNA as a promising candidate for therapeutics for disease associated miRNAs.

Taxonomy of mycotoxigenic fungi - Vankudoth, Koteswara Rao; Sivadevuni, Girisham; Reddy S. M. (Scientific Publisher, 2016)
Mycotoxins, toxic metabolites of molds elaborated during their colonization of foods and feeds, pose a threat to human and animal life. Molds are the diverse group of fungi, which grow in compatatively dry and warm environments, produce copious amount of spores and promote the elaboration of these mycotoxins. Mycotoxigenic fungi, which are unique their sporulating apparatus and exhibit wide variation in their morphology, poses a challenge in their identification. There are numerous examples of their misidentification leading to wrong conclusions. Precise information on taxonomy of these fungi is lacking. Therefore, this book fulfills the need of providing comprehensive information and keys helpful for the accurate identification of these moulds. The book also provides comprehensive account of morphology, mycotoxins produced and factors leading to the elaboration of mycotoxins. Information on their molecular detection, anamorphic and teleomorphic relationships is also included.

Temperature sensitive emission color tuning and white light emission in segmented OPV polymer: perylene bisimide supramolecular complex - Shinde, Shekhar; Asha, S. K. (Macromolecules, 2016)
An oligo(phenylenevinylene) (OPV) based segmented polymer (POPV) and its small molecule model compound (SOPV) were designed with a carboxyl functionality in the side chain. The polymer and small molecule were complexed with pyridine functiorialized perylene bisimide (UPBIPy) and the properties of the donor: acceptor (D:A) complexes were compared. Both polymer and small molecule D:A complexes formed lamellar morphologies in the <10 nm length scale, which could be visualized by TEM and AFM imaging. The flexibility of the segmented polymer architecture imparted special properties to the polymer and its complex. The polymer complex (POPVC) exhibited white light emission with CIE color coordinates (0.27, 0.32) due to partial energy transfer from POPV to UPBIPy. The analogous model OPV complex (SOPVC) continued to show characteristic blue OPV emission in the complex also. The higher sensitivity of polymers toward temperature was made use of to tune the emission color in the complex from white (0.27, 0.32) at 30 degrees C to yellow-green (0.29, 0.31) at 100 degrees C and back to white (0.27, 0.31) upon cooling to 30 degrees C. Such a temperature sensitive emission color tuning was not observed in the small molecule complex under identical conditions.

Template determines whether chemically identical nanoparticle scaffolds show elastic recovery or plastic failure - Suresh, Karthika; Patil, Shivprasad; Rajamohanan, Pattuparambil Ramanpillai; Kumaraswamy, Guruswamy (Langmuir, 2016)
Subtle variations in the preparation of ice-templated nanoparticle assemblies yield monoliths that are chemically identical but exhibit qualitatively different mechanical behavior. We ice template aqueous dispersions to prepare macroporous monoliths largely comprising silica nanoparticles held together by a crosslinked polymer mesh. When the polymer is crosslinked in the presence of ice crystals, we obtain an elastic sponge that is capable of recovery after imposition of large compressive strains (up to 80%). If, however, the ice is lyophilized before the polymer is crosslinked, we obtain a plastic monolith that fails even for modest strains (less than 10%). The elastic sponge and the plastic monolith are chemically identical; they have the same organic content, the same ratio of polymer to crosslinker, and the same average crosslink density. Atomic force microscopy (AFM) was used to probe the local mechanical properties of the crosslinked polymer mesh. These measurements indicate that plastic monoliths dissipate significantly more energy and have a larger spatial variation in local mechanical response relative to the elastic sponges. We believe that this behavior might correlate with a wider spatial distribution of crosslinks in plastic scaffolds relative to elastic scaffolds.

Thermal stimuli-responsive behavior of pyrene end-functionalized PDMS through tunable P–P interactions - Ha, Heonjoo; Shanmuganathan, Kadhiravan; Fei, Yunping; Ellison, Christopher J. (Journal of Polymer Science Part B-Polymer Physics, 2016)
Pyrene end-functionalized, telechelic poly(dimethyl siloxane) (PDMS) materials were synthesized and their response to different thermal stimuli was evaluated. The incorporation of pyrene end groups introduces strong pi-pi interactions that facilitated a broad range of thermally responsive properties, in some circumstances forming pyrene nanocrystals that serve as physical crosslinks leading to elastic materials. By synthesizing different chain lengths, samples exhibiting a 7 orders of magnitude change in storage modulus in response to thermal stimuli were produced by modifying only the end-groups (0.6 wt % of all polymer segments). Repeated thermal cycling during rheological experiments revealed that pi-pi interaction and crystallization/melting kinetics of pyrene chain-ends plays a key role in their thermal responsiveness. The properties of these materials were tuned by adding free pyrene, neat PDMS, or graphene oxide (GO) nanoparticles, making them attractive for many applications (e.g., tunable damping materials, heat/light sensors, conductive gels, or light repositionable adhesives). For example, nanocomposites containing 1 wt % GO caused the melting temperature for pyrene crystal domains to more than double, and even induced pyrene end-group crystallization in samples that did not exhibit crystals in neat form. It is hypothesized that these features originate from pi-pi interactions between pyrene ends and GO surfaces. (C) 2015 Wiley Periodicals, Inc.

Transferability of different classical force fields for right and left handed alpha-helices constructed from enantiomeric amino acids - Biswas, Santu; Sarkar, Sujit; Pandey, Prithvi Raj; Roy, Sudip (Physical Chemistry Chemical Physics, 2016)
Amino acids can form D and L enantiomers, of which the L enantiomer is abundant in nature. The naturally occurring L enantiomer has a greater preference for a right handed helical conformation, and the D enantiomer for a left handed helical conformation. The other conformations, that is, left handed helical conformations of the L enantiomers and right handed helical conformations of the D enantiomers, are not common. The energetic differences between left and right handed alpha helical peptide chains constructed from enantiomeric amino acids are investigated using quantum chemical calculations (using the M06/6-311g(d,p) level of theory). Further, the performances of commonly used biomolecular force fields (OPLS/AA, CHARMM27/CMAP and AMBER) to represent the different helical conformations (left and right handed) constructed from enantiomeric (D and L) amino acids are evaluated. 5- and 10-mer chains from D and L enantiomers of alanine, leucine, lysine, and glutamic acid, in right and left handed helical conformations, are considered in the study. Thus, in total, 32 a-helical polypeptides (4 amino acids x 4 conformations of 5-mer and 10-mer) are studied. Conclusions, with regards to the performance of the force fields, are derived keeping the quantum optimized geometry as the benchmark, and on the basis of phi and psi angle calculations, hydrogen bond analysis, and different long range helical order parameters.

Transition metal doped aluminum clusters: an account of spin - Sengupta, Turbasu; Das, Susanta; Pal, Sourav (Journal of Physical Chemistry C, 2016)
The influence of spin on the properties of small sized transition metal doped aluminum clusters are investigated in the framework of density functional theory (DFT). Detailed analysis on minimum spin doped aluminum clusters has shown prominent indication of odd even oscillation in various calculated properties, supporting the presence of jellium shell structures within them. However, optimized high spin ground state counterparts, on the other hand, show rather smooth trends consistent with the properties of bulk materials. Resemblance to the bulk transition metals is further reflected in the gradual declining trends of heat of adsorption of CO2 molecule on cluster surface by sequentially changing the dopant atom from scandium to zinc. All the observations are also compared and found to be consistent with the earlier theoretical and experimental findings as obtained in the current literature. The similarities in the properties between atomic clusters and the bulk material is of utter importance and indeed precious considering the promising influence of the acquired information in understanding the process of evolution of nanoparticles from constituent atoms.

Treatment of the pesticide industry effluent using hydrodynamic cavitation and its combination with process intensifying additives (H2O2 and ozone) - Raut-Jadhav, Sunita; Badve, Mandar P.; Pinjari, Dipak V.; Saini, Daulat R.; Sonawane, Shirish H.; Pandit, Aniruddha B. (Chemical Engineering Journal, 2016)
Hydrodynamic cavitation (HC) and its combination with H2O2 and ozone have been applied in the present work for the treatment of industrial pesticide effluent. Initially, the effect of dilution of the effluent on the efficacy of hydrodynamic cavitation has been studied using circular venturi as a cavitator. Although an increase in the extent of dilution has not shown any beneficial effect on the actual moles of pollutant degraded, hybrid processes have been studied using 1:5 dilution due to very high TDS content of the effluent. Treatment of the industrial pesticide effluent using HC + ozone (3 gbh) process has demonstrated that the biodegradability index (BI) of the effluent increases from 0.123 to 0.324 after 2 h of operation. The rate of COD and TOC reduction has also increased by many folds by using HC in combination with ozone. In addition this, the treatment of industrial pesticide effluent using HC + H2O2 has also indicated that the rate of COD and TOC reduction increases significantly by using HC in combination with various loadings of H2O2. The study of interference of added H2O2 on the COD analysis has exhibited that the COD equivalence is 0.441 mg/L for 1 mg/L of H2O2. The energy efficiency and operating cost of various hybrid processes have been compared based on the cavitational yield and the cost of electricity. The combined process of HC and H2O2 has observed to be the most cost-effective one due to its higher cavitational yield and lower power consumption. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Biodegradability index; Hydrodynamic cavitation; Hydrogen peroxide; Industrial pesticide effluent; Ozone; Venturi

Two chitotriose-specific lectins show anti-angiogenesis, induces caspase-9-mediated apoptosis and early arrest of pancreatic tumor cell cycle - Singh, Ruby; Nawale, Laxman; Sarkar, Dhiman; Suresh, C. G. (Plos One, 2016)
The antiproliferative activity of two chito-specific agglutinins purified from Benincasa hispida (BhL) and Datura innoxia (DiL9) of different plant family origin was investigated on various cancer cell lines. Both lectins showed chitotriose specificity, by inhibiting lectin hemagglutinating activity. On further studies, it was revealed that these agglutinins caused remarkable concentration-dependent antiproliferative effect on human pancreatic cancerous cells but not on the normal human umbilical vein endothelial cells even at higher doses determined using MTT assay. The GI(50) values were approximately 8.4 mu g ml(-1) (0.247 mu M) and 142 mu g ml(-1) (14.8 mu M) for BhL and DiL9, respectively, against PANC-1 cells. The growth inhibitory effect of these lectins on pancreatic cancer cells were shown to be a consequence of lectin cell surface binding and triggering G(0)/G(1) arrest, mitochondrial membrane depolarization, sustained increase of the intracellular calcium release and the apoptotic signal is amplified by activation of caspases executing cell death. Interestingly, these lectins also showed anti-angiogenic activity by disrupting the endothelial tubulogenesis. Therefore, we report for the first time two chito-specific lectins specifically binding to tumor glycans; they can be considered to be a class of molecules with antitumor activity against pancreatic cancer cells mediated through caspase dependent mitochondrial apoptotic pathway.

Two-layer spin coating flow of newtonian liquids: a computational study - Sahoo, Subhadarshinee; Arora, Akash; Doshi, Pankaj (Computers & Fluids, 2016)
Spin coating is the most commonly used method in industries to form coating films of desired thickness and functionality. In case of two-layer spin coating process, stratified layers of two immiscible liquids are deposited onto the substrate simultaneously, which spread and thin to form two-layer coating film of finite thickness. Questions concerning the effect of surface/interfacial tension on uniformity of these films and contact line evolution are relevant and need thorough investigation. Therefore, an axisymmetric model governing the flow of two-layer spin coating process is developed here. Liquids used for the study are assumed to be Newtonian and fully wetting. The contact line singularity is resolved using a precursor layer model and the governing equations are simplified using lubrication approximation. A Galerkin finite-element method (G/FEM) based scheme is developed to solve the resulting fourth order non-linear PDEs. Simulation results reveal that the fluid properties like ratio of the viscosity of upper layer fluid to lower layer and ratio of the upper gas-liquid surface tension to inner liquid-liquid interfacial tension have profound impact on the time evolution of the film profile, contact radius and shape of the capillary ridges. It is observed that a uniform two-layer film surrounded by thin single layer film is formed when the viscosity ratio is small. On the contrary, when viscosity ratio is large, a thin two-layer film surrounded by bulky capillary ridges is formed. Similarly, the results also show that sharpness of capillary ridge increases with decrease in the surface tension ratio. Further, it is found that increase in the precursor layer thickness increases the spreading rate, thereby making the film more uniform. Finally, the uniformity of the final two-layer film does not get affected by the initial volume of fluid present in the upper layer. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: Axisymmetric flow; Mathematical modeling; Multi-layer coating; Precursor layer model; Thin-film flow; Two-layer spin coating

Two-phase flow boiling in 19mm tube: experiments and CFD modelling - Sardeshpande, Madhavi V.; Raymond, Barlev; Ranade, Vivek V. (Canadian Journal of Chemical Engineering, 2016)
Boiling flows are encountered in a wide range of industrial applications such as boilers, nuclear reactors, electronic cooling, and various types of chemical reactors. Heat transfer coefficients, flow boiling regimes, flow instabilities, pressure drops, and conditions like dry-out are some of the key issues in every boiling flow study. It is observed that a limited experimental database is available for the 19mm ID channel diameter, i.e. a typical tube diameter of steam generator. Therefore, in the present work, the experimental setup was designed for studying boiling flows in a 19mm ID tube in such a way that different flow regimes occurring in a steam generator tube (from pre-heating of sub-cooled water to dry-out) could be investigated by varying inlet conditions. The reported results cover a reasonable range: 8-27kW/m(2) and 2.9-5.9kg/m(2)s heat and mass flux conditions, respectively. A basic computational flow model was also developed to facilitate interpretation of the obtained data. The presented design of the experimental setup and the approach of mimicking different types of steam generator tubes as well as presented experimental and simulated results are useful for gaining insight into complex boiling flows in tubes, and provide a sound basis for further work in this area.
Keywords: CFD; Flow regimes; two-phase flow boiling; vapour quality

Two-phase flow boiling pressure drop in small channels - Sardeshpande, Madhavi V.; Shastri, Parikshit; Ranade, Vivek V. (International Journal of Heat and Fluid Flow, 2016)
Two-phase flow boiling in small channels finds a variety of applications in power and process industries. Heat transfer, boiling flow regimes, flow instabilities, pressure drop and dry out are some of the key issues related to two-phase flow boiling in channels. In this work, the focus is on pressure drop in two-phase flow boiling in tubes of 19 mm diameter. These tubes are typically used in steam generators. Relatively limited experimental database is available on 19 mm ID tube. Therefore, in the present work, the experimental set-up is designed for studying flow boiling in 19 mm ID tube in such a way that any of the different flow regimes occurring in a steam generator tube (from pre-heating of sub-cooled water to dry-out) can be investigated by varying inlet conditions. The reported results cover a reasonable range of heat and mass flux conditions such as 9-27 kW/m(2) and 2.9-5.9 kg/m(2) s respectively. In this paper, various existing correlations are assessed against experimental data for the pressure drop in a single, vertical channel during flow boiling of water at near-atmospheric pressure. A special feature of these experiments is that time-dependent pressures are measured at four locations along the channel. The steady-state pressure drop is estimated and the identification of boiling flow regimes is done with transient characteristics using time series analysis. Experimental data and corresponding results are compared with the reported correlations. The results will be useful for understanding key aspects of flow boiling in small channels. (C) 2016 Elsevier Inc. All rights reserved.

Ultrahydrophobic fluorous metal-organic framework derived recyclable composite as apromising platform to tackle marine oil spills - Mukherjee, Soumya; Kansara, Ankit M.; Saha, Debasis; Gonnade, Rajesh; Mullangi, Dinesh; Manna, Biplab; Desai, Aamod V.; Thorat, Shridhar H.; Singh, Puyam S.; Mukherjee, Arnab; Ghosh, Sujit K. (Chemistry-A European Journal, 2016)
Derived from a strategically chosen hexafluorinated dicarboxylate linker aimed at the designed synthesis of a superhydrophobic metal-organic framework (MOF), the fluorine-rich nanospace of a water-stable MOF (UHMOF-100) exhibits excellent water-repellent features. It registered the highest water contact angle (approximate to 176 degrees) in the MOF domain, marking the first example of an ultrahydrophobic MOF. Various experimental and theoretical studies reinforce its distinc-tive water-repellent characteristics, and the conjugation of superoleophilicity and unparalleled hydrophobicity of a MOF material has been coherently exploited to achieve real-time oil/water separation in recyclable membrane form, with significant absorption capacity performance. This is also the first report of an oil/water separating fluorinated ultrahydrophobic MOF-based membrane material, with potential promise for tackling marine oil spillages.

Ultrasound- and molecular sieves-assisted synthesis, molecular docking and antifungal evaluation of 5-(4-(benzyloxy)-substituted phenyl)-3-((phenylamino)methyl)-1,3,4-oxadiazole-2(3H)-thiones - Nimbalkar, Urja D.; Tupe, Santosh G.; Seijas Vazquez, Julio A.; Khan, Firoz A. Kalam; Sangshetti, Jaiprakash N.; Nikalje, Anna Pratima G. (Molecules, 2016)
A novel series of 5-(4-(benzyloxy) substituted phenyl)-3-((phenyl amino) methyl)-1,3,4-oxadiazole-2(3H)-thione Mannich bases 6a-o were synthesized in good yield from the key compound 5-(4-(benzyloxy) phenyl)-1,3,4-oxadiazole-2(3H)-thione by aminomethylation with paraformaldehyde and substituted amines using molecular sieves and sonication as green chemistry tools. The antifungal activity of the new products was evaluated against seven human pathogenic fungal strains, namely, Candida albicans ATCC 24433, Candida albicans ATCC 10231, Candida glabrata NCYC 388, Cryptococcus neoformans ATCC 34664, Cryptococcus neoformans PRL 518, Aspergillus fumigatus NCIM 902 and Aspergillus niger ATCC 10578. The synthesized compounds 6d, 6f, 6g, 6h and 6j exhibited promising antifungal activity against the tested fungal pathogens. In molecular docking studies, derivatives 6c, 6f and 6i showed good binding at the active site of C. albicans cytochrome P450 enzyme lanosterol 14 alpha-demethylase. The in vitro antifungal activity results and docking studies indicated that the synthesized compounds have potential antifungal activity and can be further optimized as privileged scaffolds to design and develop potent antifungal drugs.
Keywords: 1; 3; 4-oxadiazoles; Antifungal activity; Mannich reaction; Molecular docking; Molecular sieves; Ultrasound

Understanding endothelial dysfunction in diabetic cardiovascular complications using mass spectrometry-based proteomics - Banarjee, Reema; Sharma, Akshay; Bai, Shakuntala; Deshmukh, Arati; Kazi, Rubina; Kulkarni, Mahesh J. (Heart, 2016)

Unified strategy for nickel-catalyzed C-2 Alkylation of indoles through chelation assistance - Soni, Vineeta; Jagtap, Rahul A.; Gonnade, Rajesh G.; Punji, Benudhar (ACS Catalysis, 2016)
A nickel-catalyzed direct C-2 alkylation of indoles through monodentate-chelation assistance has been described. This reaction proceeds via an unusual strategy by the use of a well-designed and defined (quinolinyl)amido–nickel catalyst, [{κN,κN,κN-Et2NCH2C(O)(μ-N)C9H6N}Ni(OAc)], providing a solution to the limitations associated with bidentate-chelate auxiliaries. The method allows coupling of indoles with various unactivated primary and secondary alkyl halides with ample substrate scope. This uniquely strategized alkylation proceeded through crucial C–H activation and via an alkyl radical intermediate. The reaction by this approach represents a rare example of Ni-catalyzed monodentate-chelate-assisted C–H functionalization.

Unraveling origins of the heterogeneous curvature dependence of polypeptide interactions with carbon nanostructures - Jana, Asis K.; Tiwari, Mrityunjay K.; Vanka, Kumar; Sengupta, Neelanjana (Physical Chemistry Chemical Physics, 2016)
Emerging nanotechnology has rapidly broadened interfacial prospects of biological molecules with carbon nanomaterials (CNs). A prerequisite for effectively harnessing such hybrid materials is a multifaceted understanding of their complex interfacial interactions as functions of the physico-chemical characteristics and the surface topography of the individual components. In this article, we address the origins of the curvature dependence of polypeptide adsorption on CN surfaces (CNSs), a phenomenon bearing an acute influence upon the behavior and activity of CN-protein conjugates. Our benchmark molecular dynamics (MD) simulations with the amphiphilic full-length amyloid beta (A beta) peptide demonstrate that protein adsorption is strongest on the concave (inner) CN-surface, weakest on the convex (outer) surface, and intermediary on the planar surface, in agreement with recent experimental reports. The curvature effects, however, are found to manifest non-uniformly between the amino acid subtypes. To understand the underlying interplay of the chemical nature of the amino acids and surface topography of the CNs, we performed high-level quantum chemical (QM) calculations with amino acid analogs (MA) representing their five prominent classes, and convex, concave and planar CN fragments. Molecular electrostatic potential maps reveal pronounced curvature dependence in the mixing of electron densities, and a resulting variance in the stabilization of the non-covalentty bound molecular complexes. Interestingly, our study revealed that the interaction trends of the high-level QM calculations were captured well by the empirical force field. The findings in this study have important bearing upon the design of carbon based bio-nanomaterials, and additionally, provide valuable insights into the accuracy of various computational techniques for probing non-bonded interfacial interactions.

Unravelling the mechanism of electrochemical degradation of PANI in supercapacitors: achieving a feasible solution - Sekar, Pandiaraj; Anothumakkool, Bihag; Vijayakumar, Vidyanand; Lohgaonkar, Apurva; Kurungot, Sreekumar (Chemelectrochem, 2016)
Herein, we have investigated the mode of electrochemical degradation of polyaniline (PANI) when it was utilized as electrodes for supercapacitors. The PANI-based electrodes in supercapacitor devices were biased at a constant potential of 0.80 V, and the performance characteristics and property changes were carefully investigated as a function of the difference in the polarity of the electrodes. Subsequent to this, the analysis of the individual electrodes [positive (POS-PANI) and negative (NEG-PANI)] shows that the degradation mainly occurs at POS-PANI in comparison to NEG-PANI. Moreover, NEG-PANI retains a maximum capacitance of 510 Fg(-1), with a low charge-transfer resistance (R-CT) of 1.84 Omega and similar redox behavior in comparison to the fresh PANI (f-PANI). In contrast to this case, POS-PANI shows significant loss in capacitance (250 Fg(-1)) and increase in R-CT (3.5 Omega) with a disappearance of the characteristic redox behavior normally displayed by PANI. Furthermore, the drastic drop in the electrical conductivity for POS-PANI (1.2 Scm(-1)) compared to f-PANI (3.4 Scm(-1) and NEG-PANI (2.4 Scm(-1)) shows that the degradation of PANI occurs mainly at the anode (POS-PANI) and, thus, contributes to reduce the net performance of the cell. Hence, to ensure this potential-induced degradation of PANI in supercapacitors and also to promote the system stability, we made an asymmetric supercapacitor (ASC) by keeping PANI as a negative electrode and using carbon as a positive electrode. The derived system is found to display stable capacitance behavior before and after the potential application, in contrast to the ASC fabricated by using conventional method, that is, by keeping PANI as the positive electrode and carbon as the negative electrode. Furthermore, the durability analysis of the prototype solid-state ASC shows an enhanced durability of 27000 cycles with excellent columbic efficiency. The findings of the present study will be helpful in the development of highly stable supercapacitors and other similar energy systems when a material like PANI should be utilized for the electrode applications.
Keywords: asymmetric supercapacitors; cycle stability; electrochemical degradation; polarization; redox chemistry

Urinary proteome alterations in HER2 enriched breast cancer revealed by multipronged quantitative proteomics - Gajbhiye, Akshada; Dabhi, Raju; Taunk, Khushman; Vannuruswamy, Garikapati; RoyChoudhury, Sourav; Adhav, Ragini; Seal, Shubhendu; Mane, Anupama; Bayatigeri, Santhakumari; Santra, Manas K.; Chaudhury, Koel; Rapole, Srikanth (Proteomics, 2016)
Globally, breast cancer is the second most common cancer among women. Although biomarker discoveries through various proteomic approaches of tissue and serum samples have been studied in breast cancer, urinary proteome alterations in breast cancer are least studied. Urine being a noninvasive biofluid and a significant source of proteins, it has the potential in early diagnosis of breast cancer. This study used complementary quantitative gel-based and gel-free proteomic approaches to find a panel of urinary protein markers that could discriminate HER2 enriched (HE) subtype breast cancer from the healthy controls. A total of 183 differentially expressed proteins were identified using three complementary approaches, namely 2D-DIGE, iTRAQ, and sequential window acquisition of all theoretical mass spectra. The differentially expressed proteins were subjected to various bioinformatics analyses for deciphering the biological context of these proteins using protein analysis through evolutionary relationships, database for annotation, visualization and integrated discovery, and STRING. Multivariate statistical analysis was undertaken to identify the set of most significant proteins, which could discriminate HE breast cancer from healthy controls. Immunoblotting and MRM-based validation in a separate cohort testified a panel of 21 proteins such as zinc-alpha2-glycoprotein, A2GL, retinol-binding protein 4, annexin A1, SAP3, SRC8, gelsolin, kininogen 1, CO9, clusterin, ceruloplasmin, and alpha 1-antitrypsin could be a panel of candidate markers that could discriminate HE breast cancer from healthy controls.
Keywords: 2D-DIGE; Biomedicine; Breast cancer; HER2 enriched; SWATH; Urinary biomarkers

Validation of force fields of rubber through glass-transition temperature calculation by microsecond atomic-scale molecular dynamics simulation - Sharma, Pragati; Roy, Sudip; Karimi-Varzaneh, Hossein Ali (Journal of Physical Chemistry B, 2016)
Microsecond atomic-scale molecular dynamics simulation has been employed to calculate the glass-transition temperature (T-g) of cis- and trans-1,4-polybutadiene (PB) and 1,4-polyisoprene (PI). Both all-atomistic and united-atom models have been simulated using force fields, already available in literature. The accuracy of these decade old force fields has been tested by comparing calculated glass-transition temperatures to the corresponding experimental values. T-g depicts the phase transition in elastomers and substantially affects various physical properties of polymers, and hence the reproducibility of T-g becomes very crucial from a thermodynamic point of view. Such validation using T-g also evaluates the ability of these force fields to be used for advanced materials like rubber nanocomposites, where T-g is greatly affected by the presence of fillers. We have calculated T-g for a total of eight systems, featuring all-atom and united-atom models of cis- and trans-PI and-PB, which are the major constituents of natural and synthetic rubber. Tuning and refinement of the force fields has also been done using quantum-chemical calculations to obtain desirable density and T-g. Thus, a set of properly validated force fields, capable of reproducing various macroscopic properties of rubber, has been provided. A novel polymer equilibration protocol, involving potential energy convergence as the equilibration criterion, has been proposed. We demonstrate that not only macroscopic polymer properties like density, thermal expansion coefficient, and T-g but also local structural characteristics like end-to-end distance (R) and radius of gyration (R-g) and mechanical properties like bulk modulus have also been equilibrated using our strategy. Complete decay of end-to-end vector autocorrelation function with time also supports proper equilibration using our strategy.

Versatile Cu-II metal-organic framework exhibiting high gas storage capacity with selectivity for CO2: conversion of CO2 to cyclic carbonate and other catalytic abilities - De, Dinesh; Pal, Tapan K.; Neogi, Subhadip; Senthilkumar, S.; Das, Debasree; Sen Gupta, Sayam; Bharadwaj, Parimal K. (Chemistry-A European Journal, 2016)
A linear tetracarboxylic acid ligand, H4L, with a pendent amine moiety solvothermally forms two isostructural metal-organic frameworks (MOFs) L-M (M=Zn-II, Cu-II). Framework L-Cu can also be obtained from L-Zn by post- synthetic metathesis without losing crystallinity. Compared with L-Zn, the L-Cu framework exhibits high thermal stability and allows removal of guest solvent and metal-bound water molecules to afford the highly porous, L-Cu. At 77K, L-Cu absorbs 2.57wt% of H-2 at 1bar, which increases significantly to 4.67wt% at 36bar. The framework absorbs substantially high amounts of methane (238.38cm(3)g(-1), 17.03wt%) at 303K and 60bar. The CH4 absorption at 303K gives a total volumetric capacity of 166cm(3)(STP)cm(-3) at 35bar (223.25cm(3)g(-1), 15.95wt%). Interestingly, the NH2 groups in the linker, which decorate the channel surface, allow a remarkable 39.0wt% of CO2 to be absorbed at 1bar and 273K, which comes within the dominion of the most famous MOFs for CO2 absorption. Also, L-Cu shows pronounced selectivity for CO2 absorption over CH4, N-2, and H-2 at 273K. The absorbed CO2 can be converted to value-added cyclic carbonates under relatively mild reaction conditions (20bar, 120 degrees C). Finally, L-Cu is found to be an excellent heterogeneous catalyst in regioselective 1,3-dipolar cycloaddition reactions (click reactions) and provides an efficient, economic route for the one-pot synthesis of structurally divergent propargylamines through three-component coupling of alkynes, amines, and aldehydes.
Keywords: click reactions; CO2 absorption; cyclic carbonate; heterogeneous catalysis; metal-organic frameworks

Virtual screening techniques to probe the antimalarial activity of some traditionally used phytochemicals - Shibi, Indira G.; Aswathy, Lilly; Jisha, Radhakrishnan S.; Masand, Vijay H.; Gajbhiye, Jayant M. (Combinatorial Chemistry & High Throughput Screening, 2016)
Malaria parasites show resistance to most of the antimalarial drugs and hence developing antimalarials which can act on multitargets rather than a single target will be a promising strategy of drug design. Here we report a new approach by which virtual screening of 292 unique phytochemicals present in 72 traditionally important herbs is used for finding out inhibitors of plasmepsin-2 and falcipain-2 for antimalarial activity against P. falciparum. Initial screenings of the selected molecules by Random Forest algorithm model of Weka using the bioassay datasets AID 504850 and AID 2302 screened 120 out of the total 292 phytochemicals to be active against the targets. Toxtree scan cautioned 21 compounds to be either carcinogenic or mutagenic and were thus removed for further analysis. Out of the remaining 99 compounds, only 46 compounds offered drug-likeness as per the `rule of five' criteria. Out of ten antimalarial drug targets, only two target proteins such as 3BPF and 3PNR of falcipain-2 and 1PFZ and 2BJU of plasmepsin-2 are selected as targets. The potential binding of the selected 46 compounds to the active sites of these four targets was analyzed using MOE software. The docked conformations and the interactions with the binding pocket residues of the target proteins were understood by `Ligplot' analysis. It has been found that 8 compounds are dual inhibitors of falcipain-2 and plasmepsin-2, with the best binding energies. Compound 117 (6aR, 12aS)-12a-Hydroxy-9-methoxy-2,3-dimethylenedioxy-8-prenylrotenone (Usaratenoid C) present in the plant Millettia usaramensis showed maximum molecular docking score.
Keywords: ADME; malaria; Molecular docking; molecular operating environment; Plasmodium falciparum; virtual screening; weka

Vitro and in silico antifungal efficacy of nitrogen- doped carbon nanohorn ( NCNH) against rhizoctonia solani - Dharni, Seema; Sanchita; Unni, SreeKuttan M.; Kurungot, Sreekumar; Samad, Abdul; Sharma, Ashok; Patra, Dharani Dhar (Journal of Biomolecular Structure & Dynamics, 2016)
We have investigated in vitro antifungal efficiency of nitrogen-doped carbon nanohorn (NCNH) against Rhizoctonia solani (R. solani) plant pathogenic fungi. NCNH with size of 50-60nm and concentrations of 10, 50, 100, and 150gmL(-1) were used. The results showed that growth of fungi in the presence of NCNH was significantly (p>.05) inhibited at 150gmL(-1) (85.13 +/-.97) after 72h. The results were validated through computational approaches. Molecular docking analysis of NCNH with endochitinase protein of R. solani was performed to validate the potential of antifungal activity of NCNH. Docking results showed different conformations of interaction of NCNH with endochitinase enzyme. The conformation with least binding energy -13.54kcal/mol was considered further. It is likely that NCNH interacts with the pathogens by mechanically wrapping, which may be one of the major toxicity actions of NCNH against R. solani. The analysis showed that NCNH might interwinds to endochitinase of R. solani leading to the deactivation of the enzyme. To best of our knowledge, this is the first report of antifungal efficacy of NCNH against R. solani and provides useful information about the application of NCNH in resisting crop disease.
Keywords: docking; endochitinase; nitrogen-doped carbon nanohorn; Rhizoctonia solani

What can simulations tell us about GPCRs: integrating the scales - Sengupta, Durba; Joshi, Manali; Athale, Chaitanya A.; Chattopadhyay, Amitabha (G Protein-Coupled Receptors: Signaling, Trafficking and Regulation, 2016)
The functional dynamics of G protein-coupled receptors (GPCRs) encompasses multiple spatiotemporal scales, ranging from femtoseconds to seconds and Angstroms to micrometers. Computational approaches, often in close collaboration with experimental methods, have been invaluable in unraveling GPCR structure and dynamics at these various hierarchical levels. The binding of natural and synthetic ligands to the wild-type and naturally occurring variant receptors have been analyzed by several computational methods. The activation of receptors from the inactive to the active state has been investigated by atomistic simulations and ongoing work on several receptors will help uncover general and receptor-specific mechanisms. The interaction of GPCRs with complex membranes that contain phospholipids and cholesterol have been probed by coarse-grain methods and shown to directly influence receptor association. In this chapter, we discuss computational approaches that have been successful in analyzing each scale of GPCR dynamics. An overview of these approaches will allow a more judicious choice of the appropriate method. We hope that an appreciation of the power of current computational approaches will encourage more critical collaborations. A comprehensive integration of the different approaches over the entire spatiotemporal scales promises to unravel new facets of GPCR function.

4-Phenyl quinoline derivatives as potential serotonin receptor ligands with antiproliferative activity - Joshi, Pranaya V.; Sayed, Alim A.; RaviKumar, Ameeta; Puranik, Vedavati G.; Zinjarde, Smita S. (European Journal of Medicinal Chemistry, 2017)
Antagonists of signaling receptors are often effective non-toxic therapeutic agents. Over the years, there have been evidences describing the role of serotonin or 5-hydroxytryptamine (5-HT) in development of cancer. Although there are reports on the antiproliferative effects of some serotonin receptor antagonists, there are very few investigations related to understanding their structure-activity relationships. In this study, we report the screening of a library of 4-phenyl quinoline derivatives for their antiproliferative activities. Preliminary docking studies indicated that these ligands had the ability to bind to two of the serotonin. receptors, 5-HT1B and 5-HT2B. The results of the in silico experiments were validated by performing in vitro studies on MCF-7 breast cancer cell line. The ethylpiperazine derivatives showed maximum toxicity against this cancer cell line. The compounds inhibited Calcium ion efflux (induced by serotonin) and ERK activation. One of the most active 4-phenyl quinoline derivatives (H3a) also induced apoptosis, thereby, suggesting the use of this scaffold as a potential anticancer drug. (C) 2017 Elsevier Masson SAS. All rights reserved.

Acetone and methanol fruit extracts of terminalia paniculata inhibit HIV-1 infection in vitro - Durge, Ankita; Jadaun, Pratiksha; Wadhwani, Ashish; Chinchansure, Ashish A.; Said, Madhukar; Thulasiram, H. V.; Joshi, Swati P.; Kulkarni, Smita S. (Natural Product Research, 2017)
In this study, we report the in vitro anti-HIV1 activity of acetone and methanol extracts of fruit of Terminalia paniculata. Cytotoxicity tests were conducted on TZM-bl cells and peripheral blood mononuclear cells (PBMC), the CC50 values of both the extracts were 260g/mL. Using TZM-bl cells, the extracts were tested for their ability to inhibit replication of two primary isolates HIV-1 (X4, Subtype D) and HIV-1 (R5, Subtype C). The activity against HIV-1 primary isolate (R5, Subtype C) was confirmed using activated PBMC and by quantification of HIV-1 p24 antigen. Both the extracts showed anti-HIV1 activity in a dose-dependent manner. The EC50 values of the acetone and methanol extracts of T. paniculata were 10.3g/mL. The enzymatic assays were performed to determine the mechanism of action which indicated that the anti-HIV1 activity might be due to inhibition of reverse transcriptase (77.7% inhibition) and protease (69.9% inhibition) enzymes.

Activity tuning of cobalt ferrite nanoparticles anchored on N-doped reduced graphene oxide as a potential oxygen reduction electrocatalyst by Zn substitution in the spinel matrix - Kashyap, Varchaswal; Singh, Santosh K.; Kurungot, Sreekumar (Chemistry Select, 2017)
Development of highly efficient and durable ORR catalysts by using non-platinum group metals (such as Co, Fe, Mn, and Zn) is a challenging task in the forward path towards the realization of low-cost energy devices in the commercial stream. The present work deals with an effective strategy wherein an efficient Pt-free electrocatalyst for oxygen reduction reaction (ORR) is prepared by stoichiometrically substituting some fraction of Fe with Zn in cobalt ferrite and anchoring these spinel nanoparticles on nitrogen doped reduced graphene oxide (N-rGO). Zn substitution is found to be significantly altering the ratio of Fe2+/Fe3+ in the cobalt ferrite nanocrystal system with a concomitant promotional influence on its electrocatalytic activity towards ORR. The nanoparticle composition with a Co, Fe and Zn molar ratio of 1.0:1.7:0.3, represented by the formula CoFe1.7Zn0.3O4(CFZn(0.3)), supported over N-rGO has shown 10 mV and 20 mV positive shift in the onset and half-wave potentials, respectively, for ORR in 0.1 M KOH in comparison to the nanoparticles of CoFe2O4 supported over N-rGO (CF/N-rGO). The optimum Zn substitution is found to be narrowing down the difference with the state-of-the-art Pt/C for ORR by 100 and 110 mV in terms of the onset and half-wave potentials, respectively. Most significantly, the homemade catalyst is found to be clearly outperforming the Pt catalyst in terms of the limiting current density and electrochemical durability.
Keywords: Carbon Nano-fiber; Cathod Catalyst; CoFe2O4; Evolution; Magnetic-properties; Membrane fuel- Cell; Metal-Air Batteries; N-doped graphene; Nanocrystalline; nanocrystals; oxygen reduction reaction; performance; Platinium; solvothermal synthesis; Zn substituted cobalt ferrite

Acyclic αγα-tripeptides with fluorinated- and nonfluorinated-furanoid sugar framework: importance of fluoro substituent in reverse-turn induced self-assembly and transmembrane ion-transport activity - Burade, S. S.; Shinde, S. V.; Bhuma, N.; Kumbhar, N.; Kotmale, A.; Rajamohanan, P. R.; Gonnade, R. G.; Talukdar, P.; Dhavale, D. D. (Journal Of Organic Chemistry, 2017)
Acyclic αγα-tripeptides derived from fluorinated-furanoid sugar amino acid frameworks act as reverse-turn inducers with a U-shaped conformation, whereas the corresponding nonfluorinated αγα-tripeptides show random peptide conformations. The NMR studies showed the presence of bifurcated weak intramolecular hydrogen bonding (F···HN) and N+···Fδ- charge-dipole attraction compel the amide carbonyl groups to orient antiperiplanar to the C-F bond, thus, demonstrating the role of the fluorine substituent in stabilizing the U-shaped conformation. The NOESY data indicate that the U-shaped tripeptides self-assembly formation is stabilized by the intermolecular hydrogen bonding between C=O···HN with antiparallel orientation. This fact is supported by ESI-MS data, which showed mass peaks up to the pentameric self-assembly, even in the gas phase. The morphological analysis by FE-SEM, on solid samples, showed arrangement of fibers into nanorods. The antiparallel self-assembled pore of the fluorinated tripeptides illustrates the selective ion-transport activity. The experimental findings were supported by DFT studies.

Allostreptomyces indica sp. nov., isolated from India - Sahu, A.K. (Journal of Antibiotics, 2017)
A novel actinobacterium, designated strain YIM 75704T, was isolated from a limestone quarry located at Gulbarga, Karnataka, India. The novel strain has showed typical morphological and chemotaxonomic characteristics of the family Streptomycetaceae. Comparison of 16S rRNA gene sequences indicated that this strain represents a novel member of the family Streptomycetaceae and exhibited 99.0% 16S rRNA gene sequence similarities with the type species of the recently described novel genus Allostreptomyces, that is, Allostreptomyces psammosilenae, whereas other species of Streptomyces were below 95% sequence similarity. The cell hydrolysates contained the LL-isomer of diaminopimelic acid and the predominant quinones were MK-9 (H 6, H 8 and H 4). The polar lipid profile consisted of diphosphatidylglycerol, phosphatidylinositolmannosides and three unknown phospholipids. The DNA G+C content was 75.0 mol%. A polyphasic study of the strain with morphological, phenotypic, phylogenetic and with DNA-DNA hybridization evidence with related members showed that this strain represents novel species of Allostreptomyces for which the name Allostreptomyces indica sp. nov., is proposed. The type strain is YIM 75704 T (= DSM 41985T =CCTCC AA 209051T = NCIM 5485T).

Amaranthus caudatus lectin with polyproline II fold: conformational and functional transitions and molecular dynamics - Yadav, Priya; Shahane, Ganesh; Gaikwad, Sushama M. (Journal of biomolecular Structure & Dynamics, 2017)
Polyproline II (PPII) fold, a peculiar structural element was detected in the Amaranthus caudatus seed lectin (ACL) based on far UV circular dichroism spectrum, conformational transitions of the lectin and a distinct isodichroic point in thermal denaturation. It was confirmed by using PolyprOnline database to estimate the percentage of amino acids contributing to PPII fold and showed the values as 13.5% and 13.9% for PROSS and XTLSSTR, respectively. Investigations of the functional and conformational transitions of ACL during thermal, pH and guanidine hydrochloride (GdnHCl) induced denaturation were carried out using biochemical and biophysical techniques and molecular dynamics (MD) simulations approach. The lectin got aggregated at 60 °C with instantaneous structural alterations. The aggregation-prone regions in ACL were predicted using online servers viz. AGGRESCAN, AmylPred, FoldAmyloid and Waltz that were represented by Visual Molecular Dynamics tools. Nine conserved regions were identified by these softwares as being ‘hot-spots’ for aggregation. MD simulation studies of the lectin at 60 °C revealed increase in radius of gyration. The loss of PPII fold in 2.0 M GdnHCl was reversible. The partially unfolded intermediate of ACL with diminished PPII fold formed at pH 1.0 was stable up to 90 °C. The polyproline II fold has been rarely detected in lectins, ACL being the second after the potato lectin.

Ammonia-modified graphene sheets decorated with magnetic Fe3O4 nanoparticles for the photocatalytic and photo-Fenton degradation of phenolic compounds under sunlight irradiation - Boruah, Purna K.; Sharma, Bhagyasmeeta; Karbhal, Indrapal; Shelke, Manjusha V.; Das, Manash R. (Journal of hazardous materials, 2017)
Synthesis of easily separable and eco-friendly efficient catalyst with both photocatalytic and photo-Fenton degradation properties is of great importance for environment remediation application. Herein, ammonia-modified graphene (AG) sheets decorated with Fe3O4 nanoparticles (AG/Fe3O4) as a magnetically recoverable photocatalyst by a simple in situ solution chemistry approach. First, we have functionalized graphene oxide (GO) sheets by amide functional group and then Fe3O4 nanoparticles (NPs) are doped onto the functionalized GO surface. The AG/Fe3O4 nanocomposite showed efficient photocatalytic activity towards degradation of phenol (92.43%), 2-nitrophenol (2-NP) (98%) and 2-chlorophenol (2-CP) (97.15%) within 70–120 min. Consequently, in case of photo-Fenton degradation phenomenon, 93.56% phenol, 98.76% 2-NP and 98.06% of 2-CP degradation were achieved within 50–80 min using AG/Fe3O4 nanocomposite under sunlight irradiation. The synergistic effect between amide functionalized graphene and Fe3O4 nanoparticles (NPs) enhances the photocatalytic activity by preventing the recombination rate of electron-hole-pair in Fe3O4 NPs. Furthermore, the remarkable reusability of the AG/Fe3O4 nanocomposite was observed up to ten cycles during the photocatalytic degradation of these phenolic compounds.

Amphi-functional mesoporous silica nanoparticles for dye separation - Shinde, Pravin; Sen Gupta, Sayam; Singh, Baljeet; Polshettiwar, Vivek; Prasad, Bhagavatula L. V. (Journal of Materials Chemistry A, 2017)
Synthesis of amphi-functional mesoporous silica nanoparticles (similar to 80 nm) by stepwise chemical modifications of outer and inner pore surfaces is reported. These materials display a clear "Janus" like character and are able to selectively and completely separate hydrophobic dyes form a mixture of dyes. Our results clearly suggest a clear partition of more hydrophobic dyes into the pores from a mixture of two dyes. In addition this material displays a remarkable recycling ability for 10 cycles with up to similar to 99% dye removal from water.

Anti-proliferative effect of novel primary cetyl alcohol derived sophorolipids against human cervical cancer cells HeLa - Nawale, Laxman; Dubey, Parul; Chaudhari, Bhushan; Sarkar, Dhiman; Prabhune, Asmita (Plos One, 2017)
Sophorolipids (SLs) are glycolipid biosurfactants that have been shown to display anticancer activity. In the present study, we report anti-proliferative studies on purified forms of novel SLs synthesized using cetyl alcohol as the substrate (referred as SLCA) and their anticancer mechanism in human cervical cancer cells. Antiproliferative effect of column purified SLCA fractions (A, B, C, D, E and F) was examined in panel of human cancer cell lines as well as primary cells. Among these fractions, SLCA B and C significantly inhibited the survival of HeLa and HCT 116 cells without affecting the viability of normal human umbilical vein endothelial cells (HUVEC). The two fractions were identified as cetyl alcohol sophorolipids with non-hydroxylated tail differing in the degree of acetylation on sophorose head group. At an IC50 concentration SLCA B (16.32 mu g ml(-1)) and SLCA C (14.14 mu g ml(-1)) blocked the cell cycle progression of HeLa cells at G1/S phase in time-dependent manner. Moreover, SLCA B and SLCA C induced apoptosis in HeLa cells through an increase in intracellular Ca2+ leading to depolarization of mitochondrial membrane potential and increase in the caspase-3, -8 and -9 activity. All these findings suggest that these SLCAs could be explored for their chemopreventive potential in cervical cancer.

Assessing therapeutic potential of molecules: molecular property diagnostic suite for tuberculosis - Gaur, A. S.; Bhardwaj, A.; Sharma, A.; John, L.; Vivek, M. R.; Tripathi, N.; Bharatam, P. V.; Kumar, R.; Janardhan, S.; Mori, A.; Banerji, A.; Lynn, A. M.; et al. (Journal of Chemical Sciences, 2017)
Abstract: Molecular Property Diagnostic Suite (MPDS TB) is a web tool (http://mpds.osdd.net) designed to assist the in silico drug discovery attempts towards Mycobacterium tuberculosis (Mtb). MPDS TB tool has nine modules which are classified into data library (1–3), data processing (4–5) and data analysis (6–9). Module 1 is a repository of literature and related information available on the Mtb. Module 2 deals with the protein target analysis of the chosen disease area. Module 3 is the compound library consisting of 110.31 million unique molecules generated from public domain databases and custom designed search tools. Module 4 contains tools for chemical file format conversions and 2D to 3D coordinate conversions. Module 5 helps in calculating the molecular descriptors. Module 6 specifically handles QSAR model development tools using descriptors generated in the Module 5. Module 7 integrates the AutoDock Vina algorithm for docking, while module 8 provides screening filters. Module 9 provides the necessary visualization tools for both small and large molecules. The workflow-based open source web portal, MPDS TB 1.0.1 can be a potential enabler for scientists engaged in drug discovery in general and in anti-TB research in particular. Graphical Abstract: SYNOPSIS: A web-based MPDS TB Galaxy tool is developed for assessing therapeutic potential of molecules. MPDS TB is categorized into Data Library, Data Processing and Data Analysis. It can be a potential enabler for scientists engaged in drug discovery in general and in anti-TB research in particular. [Figure not available: see fulltext.] © 2017, Indian Academy of Sciences.
Keywords: chemical analysis; Chemoinformatics; computational chemistry; Diagnosis; Drug discovery portal; Information analysis; Libraries; Molecular graphics; Molecules; Neglected diseases; Open science; Portals; tuberculosis; Web-based technology; Websites

Automating multistep flow synthesis: approach and challenges in integrating chemistry, machines and logic - Shukla, Chinmay; Kulkarni, Amol A. (Beilstein Journal of Organic Chemistry, 2017)
The implementation of automation in the multistep flow synthesis is essential for transforming laboratory-scale chemistry into a reliable industrial process. In this review, we briefly introduce the role of automation based on its application in synthesis viz. auto sampling and inline monitoring, optimization and process control. Subsequently, we have critically reviewed a few multistep flow synthesis and suggested a possible control strategy to be implemented so that it helps to reliably transfer the laboratory-scale synthesis strategy to a pilot scale at its optimum conditions. Due to the vast literature in multistep synthesis, we have classified the literature and have identified the case studies based on few criteria viz. type of reaction, heating methods, processes involving in-line separation units, telescopic synthesis, processes involving in-line quenching and process with the smallest time scale of operation. This classification will cover the broader range in the multistep synthesis literature.

Benz-amidinato calcium iodide catalyzed aldehyde and ketone hydroboration with unprecedented functional group tolerance - Yadav, S.; Pahar, S.; Sen, S. S. (Chemical Communications, 2017)
A benz-amidinato calcium compound, [PhC(NiPr)(2)Cal] (1), catalyzed hydroboration of a wide range of aldehydes and ketones using pinacolborane (HBpin) at room temperature is reported. The catalyst shows functional group tolerance even towards OH and NH groups. The strategy was further extended to imines.

Binding selectivity of vitamin K3 based chemosensors towards nickel(II) and copper(II) metal ions - Patil, Amit; Lande, Dipali N.; Nalkar, Archana; (Gejji, Shridhar P.; Chakrovorty, Debamitra; Gonnade, Rajesh; Moniz, Tania; Rangel, Maria; Pereira, Eulalia; Salunke-Gawali, Sunita (Journal of molecular Structure, 2017)
The vitamin K3 derivatives 2-methyl-3-[(pyridin-2-ylmethyl)-amino]-1,4-naphthoquinone (M-1), 2-methyl-3-[(pyridin-2-ylethyl)-amino]-1,4-naphthoquinone (M-2), 2-methyl-3-((2-(thiophen-2-yl) methyl)amino)naphthalene-1,4-dione (M-3) and 2-methyl-3-((2-(thiophen-2-yl)ethyl)amino)naphthalene-1,4-dione (M-4) have been synthesized, characterized and studied for their chemosensor abilities towards transition metal ions. Crystal structures of M-1 to M-4 revealed a variety of N-H center dot center dot O, C-H center dot center dot center dot O, C-H center dot center dot center dot pi and pi center dot center dot center dot pi interactions. Minor variations in such interactions by chemical stimuli such as metal ions, results in change in color that can be visualized by naked eyes. It has been shown that electronic structure and H-1 NMR, vibrational as well as electronic spectra from the density functional theory agree well with the experiments. The metal ion binding in ethanol, ethanol-water and in mild base triethylamine brings forth recognizing ability of M-1 toward Ni2+ whereas M-2 exhibits large sensing ability for Cu2+ ion. Interestingly M-1 display varying metal ion binding specificity in different solvents with the association constant in ethanol being 11,786 M-1 for Ni2+ compared to 9462 M-1 for the Cu2+. A reversal in preferential binding of M-2 with the respective association constants being 4190 M-1 and 6370 M-1 is discernible. (C) 2017 Elsevier B.V. All rights reserved.
Keywords: Aminonaphthoquinone Molecular-structures; Anthraquinone; Aqueous-solution; Chemosensor; Crystal-structures; Cu(II); Derivatives; DFT; Fluorometric Chemosensors; hydrogen bonding; Naphthoquinone; pi-pi stacking; Recognition; sensors

Biology and development of xanthopimpla pedator (hymenoptera: ichneumonidae): pupal endoparasitoid of antheraea mylitta (Lepidoptera: Saturniidae) - Gathalkar, Ganesh B.; Barsagade, Deepak D.; Sen, Avalokiteswar (Annals of the Entomological Society of America, 2017)
The Antheraea mylitta (Drury) (Lepidoptera: Saturniidae) is a commercially important species for the production of tasar silk. However, the Xanthopimpla pedator (F.) (Hymenoptera: Ichneumonidae) is a major pupal endoparasitoid of A. mylitta, which affects the total tasar silk production in India. A gravid female X. pedator parasitizes the pupae of A. mylitta by depositing an egg, which produces a single offspring per host. We studied the development of immature forms of X. pedator by dissecting parasitized pupae of A. mylitta under laboratory conditions at 28-30 degrees C and 40-60% relative humidity. All immature stages of the parasitoid develop within the host in 20-22 d, by devouring the entire pupal content, resulting in dead or seedless cocoons. The total life cycle of X. pedator is completed inside the host pupa and the adult emerges out by rupturing the peduncle end of the cocoon. During development of X. pedator, five preimaginal stages, viz., egg, larval instars, prepupa, pupa, and a pharate adult, were observed. Xanthopimpla pedator passes through five larval instars identified by structural and morphometric variations. These include primary larva (L1), the intermediate larvae (L2-L4), and the finalinstar larva (L5). Biometric study and larval head width permitted the morphological separation of all five larval instars. In the present study, the biology and development of X. pedator inside the pupa of A. mylitta are reported for the first time with detailed photomicrographs. Therefore, the study may enable the information concerning physiological interactions between A. mylitta and its endoparasitoid, X. pedator.

Bronsted acid catalyzed enantioselective pericyclic reactions - Sleet, Christopher E.; Tambar, Uttam K.; Maity, Pradip (Tetrahedron, 2017)
Pericyclic reactions can be challenging processes to render asymmetric, due to the concerted and non polar nature of the transition states. Several examples have been reported in which a suitable catalyst binds to a heteroatom-containing substituent in the substrate and accelerates the reaction rate. The requirement of coordinating functionalized substrates has limited the generality of such asymmetric transformations. Multifunctional Bronsted acids are promising catalysts that represent a new paradigm in asymmetric pericyclic reactions. These chiral catalysts rely on multiple non-covalent interactions in the transition state for asymmetric induction, which has been utilized to activate more general substrate classes. In this review, we will cover recent advances in Bronsted acid catalyzed pericyclic reactions and discuss the impact of catalyst design on the expansion of substrate scope for highly enantioselective processes. (C) 2017 Elsevier Ltd. All rights reserved.

Calculation of the magnetic hyperfine structure constant of alkali metals and alkaline-earth-metal ions using the relativistic coupled-cluster method - Sasmal, Sudip (Physical Review A, 2017)
The Z-vector method in the relativistic coupled-cluster framework is used to calculate the magnetic hyperfine structure constant (A(J)) of alkali metals and singly charged alkaline earth metals in their ground state electronic configuration. The Z-vector results are in very good agreement with the experiment. The A(J) values of Li, Na, K, Rb, Cs, Be+, Mg+, Ca+, and Sr+ obtained in the Z-vector method are compared with the extended coupled-cluster results taken from Phys. Rev. A 91, 022512 (2015). The same basis and cutoff are used for the comparison purpose. The comparison shows that the Z-vector method with the single and double approximation can produce a more precise wave function in the nuclear region than the ECC method.

Calixarene based nanocomposite materials for high performance supercapacitor electrode - Waghmode, Babasaheb J.; Soni, Roby; Patil, Kashinath Rangu; Malkhede, Dipalee D. (New Journal of Chemistry, 2017)
A functionalised calixarene {4-Sulphatocalix [6] arene Hydrate (SC6)} stabilises MoS2/partially reduced graphene oxide (rGO) nanosheet. Such stabilised SC6-rGO/SC6-MoS2 and SC6 doped polyaniline (PANI) together forms a nanocomposite hybrid material for supercapacitor electrode. It was fabricated by an in situ polymerization method. Transmission electron microscopy (TEM) results suggest that PANI nanostructures grow homogeneously onto the surfaces of SC6 functionalised MoS2. Calixarene acts as a dopant for PANI as well as a stabiliser for the 2D nanosheets of rGO/MoS2. The characterisation of composites together with basic components was done by using various techniques namely, solid-state FT-IRspectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The electrochemical performance was analysed by cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectrometry (EIS). It was found that the SC6 functionalised MoS2 and SC6 doped PANI formed a uniform nanocomposite. The synthesised composites show high specific capacitance (691 F/g) and good cycling stability during the charge-discharge process when used as supercapacitor electrodes. The improvement in electrochemical performance of composites is assigned to synergistic effect of SC6 stabilised MoS2 and doped PANI. Our investigation highlighted the importance of use of calixarene in composites for above stated supercapacitor performance. The role of calixarene in the present study opens a way for the application of alike materials in the composite supercapacitors for energy storage applications.

Camptothecin-producing endophytic bacteria from pyrenacantha volubilis hook. (Icacinaceae): a possible role of a plasmid in the production of camptothecin - Soujanya, K. N.; Siva, R.; Kumara, P. Mohana; Srimany, Amitava; Ravikanth, G.; Mulani, F. A.; Aarthy, T.; Thulasiram, H. V.; Santhoshkumar, T. R.; Nataraja, Karaba N.; Shaanker, R. Uma (Phytomedicine, 2017)
Background: Camptothecin (CPT), a quinoline alkaloid, is a potent inhibitor of eukaryotic topoisomerase I. Because of this property, several derivatives of CPT are used as chemotherapeutic agents. CPT is produced by several plant species belonging to the Asterid clade as well as by a number of endophytic fungal associates of these plants. In this study, we report the production of CPT by four bacterial endophytes and show the possible role of a plasmid in the biosynthesis of CPT. Methods: Endophytic bacteria were isolated from leaves, stems and fruits of Pyrenacantha volubilis Hook. (Icacinanceae). The bacterial isolates were purified and analyzed for production of CPT by ESI-MS/MS and NMR analysis. Bacterial identity was established based on the morphology and 16s rRNA sequence analysis. Crude extracts of the bacterial endophytes were evaluated for their cytotoxicity using colon cancer cell lines. The role of plasmid in the production of CPT was studied by purging the plasmid, using acriflavine, as well as reconstituting the bacteria with the plasmid. Results: Four bacterial isolates, Bacillus sp. (KP125955 and KP125956), Bacillus subtilis (KY741853) and Bacillus amyloliquefaciens (KY741854) were found to produce CPT in culture. Both based on ESI-MS/MS and NMR analysis, the identity of CPT was found to be similar to that produced by the host plant. The CPT was biologically active as evident by its cytotoxicity against colon cancer cell line. The production of CPT by the endophyte (Bacillus subtilis, KY741853) attenuated with sub-culture. A likely role of a plasmid in the production of CPT was established. A 5 kbp plasmid was recovered from the bacteria. Bacterial isolate cured of plasmid failed to produce CPT. Conclusion: Our study implies a possible role of a plasmid in the production of CPT by the endophytic bacteria and opens up further work to unravel the exact mechanisms that might be involved.

Carboxymethyl cellulose-grafted mesoporous silica hybrid nanogels for enhanced cellular uptake and release of curcumin - Tiwari, Neha; Nawale, Laxman U.; Sarkar, Dhiman; Badiger, Manohar V. (Gels, 2017)
Mesoporous silica nanoparticles (MSNs) with ordered pore structure have beensynthesized and used as carriers for the anticancer drug curcumin. MSNs were functionalizedwith amine groups and further attached with carboxymethyl cellulose (CMC) using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) coupling chemistry, which increased the hydrophilicityand biocompatibility of MSNs. The functionalized MSNs (MSN-NH2and MSN-CMC) werecharacterized using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM),Dynamic Light Scattering (DLS), N2adsorption, X-Ray Diffraction (XRD), Thermo GravimetricAnalysis (TGA) and Fourier Transform Infrared Spectroscopy (FT-IR). Thein vitrorelease of curcuminfrom the –NH2and CMC functionalized MSNs (MSN-cur-NH2and MSN-cur-CMC) was performedin 0.5% aqueous solution of sodium lauryl sulphate (SLS). The effect of CMC functionalization ofMSNs towards cellular uptake was studied in the human breast cancer cell line MDA-MB-231 andwas compared with that of MSN-NH2and free curcumin (cur). Both MSN-NH2and MSN-CMCshowed good biocompatibility with the breast cancer cell line. The MTT assay study revealedthat curcumin-loaded MSN-cur-CMC showed better uptake as compared to curcumin-loadedMSN-cur-NH2. Free curcumin was used as a control and was shown to have much less internalizationas compared to the curcumin-loaded functionalized MSNs due to poor bioavailability. Fluorescencemicroscopy was used to localize the ﬂuorescent drug curcumin inside the cells. The workdemonstrates that CMC-functionalized MSNs can be used as potential carriers for loading and releaseof hydrophobic drugs that otherwise cannot be used effectively in their free form for cancer therapy.

Cascade reductive etherification of bioderived aldehydes over Zr-based catalysts - Shinde, Suhas; Rode, Chandrashekhar (ChemSusChem, 2017)
An efficient one-pot catalytic cascade sequence has been developed for the production of value-added ethers from bioderived aldehydes. Etherification of 5-(hydroxymethyl)furfural with different aliphatic alcohols over acidic Zr-montmorillonite (Zr-Mont) catalyst produced a mixture of 5-(alkoxymethyl)furfural and 2-(dialkoxymethyl)-5-(alkoxymethyl)furan. The latter was selectively converted back into 5-(alkoxymethyl)furfural by treating it with water over the same catalyst. The synthesis of 2,5-bis(alkoxymethyl)furan was achieved through a cascade sequence involving etherification, transfer hydrogenation, and re-etherification over a combination of acidic Zr-Mont and the charge-transfer hydrogenation catalyst [ZrO(OH)(2)]. This catalyst combination was further explored for the cascade conversion of 2-furfuraldehyde into 2-(alkoxymethyl)furan. The scope of this strategy was then extended for the reductive etherification of lignin-derived arylaldehydes to obtain the respective benzyl ethers in >80% yield. Additionally, the mixture of Zr-Mont and ZrO(OH)(2) does not undergo mutual destruction, which was proved by recycling experiments and XRD analysis. Both the catalysts were thoroughly characterized using BET, temperature-programmed desorption of NH3 and CO2, pyridine-FTIR, XRD, inductively coupled plasma optical emission spectroscopy, and X-ray photoelectron spectroscopy techniques.

Catalytic ozonation of clofibric acid over copper-based catalysts: in situ ATR-IR studies - Sable, Shailesh S.; Ghute, P. P.; Fakhrnasova, D.; Mane, R. B.; Rode, Chandrashekhar V.; Medina, F.; Contreras, S. (Applied Catalysis B-Environmental, 2017)
The current study describes the catalytic ozonation of clofibric acid (CFA) under ambient conditions using copper oxide catalysts synthesized by different methods. The objective of this study is to provide novel catalysts and reaction mechanism for the degradation of emerging pharmaceutical compounds in aqueous solution. Among the various Cu catalysts screened in this study, the Cut-Ali oxide catalyst showed an excellent activity and stability in the degradation and mineralization of CFA. In situ attenuated total reflection IR (ATR-IR) spectroscopy was used to examine the interaction of ozone with the active sites of the catalyst in presence of water and to investigate the possible catalytic mechanism. The presence of Lewis acid sites in the Cut-Ali catalyst increased the amount of chemisorbed water enhancing stronger interaction of ozone to form surface activated species, resulting in higher catalytic activity. The results obtained from in-situ ATR-IR study indicate that surface hydroxyl groups and Lewis acid sites are responsible for promoting the generation of hydroxyl radicals (OHS) from aqueous ozone. (C) 2017 Elsevier B.V. All rights reserved.

Cerium-based metal-organic framework having inherent oxidase-like activity applicable for colorimetric sensing of biothiols and aerobic oxidation of thiols - Dalapati, Rana; Sakthivel, Balasubramanian; Ghosalya, Manoj K.; Dhakshinamoorthy, Amarajothi; Biswas, Shyam (Crystengcomm, 2017)
A cerium-basedmetal-organic framework (MOF; 1) with a UiO-66 (UiO: University of Oslo) framework topology was synthesized solvothermally by employing 3,4-dimethylthieno[2,3-b] thiophene-2,5-dicarboxylic acid as a ligand. The MOF was thoroughly characterized by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction, infrared spectroscopy, and thermogravimetric and N-2 sorption analyses. The activated material (1') retained its structural integrity in water, acetic acid and 1 M HCl solution. XPS investigation reveals the presence of both Ce(III) and Ce(IV) ions in 1. Owing to the presence of mixed-valence cerium ions, 1' was able to oxidize the chromogenic peroxidase substrate 3,3', 5,5'-tetramethylbenzidine (TMB) or 2,2'azinobis.3- ethylbenzothizoline-6-sulfonic acid) (AzBTS) in the absence of an external oxidizing agent. Thus, it showed inherent oxidase-like catalytic properties. Inspired by the excellent oxidase-mimicking activity of 1', a protocol was developed for the rapid colorimetric sensing of biothiols in NaAc buffer (0.2 M, pH = 4). The sensing ability of 1' towards cysteine was also demonstrated in human blood plasma. Furthermore, the redox-active cerium ions enabled 1' to exhibit excellent heterogeneous catalytic performance in aerobic oxidation catalysis of thiol compounds. The material is reusable (both as a sensor and as a catalyst), lowcost and highly stable, which renders it a promising candidate for the monitoring of biothiols in immunoassays and medical diagnosis as well as for industrial oxidation catalysis.

Chapter 5: Experimental and computational approaches to study membranes and lipid-protein interactions - Sengupta, Durba; Kumar, G. Aditya; Prasanna, Xavier; Chattopadhyay, A. (Computational biophysics of membrane proteins, 2017)
Biological membranes are complex two-dimensional, non-covalent assemblies of a diverse variety of lipids and proteins. A hallmark of membrane organization is varying degrees of spatiotemporal heterogeneity spanning a wide range. Membrane proteins are implicated in a wide variety of cellular functions, and comprise ∼30% of the human proteome and ∼50% of the current drug targets. Their interactions with membrane lipids are recognized as crucial elements in their function. In this article, we provide an overview of experimental and theoretical approaches to analyze membrane organization, dynamics, and lipid-protein interactions. In this context, we highlight the wide range of time scales that membrane events span, and approaches that are suitable for a given time scale. We discuss representative fluorescence-based approaches (FRET and FRAP) that help to address questions on lipid-protein and protein-cytoskeleton interactions in membranes. In a complimentary fashion, we discuss computational methods, atomistic and coarse-grain, that are required to address a given membrane problem at an appropriate scale. We believe that the synthesis of knowledge gained from experimental and computational approaches will enable us to probe membrane organization, dynamics, and interactions at increasing spatiotemporal resolution, thereby providing a robust model for the membrane in health and disease.

Characterizing clinically relevant natural variants of GPCRs using computational approaches - Sengupta, Durba; Sonar, Krushna; Joshi, Manali (Methods in cell biology, 2017)
G protein-coupled receptors (GPCRs) are an important class of drug targets owing to their physiological role. A large number of clinically relevant single nucleotide polymorphisms (SNPs) have been observed in GPCRs that are linked to disease susceptibility and adverse drug response. It is therefore important to characterize the variants in order to improve GPCR therapeutics. Here, we discuss computational methods coupling molecular dynamics simulations with docking and free energy calculations to characterize the functional differences in GPCR variants. The hallmark of this approach is the explicit incorporation of receptor and membrane dynamics that allows us to analyze short- and long-range effects in the variant receptors. We use the SNPs reported in β2-adrenergic receptor (β2AR) as a test case and highlight the recent successes in analyzing structural and dynamic differences in a series of population variants. The computational approach we discuss here has a twofold benefit: it helps to unravel the molecular mechanisms underlying hypo- or hyperfunctionality of variant receptors as well as prioritizing novel variants that must be experimentally tested.

Chitosan intercalated metal organic gel as a green precursor of fe entrenched and fe distributed N-doped mesoporous graphitic carbon for oxygen reduction reaction - Shijina, Kottarathil; Illathvalappil, Rajith; Kurungot, Sreekumar; Nair, Balagopal N.; Mohamed, A. Peer; Yamaguchi, Takeo; Anilkumar, Gopinathan M.; Hareesh, U. S.; Sailaja, G. S. (Chemistryselect, 2017)
Herein, we present Metal-Organic Gel intercalated with chitosan, a `green'' precursor for the synthesis of intrinsic N-doped Fe entrenched (CHI-TMA-Fe-CW) and Fe distributed mesoporous graphitic carbon structures (CHI-TMA-Fe-CW-M1) with appreciable Oxygen Reduction Reaction (ORR) activity in alkaline medium. Modulation of the synthetic protocol as a function of reaction kinetics and gelation time while maintaining identical pyrolysis conditions (900 degrees C, flowing N-2 atmosphere) improves the microstructure, surface area and Fe distribution of the graphitic structures (CHI-TMA-Fe-CW-M1). CHI-TMA-Fe-CW has a Fe entrenched graphitic nanocapsule like morphology while Fe distributed mesoporous graphitic carbon sheets, with a specific surface area value of 565 m(2) g(-1) obtained by modulating the synthesis chemistry in CHI-TMA-Fe-CW-M1. The higher percentage of graphitic N in CHI-TMA-Fe-CW-M1 apparent from the XPS data validate that the modified synthetic method favours creation of more graphitic N sites contributing for better catalytic performance. CHI-TMA-Fe-CW-M1 catalyst exhibited comparable electrocatalytic activity with that of the commercially available Pt/C via an efficient four-electron-dominant ORR pathway with a positive onset potential value of 0.925 V vs RHE. Good durability of CHI-TMA-Fe-CW-M1 after 5000 cycles further confirm the prospects of MOG-chitosan and the feasibility to be used as a potential catalyst for ORR.
Keywords: electrocatalyst; fuel cell; Metal-Organic-Gel; oxygen reduction reaction

Cisplatin-induced self-assembly of graphene oxide sheets into spherical nanoparticles for damaging sub-cellular DNA - Nandi, Aditi; Mallick, Abhik; More, Piyush; Sengupta, Poulomi; Ballav, Nirmalya; Basu, Sudipta (Chemical Communications, 2017)
This report describes the hitherto unobserved cisplatin induced self-assembly of 2D-graphene oxide sheets into 3D-spherical nano-scale particles. These nanoparticles can encompass dual DNA damaging drugs simultaneously. A combination of confocal microscopy, gel electrophoresis and flow cytometry studies clearly demonstrated that these novel nanoparticles can internalize into cancer cells by endocytosis, localize into lysosomes, and damage DNA, leading to apoptosis. Cell viability assays indicated that these nanoparticles were more cytotoxic towards cancer cells compared to healthy cells.

Click-chemistry-based multicomponent condensation approach for design and synthesis of spirochromene-tethered 1,2,3-triazoles as potential antitubercular agents - Chavan, Pramod V.; Pandit, Kapil S.; Desai, Uday V.; Wadgaonkar, Prakash P.; Nawale, Laxman; Bhansali, Sujit; Sarkar, Dhiman (Research on Chemical Intermediates, 2017)

Clues from crystal structures pave the way to access chiral myo-inositol derived versatile synthons: resolution of racemic 4-o-allyl-myo-inositol-1,3,5-orthoesters via corresponding dicamphanates by crystallization - Patil, Nivedita T.; Shashidhar, Mysore S.; Tamboli, Majid I.; Gonnade, Rajesh G. (Crystal Growth & Design, 2017)
Racemic 4-O-allyl-myo-inositol-1,3,5-orthoesters were resolved as the corresponding diastereomeric dicamphanates by crystallization from alcoholic solvents. Crystals of the two diastereomers of myo-inositol orthoacetate and one diastereomer each of myo-inositol orthoformate and myo-inositol orthobenzoate were obtained in >99% purity, on gram scale. The configuration of all these diastereomers was established by conversion to known chiral myo-inositol derivatives as well as by single crystal structure analysis. It is interesting to note that the procedures for the separation of diastereomeric myo-inositol orthoesters could be evolved due to the knowledge of crystal growth and crystal structures of inositol derivatives of comparable molecular structures. Due to the synthetic versatility of myo-inositol orthoesters, the methods described provide rapid and convenient access to a variety of chiral inositol derivatives with high synthetic potential.

Co-catalytic metal oxide nanoparticles decorated silicon/hematite core shell nanowire arrays as efficient photo electrodes for water splitting - Devarapalli, Rami Reddy; Kamaja, Chaitanya Krishna; Shelke, Manjusha V. (ChemistrySelect, 2017)
By looking global energy demands, development of highly efficient stable semiconductor photoelectrodes for photoelectrochemical (PEC) water splitting is highly desirable. Herein, we have fabricated co-catalytic nanoparticles decorated Silicon nanowire (SiNWs)/Hematite(Fe2O3) core sell structures as photo anodes and studied the PEC water oxidation properties. As, Fe2O3 possess weak oxidation kinetics, decoration of NiO and Co3O4 nanoparticles on SiNW/Fe2O3 by hydrothermal method, which acts as co-catalysts to improves the water oxidation reactions. It was found that decoration of Co3O4 nanoparticles enhances the photocurrent up to 2.6 times, whereas for NiO nanoparticles improvement is of 1.5 times when compared to the undecorated electrodes. Along with enhancement of photocurrents, it also shows shift of onset potentials. The effect of the co-catalytic nanoparticles on the enhancement of photocurrent and charge transfer resistance at the interface of electrode-electrolyte have been studied by electrochemical impedance spectroscopy. Further, flat band potentials of the photo electrodes have been measured by using Mott-schottky analysis.
Keywords: Co-catalysts; photo anodes; Photoelectrochemical cell; silicon nanowires; water splitting

Colloidal nanocomposite of TiN and N-doped few-layer graphene for plasmonics and electrocatalysis - Shanker, G. Shiva; Markad, Ganesh B.; Jagadeeswararao, Metikoti; Bansode, Umesh; Nag, Angshuman (ACS Energy Letters, 2017)
A combination of high carrier density, high surface area, solution processability, and low cost is desired in a material for electrocatalytic applications, including H-2 evolution and a counter electrode of a solar cell. Also, plasmonic-based applications in biological systems can be derived from such material. In this regard, a colloidal nanocomposite of TiN and N-doped few-layer graphene (TiN NFG) is synthesized from molecular precursors. TiN nano crystals (NCs) provide free electrons for electrical conductivity and plasmonics, whereas NFG is responsible for charge transport, high surface area, and colloidal stability. Colloidal TiN NFG nano composites exhibit a localized surface plasmon resonance band at around 700 nm. Coatings of the nanocomposite form a counter electrode for efficient (8.9%) dye-sensitized solar cells. Furthermore, the nanocomposite acts as an efficient electrocatalyst for hydrogen evolution reaction, exhibiting an overpotential similar to 161 mV at a current density of 10 mA/cm(2).

Computational strategies to explore antimalarial thiazine alkaloid lead compounds based on an australian marine sponge plakortis lita - Lilly, Aswathy; Jisha, R. S.; Masand, Vijay H.; Gajbhiye, Jayant M.; Shibi, Indira G. (Journal of biomolecular Structure & Dynamics, 2017)
In this work, an attempt was made to propose new leads based on the natural scaffold Thiaplakortone-A active against malaria. The 2D QSAR studies suggested that three descriptors correlate with the anti-malarial activity with an R2 value of 0.814. Robustness, reliability and predictive power of the model were tested by internal validation, external validation, Y-scrambling and Applicability domain analysis. HQSAR studies were carried out as an additional tool to find the sub-structural fingerprints. The CoMFA and CoMSIA models gave Q2 values of 0.813 and 0.647, and R2ncv values of 0.994 and 0.984, respectively. Using the 2D-QSAR equation, the activity values of the seven modified compounds were calculated and it was found that three molecules showed good anti-malarial activity. Molecular docking of the 42 Thiaplakortone-A derivatives with P. falciparum calcium-dependent protein kinase 1 (PfCDPK1) was carried out to find out protein-ligand interactions. Data mining of the bioassay dataset AID: 504850 using the classifier based on Random Forest (RF) of Weka suggested that all of the eight molecules selected and three out of the seven virtual molecules were anti-malarial active. Both the virtual molecules and drug molecules were docked with CYP3A4, indicating that the virtual molecules could metabolize easily. Toxicity studies using Osiris shows that three molecules showed no toxic characters.

Concise enantioselective synthesis of 1,4-dideoxy-1,4-imino-D-arabinitol using Co(III)(salen)-catalyzed hydrolytic kinetic resolution of a two-stereocentered anti-azido epoxide - Reddi, Rambabu N.; Prasad, Pragati K.; Kalshetti, Rupali G.; Sudalai, Arumugam (Tetrahedron-Asymmetry, 2017)
A concise enantioselective synthesis of 1,4-dideoxy-1,4-imino-D-arabinitol, (+)-DAB-1, has been described in good overall yield (18.1%) and with high enantiomeric purity (up to 98% ee) starting from a simple raw material, cis-2-butene-1,4-diol. The Co-catalyzed hydrolytic kinetic resolution of a two-stereocentered racemic azido epoxide followed by asymmetric dihydroxylation of the alkene and 'one pot' reductive cyclisation of the azido diol are key reactions in the synthetic sequence. (C) 2016 Elsevier Ltd. All rights reserved.

Concurrent synthesis of SnO/SnO2 nanocomposites and their enhanced photocatalytic activity - Roy, Animesh; Arbuj, Sudhir; Waghadkar, Yogesh; Shinde, Manish; Umarji, Govind; Rane, Sunit; Patil, Kashinath; Gosavi, Suresh; Chauhan, Ratna (Journal of Solid State Electrochemistry, 2017)
The SnO/SnO2 nanocomposites were synthesized using semisolvothermal reaction technique. These nanocomposites were prepared using different combination of solvents viz., ethanol, water, and ethylene glycol at 180 A degrees C for 24 h. The synthesized nanocomposites were analyzed with various characterization techniques. Structural analysis indicates the formation of tetragonal phase of SnO2 for the sample prepared in ethanol, whereas for other solvent combinations, the mixture of SnO and SnO2 having tetragonal crystal structures were observed. The optical study shows enhanced absorbance in the visible region for all the prepared SnO/SnO2 nanocomposites. The observed band gap was found to be in the range of 3.0 to 3.25 eV. Microstructural determinations confirm the formation of nanostructures having spherical as well as rod-like morphology. The size of nanoparticles in ethanol-mediated solvent was found to be in the range of 5 to 7 nm. Thermogravimetric analysis indicate the weight gain around 1.3 wt% confirming the conversion of SnO to SnO2 material. The photocatalytic activity of synthesized nanocomposites was evaluated by following the aqueous methylene blue (MB) degradation. The sample prepared in ethylene glycol-mediated solvent showed highest photoactivity having apparent rate constant (K-app) 0.62 x 10(-2) min(-1).
Keywords: Dye-degradation; Nanocomposite; Photocatalysis; tin oxide

Conformational and functional transitions and in silico analysis of a serine protease from conidiobolus brefeldianus (MTCC 5185) - Shukla, Ekta; Agrawal, Sanskruthi B.; Gaikwad, Sushama M. (International Journal of Biological Macromolecules, 2017)
This work describes functional and structural transitions of a novel protease isolated from Conidiobolus brefeldianus MTCC 5185 (Cprot), in detail using biophysical and bioinformatics tools. The commercial importance of Cprot in silk and leather industries made it an interesting candidate for structural investigations. Cprot possesses 8.2%alpha-helix, 31.1% beta-sheet and 23.8% turns. The enzyme was found to be active over a wide pH range and up to 55 degrees C. The protease was also stable in organic solvents up to 50% (v/v) concentration of alcohols and DMSO for >24 h and in 2 M guanidine hydrochloride for >12 h. Cprot was also resistant to trypsin, chymotrypsin, proteinase K and fluorinated alcohols (5-10%). The melting temperatures observed for the native Cprot and for the enzyme treated under various stress conditions correlated well with the corresponding structural and functional transitions obtained. The structural information was supported by the homology model of its closest homologue from C. coronatus; revealing its similarity to PA clan of proteases (Proteases of mixed nucleophile, superfamily A), with His-64, Asp-113 and Ser-208 as putative catalytic triad. Three tryptophan residues in Cprot are surrounded by positively charged residues, as evident from solute quenching studies and homology model. (C) 2017 Elsevier B.V. All rights reserved.

Constructing ultraporous covalent organic fameworks in seconds via an organic terracotta process - Karak, S.; Kandambeth, S.; Biswal, B. P.; Sasmal, H. S.; Kumar, S.; Pachfule, P.; Banerjee, R. (Journal of the American Chemical Society, 2017)
Research on covalent organic frameworks (COFs) has recently gathered significant momentum by the virtue of their predictive design, controllable porosity, and long-range ordering. However, the lack of solvent-free and easy-to-perform synthesis processes appears to be the bottleneck toward their greener fabrication, thereby limiting their possible potential applications. To alleviate such shortcomings, we demonstrate a simple route toward the rapid synthesis of highly crystalline and ultraporous COFs in seconds using a novel salt-mediated crystallization approach. A high degree of synthetic control in interlayer stacking and layer planarity renders an ordered network with a surface area as high as 3000 m(2) g-(1). Further, this approach has been extrapolated for the continuous synthesis of COFs by means of a twin screw extruder and in situ processes of COFs into different shapes mimicking the ancient terracotta process. Finally, the regular COF beads are shown to outperform the leading zeolites in water sorption performance, with notably facile regeneration ability and structural integrity.

Continuous flow telescopic oxidation of alcohols via generation of chlorine and hypochlorite - Sharma, Y.; Moolya, S.; Joshi, Ramesh A.; Kulkarni, Amol A. (Reaction Chemistry & Engineering, 2017)
A 3-step continuous flow oxidation of alcohols is demonstrated with continuous generation of chlorine as the first step followed by its use for the flow synthesis of high strength sodium hypochlorite. The solution is subsequently used for oxidation of alcohols in the presence of a catalytic amount of the nitroxyl radical “TEMPO”, which inhibits oxidation at the aldehyde stage. Selective oxidations of eight different alcohols were demonstrated. To achieve identical yields, the aromatic alcohols containing electron withdrawing groups needed a longer residence time than aliphatic alcohols.

Control of polymerization reactors - Schurk, F. J; Deshpande, P. B; Leffew, K. W.; Nadkarni, V. M. (CRC Press, 2017)
This reference and text provides an in-depth description of developments in control techniques and their application to polymerization reactors and offers important introductory background information on polymerization reaction engineering.;Discussing modelling, identification, linear, nonlinear and multivariable schemes, Control of Polymerization Reactors: presents all available techniques that can be used to control reactors properly for optimal performance; shows how to manipulate pivotal variables that affect reactor control; examines methods for deriving dynamic process models to improve reactor efficiency; reviews reactor control problems and points out end-use properties; supplies methods for measuring process variables, and ways to estimate variables that can’t be measured; and explains how single-input, single-output (SISO) strategies can be effectively used for control.;Filled with illustrative examples to clarify concepts, including more than 730 figures, tables and equations, Control of Polymerization Reactors is intended for use as a reference for chemical, process development, process design, research and development, control systems, and polymer engineers; and polymer chemists and physicists; as well as a text for upper-level undergraduate and graduate students in polymerization reactor control courses.

Controlling necking in extrusion film casting using polymer nanocomposites - Rokade, Dhammaraj; Azad, Lal B.; Poddar, Suparna; Mishra, Satyendra; Pol, Harshawardhan V.; Shukla, Rishab (Journal of Macromolecular Science Part B-Physics, 2017)
The research described was concerned with the effect of layered-silicate-based organically modified nanoclay fillers on controlling the extent of necking in a polymer melt extrusion film casting (EFC) process. We show that a linear polythylene resin (such as a linear low-density polyethylene-LLDPE) filled with a very low percentage of well-dispersed (or intercalated) nanoclay displays an enhanced resistance to the necking phenomenon. In general, melt-compounded nanoclay-filled LLDPE resin formulations displayed a higher final film width (less necking), thus a lower final film thickness (greater draw down for the same draw ratio), and cooled down faster when compared to the base LLDPE resin. Incorporation of nanoclay filler in the mainly linear chain LLDPE resin led to significant modification of the melt rheological properties that, in turn, affected the melt processability of these formulations. Primarily, the intercalated nanoclay-filled LLDPE formulations displayed the presence of strain-hardening in unaxial extensional rheology. Additionally, the presence of well-dispersed nanoclay in the LLDPE resin led to a display of prominent extrudate swell indicating the presence of melt elasticity in such formulations. The presence of melt elasticity, as shown by shear rheology and strain-hardening, observed by uniaxial extensional rheology, contributed to the LLDPE nanoclay formulations displaying an enhanced resistance to necking for these films. It can be concluded that linear chain polymers susceptible to necking in an EFC process can be made more resistant to such necking by using nanoclay fillers at very low levels of loading.

Convenient new and efficient commercial synthetic route for dasatinib (sprycel®) - Suresh, Garbapu; Nadh, Ratnakaram Venkata; Srinivasu, Navuluri; Yennity, Durgaprasad (Synthetic Communications, 2017)
A new and efficient synthetic route for dual Src/Abl kinase inhibitor Dasatinib (Sprycel®), an anticancer drug, is described. This commercially viable process yields Dasatinib monohydrate free of potential impurities with consistent yield of 68% in route A and 61% in route B with HPLC purity >99.80% over 4 stages.

Convenient route for Au@Ti-SiO2 nanocatalyst synthesis and its application for room temperature CO oxidation - Soni, Yogita; Kumar, Anumol Erumpukuthical Ashok; Nayak, Chandrani; Deepak, Francis Leonard; Vinod, C. P. (Journal of Physical Chemistry C, 2017)
Small gold nanoparticles.of size less than 5 nm encapsulated inside titanium modified silica shell have been reported. Here, a modified sol-gel method, which is a one-step process, produces Au@Ti-SiO2 nanocatalyst with a good control of titanium loading. With a titanium loading of 0.9 and 2.2 wt % in silica, unprecedented low temperature activity (full conversion) is observed for this catalyst for CO oxidation reaction compared to Au@SiO2 catalyst. A combination of optimum sized gold nanoparticles with a large amount of oxygen vacancies created due to Ti incorporation in silica matrix is considered to be the reason for this enhanced catalytic activity. The size of.gold nanoparticles is maintained even after high temperature pretreatments, which show the benefit of encapsulation. The effect of the various pretreatments on the catalytic activity has also been reported.

Copper oxide supported on three-dimensional ammonia-doped porous reduced graphene oxide prepared through electrophoretic deposition for non-enzymatic glucose sensing - Maaoui, H.; Singh, S. K.; Teodorescu, F.; Coffinier, Y.; Barras, A.; Chtourou, R.; Kurungot, S.; Szunerits, S.; Boukherroub, R. (Electrochimica Acta, 2017)
The paper reports on the preparation of N-doped porous reduced graphene oxide/copper oxide (ammonia-doped-prGO/CuO) nanocomposite on gold electrodes using electrophoretic deposition (EPD) from an ethanolic suspension of ammonia-doped-prGO and Cu(ClO4)(2) by applying a DC voltage. The ammonia-doped-prGO/CuO nanocomposite film thickness is controlled by varying the deposition time. Morphological analysis using scanning electron microscopy (SEM) showed the formation of a 3 dimensional structure with CuO nanoparticles being homogeneously embedded in the graphene layer. Xray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman analysis revealed that the deposited copper was in its oxidized form, mainly CuO. The Au/ammonia-doped-prGO/CuO electrode was successfully applied for non-enzymatic amperometric detection of glucose. Under optimized conditions, the electrode exhibited a sensitivity of 1210 mu mM(-1) cm(-2) with a detection limit of 0.25 p,M (S/N =3) over a wide concentration range (0.25 mu M to 6 mM) at an applied potential of +0.50 V vs. Ag/AgCl. The electrode material displayed good stability, excellent selectivity, and accurate measurement in healthy and diabetic human serum samples.

Coumarin-appended stable fluorescent self-complementary quadruple-hydrogen-bonded molecular duplexes - Kheria, Sanjeev; Rayavarapu, Suresh; Kotmale, Amol S.; Shinde, Dinesh R.; Gonnade, Rajesh G.; Sanjayan, Gangadhar J. (Journal of Organic Chemistry, 2017)
In this paper we report a coumarin-conjugated self-assembling system adorned with valuable features such as high duplex stability and a built-in fluorophore, which would augment its application potential. This system forms a highly :stalik molecular duplex in a nonpolar solvent (K-dim > 1.9 X 10(7) M-1 in CDCl3). Due to the fluorescent property of coumarin, these new structural motifs may find potential application in material chemistry and supramolecular chemistry.

Crystallisation-enhanced bulk hole mobility in phenothiazine-based organic semiconductors - Shinde, D. B.; Salunke, Jagadish K.; Candeias, Nuno R.; Tinti, Francesca; Gazzano, Massimo; Wadgaonkar, P. P.; Priimagi, Arri; Camaioni, Nadia; Vivo, Paola (Scientific Reports, 2017)
A series of three novel donor-acceptor systems based on C(3)-malononitrile-substituted phenothiazines was synthesised in good overall yields and their thermal, spectroscopic, and electrochemical properties were characterised. The compounds were prepared through a sequence of Ullmann-coupling, Vilsmeier-Haack formylation and Knoevenagel-condensation, followed by Suzuki-coupling reactions for introduction of aryl substitutents at C(7) position of the phenothiazine. The introduction of a donor unit at the C(7) position exhibited a weak impact on the optical and electrochemical characteristics of the compounds and led to amorphous films with bulk hole mobilities in the typical range reported for phenothiazines, despite the higher charge delocalisation as attested by computational studies. In contrast, highly ordered films were formed when using the C(7)-unsubstituted 3-malononitrile phenothiazine, exhibiting an outstanding mobility of 1 x 10(-3) cm(2) V-1 s(-1), the highest reported for this class of compounds. Computational conformational analysis of the new phenothizanes suggested that free rotation of the substitutents at the C(7) position suppresses the ordering of the system, thereby hampering suitable packing of the new materials needed for high charge carrier mobility.

C(sp(3))-F, C(sp(2))-F and C(sp(3))-H bond activation at silicon(II) centers - Swamy, V. S. V. S. N.; Parvin, Nasrina; Raj, K. Vipin; Sen, Sakya S. (Chemical Communication, 2017)
Silylene [PhC(NtBu)(2)SiN(SiMe3)(2)] (1) cleaves the C(sp(3))-H and C-F bonds of acetophenone and 1,1,1-trifluoroacetophenone, respectively, under mild conditions. The reaction is initiated via a nucleophilic attack from the oxygen to the silicon atom followed by C-F/H bond cleavage. The scope of C-F bond activation has further been extended with C6F6 and C6F5CF3.
Keywords: Boron triple bond; C-F Bond; Fluorinated Building-Block; H Activation; Ketones; N-heterocyclic carbenes; Oxodative Addition; Perfluorinated Arenes; Selective Activation; Transition-Metal Centers

CuCo2O4 nanowall morphology as Li-ion battery anode: Enhancing electrochemical performance through stoichiometry control - Bhardwaj, M.; Suryawanshi, A.; Fernandes, R.; Tonda, S.; Banerjee, A.; Kothari, D.; Ogale, S. (Materials Research Bulletin, 2017)
We have employed template-free synthesis of CuCo2O4 (CCO) system to achieve unique ultrathin porous nanowall type morphology, and evaluated for Li-Ion battery anode application. We observe that under the hydrothermal growth a starting stoichiometric mixture of cationic precursor's leads to a bi-phasic constitution comprising of defect-spinel CCO and a small quantity of CuO. Use of the excess but optimum cobalt in the precursor mix leads to single phase defect-spinel. We have carefully examined the implications of off-stoichiometry for different cases of interest (including the case of Cu-excess) for morphology, microstructure, the physical/electrochemical properties, and the evolution of the Li-ion battery anode under cycling for different active materials loading. In case of optimum Cu excess based CCO renders an impressive performance as Li-ion battery anode with high rate performance, 836 mAh g−1 and 757 mAh g−1 at 1.25C and 2.5C, respectively, and good cycling stability. © 2016 Elsevier Ltd

Cyclization mechanism of phomopsene synthase: mass spectrometry based analysis of various site-specifically labeled terpenes - Shinde, Sandip S.; Minami, Atsushi; Chen, Zhi; Tokiwano, Tetsuo; Toyomasu, Tomonobu; Kato, Nobuo; Sassa, Takeshi; Oikawa, Hideaki (Journal of Antibiotics, 2017)
Elucidation of the cyclization mechanism catalyzed by terpene synthases is important for the rational engineering of terpene cyclases. We developed a chemoenzymatic method for the synthesis of systematically deuterium-labeled geranylgeranyl diphosphate ( GGPP), starting from site-specifically deuterium-labeled isopentenyl diphosphates (IPPs) using IPP isomerase and three prenyltransferases. We examined the cyclization mechanism of tetracyclic diterpene phomopsene with phomopsene synthase. A detailed EI-MS analysis of phomopsene labeled at various positions allowed us to propose the structures corresponding to the most intense peaks, and thus elucidate a cyclization mechanism involving double 1,2-alkyl shifts and a 1,2-hydride shift via a dolabelladien-15-yl cation. Our study demonstrated that this newly developed method is highly sensitive and provides sufficient information for a reliable assignment of the structures of fragmented ions.

Deciphering structural stability and binding mechanisms of potential antagonists with smoothened protein - Sinha, N. (Journal of Biomolecular Structure and Dynamics, 2017)
Identification of new potential inhibitors against Hedgehog pathway activator protein Smoothened (SMO) is considered to be of higher importance to improvise the future cancer therapeutics. Different SMO inhibitors/drugs (e.g. Cyclopamine, Vismodegib, Taladegib) used till date are found to be associated with several drug-related resistivity and toxicity. To explore the ability of new drug/inhibitor molecules, which can show better/similar binding and dynamic stability as compared to known inhibitors, virtual screening against SMO is performed followed by the comparative docking and molecular dynamic studies. ‘ZINC12368305’ is found to be the best molecule among the entire data-set, as it shows the highest binding affinity and stable conformations. Here, an integrative approach using Dynamic Graph Theory is introduced to gain the molecular insights of the structural integrity of these protein complexes at the residue level by analyzing the corresponding Protein Contact Networks along the Molecular Dynamics trajectories. The study further focuses to understand the detailed binding mechanisms of available inhibitor/drug molecules along with the newly predicted molecule. It is observed that a unique big cluster of low fluctuating residues at the vicinity of the drug binding pocket of the SMO in ZINC12368305-bound complex is present and driving it toward a more stable region. A close inspection on this site reveals the presence of a stable Pi–Pi interaction between the pyrazole group-associated phenanthrene ring of ZINC12368305 and aromatic ring of Phe484 of SMO, which could be the potential factor of ZINC12368305 to create a more stable complex with SMO as compared to the other inhibitors.
Keywords: inhibitors; Pi–Pi Interaction; Smoothened Protein; Structural stability

Defluoridation of drinking water using fe-al mixed metal hydroxides - Telang, T.; Deosarkar, M.P.; Shetty, R.; Kamble, S.P. (Novel Water Treatment and Separation Methods: Simulation of Chemical Processes, 2017)
In this chapter, we report findings from study carried out on removal of fluoride from drinking or potable water using Fe-Al mixed metal hydroxides. For experimental analysis, the product mixed Fe-Al hydroxides was prepared by applying a co-precipitation method. The resulting metal hydroxide was thoroughly characterized using analytical tests of X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area analysis. In order to characterize the equilibrium behavior of adsorbent, we study experimentally the effects of different operating parameters. The selected parameters for analysis are adsorbent loading, initial fluoride concentration, pH of the solution, and interfering ions (usually present in groundwater). The equilibrium adsorption data was later fitted for Langmuir adsorption isotherm, and experimental observations show a maximum fluoride adsorption capacity of 2.05 mg.g-1. The experimental results reveal that the adsorption dynamics follows a pseudo-second-order kinetic model.

On demand electrochemical release of drugs from porous reduced graphene oxide modified flexible electrodes - Boulahneche, Samia; Jijie, Roxana; Barras, Alexandre; Chekin, Fereshteh; Singh, Santosh K.; Bouckaert, Julie; Medjram, Mohamed Salah; Kurungot, Sreekumar; Boukherroub, Rabah; Szunerits, Sabine (Journal of Materials Chemistry B, 2017)
Despite the advantages of an electrochemical control for drug release, only a handful of electrochemical-based release systems have been developed so far. We report herein on the development of an electrochemically activatable platform for on-demand delivery of drugs. It is based on flexible gold thin film electrodes coated with porous reduced graphene oxide (prGO) nanosheets onto which the drug of interest has been integrated beforehand. Two different drugs are investigated here: ondansetron hydrochloride (ODS), a selective 5-HT3 receptor antagonist used for preventing nausea and vomiting caused by chemotherapy and radiotherapy, and ampicillin (AMP), an antibiotic to prevent and treat a number of bacterial infections such as respiratory tract infections, urinary tract infections, and meningitis. In the case of ODS, application of a negative potential bias of -0.8 V results in a sustained slow ODS release with an ODS flux of 47 mu g cm(-2) h(-1). In the case of AMP, we show that polyethyleneimine modified prGO (prGO/PEI) is an extremely efficient matrix. Upon the application of +0.8 V, 24% of AMP could be released from the electrical interface in a time span of 2 h. The released AMP kept its antibacterial activity as demonstrated by antimicrobial tests. These examples illustrate the major benefits of the developed approach for biomedical applications.

Deployment of underground coal gasification in India - Singan, Akshay; Ranade, Vivek V. (Current Science, 2017)

Description of Lysinibacillus telephonicus sp nov., isolated from the screen of a cellular phone - Rahi, Praveen; Kurli, Rashmi; Khairnar, Mitesh; Jagtap, Shubhangi; Pansare, Aabeejjeet N.; Dastager, Syed G.; Shouche, Yogesh S. (International Journal of Systematic and Evolutionary Microbiology, 2017)
A novel bacterial strain, designate dS5H2222(T), was isolated form the screen of a cellular phone. The cells were Gram-stainpositive, rod-shaped, aerobic and motile, and endospores are formed. S5H2222(T) grew as pale white colonies on trypticase soy agar and the best growth was observed at 37 degrees C (10- 55 degrees C) and at pH 7.0 (5.0-9.0). S5H2222(T) could tolerate up to 10% (w/v) NaCl. Phylogenetic analysis based on 16S rRNA gene sequences placed this strain within the genus Lysinibacillus and it exhibited high 16S rRNA gene sequence similarity to Lysinibacillus halotolerans LAM612(T) (97.8 %), Lysinibacillus chungkukjangi2RL3-2(T) (97.4 %) and Lysinibacillus sinduriensis BLB-1(T) (97.2 %). TheDNA- DNA relatedness of the strain with L. halotolerans JCM 19611(T), L. chungkukjangi KACC 16626(T) and L. sinduriensis KACC 16611(T) was 57, 64 and 55% respectively. The genomic DNA G+C content was 39.8 mol%. The major fatty acids of S5H2222(T) were iso-C-15:0, anteiso-C-15:0, iso-C-16:0 and anteiso-C-17:0. MK-7 was the only menaquinone and the main polar lipids were diphosphatidylglycerol, phosphatidylglycerol and phosphatidylethanolamine, four unidentified polar lipids were also present. The diagnostic amino acids in the cell wall peptidoglycan contained Lys-Asp (type A4 alpha). On the basis of the results of the phenotypic and genotypic characterizations, it was concluded that S5H2222(T) represents a novel species of the genus Lysinibacillus, for which the name Lysinibacillus telephonicus sp. nov. is proposed. The type strain is S5H2222(T) (=MCC 3065 T =KACC 18714(T)=LMG 29294(T)).

Determination of onset temperature from the entropy for fragile to strong liquids - Banerjee, Atreyee; Nandi, Manoj Kumar; Sastry, Srikanth; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2017)
In this paper, we establish a connection between the onset temperature of glassy dynamics with the change in the entropy for a wide range of model systems. We identify the crossing temperature of pair and excess entropies as the onset temperature. Below the onset temperature, the residual multiparticle entropy, the difference between excess and pair entropies, becomes positive. The positive entropy can be viewed as equivalent to the larger phase space exploration of the system. The new method of onset temperature prediction from entropy is less ambiguous, as it does not depend on any fitting parameter like the existing methods. Published by AIP Publishing.

Determination of the absolute configuration of gliomasolide D through total syntheses of the C-17 epimers - Seetharamsingh, B.; Ganesh, Routholla; Reddy, D. Srinivasa (Journal of Natural Products, 2017)
The absolute configuration at C-17, the carbon bearing the distal hydroxy group of the 14-membered natural product gliomasolide D, was assigned as R by comparison of C-13 NMR shifts and specific rotation values of the epimers at C-17. The first total synthesis of gliomasolide D along with its C-17 epimer, regioselective macrocyclization (18 membered vs 14 membered), and regioselective Wacker oxidation are highlights of the present work.

Determination of triazines and triazoles in grapes using atmospheric pressure matrix-assisted laser desorption/ionization high-resolution mass spectrometry - Mahale, Vishal; Singh, Ajeet; Phadke, Gayatri S.; Ghanate, Avinash D.; Oulkar, Dasharath P.; Banerjee, Kaushik; Panchagnula, Venkateswarlu (Journal of Aoac International, 2017)
A chromatography-free atmospheric pressure matrix-assisted laser desorption/ionization high-resolution mass spectrometry (AP-MALDI HRMS) method is described for the simultaneous and quantitative detection of triazines and triazoles in grapes. The analytes were detected reproducibly with high mass accuracy (mass error within 5 ppm) and further confirmed by collision-induced dissociation fragmentation in tandem MS. The LODs and LOQs for all the analytes were found to be in the nanogram per gram level (15-20 ng/g LOQ). Internal standard normalized high-resolution accurate mass extracted (HR-AM) peak intensities of the detected ions were used to generate the concentration response curves. Linearity (with R-2 values around 0.99) was obtained for these curves within a concentration range of 20-200 ng/g of the individual analytes. The accuracy and precision of the method were further established using QC samples. Validation and performance comparison of the AP-MALDI HRMS method with an existing standard method using LC with :triple quadrupole MS was carried out (evaluating sensitivity, accuracy, precision, and analysis time) using 20 table-grape field samples after QuEChERS extraction.

Developing techno-economically sustainable methodologies for deep desulfurization using hydrodynamic cavitation - Suryawanshi, N.B. (Fuel, 2017)
The present work, for the first time, describes the efficacy of the cavitation process and compares the cavitation yield for two types of cavitation devices-one employing linear flow for the generation of cavities and other employing vortex flow. The process involves pre-programmed mixing of the organic and aqueous phases, and can be carried out using simple mechanical cavitating devices such as orifice or vortex diode. The process essentially exploits in situ generation of oxidising agents such as hydroxyl radicals for oxidative removal of sulfur. The efficiency of the process is strongly dependent on the nature of device apart from the nature of the organic phase. The effects of process parameters and engineering designs were established for three organic solvents (n-octane, toluene, n-octanol) for model sulfur compound-Thiophene. A very high removal to the extent of 95% was demonstrated. The results were also verified using commercial diesel. The cavitation yield is significantly higher for vortex diode compared to the orifice. The process has potential to provide a green approach for desulfurization of fuels or organics without the use of catalyst or external chemicals/reagents apart from newer engineering configurations for effective implementation of hydrodynamic cavitation in industrial practice and also appears to be economically sustainable.
Keywords: Fuel; Oxidation; Petroleum; Pollution Control; Sulphur Removal

Development of ARM based embedded controller for mass flow controller system - Iyer, N.; Shinde, S.; Dhawale, T.; Shelar, N. (9th International Conference on Trends in Industrial Measurement and Automation, TIMA 2017., 2017)
The purpose for this paper is to describe the central Embedded Controller development done for Mass Flow Controllers (MFCs) M100B system. Work caters to control M100B MFCs being used for one of the systems at National Chemical Laboratory. M100B MFC accurately measures and controls the mass flow rates of gases. The central controller for this system is non functional and technology is outdated and hence new central embedded controller is developed for the system. Development is done using ARM7 32-bit RISC microcontroller Philips LPC2148, as low power and high frequency design. Serial ADCs are interfaced to ARM microcontroller. LCD display 20×4 is used for display of run status, diagnostic and error messages. Touch keypad is designed and interfaced for setting of mass flow rate for different MFCs against MFC number selected by keypad. The software development is done using Keil micro vision 4. This ARM based controller is a real time system with display of diagnostic and error messages.

Development of (quinolinyl)amido-based pincer palladium complexes: a robust and phosphine-free catalyst system for C–H arylation of benzothiazoles - Pandiri, Hanumanprasad; Soni, Vineeta; Gonnade, Rajesh G.; Punji, Benudhar (New Journal of Chemistry, 2017)
(Quinolinyl)amido-ligated palladium(II) complexes have been synthesized and applied in the catalytic C–H bond arylation of benzothiazoles. The tridentate ligand precursors R2N-C(O)CH2-(NH)-C9H6N [(R2NNN8-Q)–H; R2N = morpholinyl, Me-N-piperazinyl] and the pincer palladium complexes [κN,κN,κN-{R2N-C(O)CH2-(μ-N)-C9H6N}]PdX [(R2NNN8-Q)PdX {R2N = Et2N, morpholinyl, Me-N-piperazinyl; X = OAc or Cl}] were efficiently synthesized, and characterized by various analytical techniques. The iodo derivative (Et2NNN8-Q)PdI was obtained in excellent yield by the treatment of the complex (Et2NNN8-Q)PdCl with KI. The molecular structures of complexes (Et2NNN8-Q)Pd(OAc) (2a), (Et2NNN8-Q)PdCl (3a) and (Et2NNN8-Q)PdI (4a) were elucidated by X-ray crystallography. Complex 3a was found to be the most efficient catalyst for direct C–H bond arylation of substituted benzothiazoles with diverse aryl iodides using a mild base, K2CO3. The working catalyst system 3a is highly robust and can be recycled and reused several times for the arylation of benzothiazole without loss of catalytic activity. Preliminary mechanistic investigations using controlled studies and kinetic analysis have been performed, which greatly support a molecular mechanism for the arylation.

Diastereoselective synthesis of chiral 2,3-disubstituted lndolines via formal [3+2]-cycloaddition of arynes with gamma-amino-alpha,beta-unsaturated esters - Aher, Ravindra D.; Suryavanshi, Gurunath M.; Sudalai, Arumugam (Journal of Organic Chemistry, 2017)
A one step formal [3+2]-annulation protocol for the synthesis of 2,3-disubstituted indolines is described. The in situ generated aryne acts as a two-atom component, and gamma-amino-alpha,beta-unsaturated esters acting as a three-atom component to construct indoline units in a highly regio- and diastereoselective manner with yields ranging from 63 to 80%.

Differential rubisco content and photosynthetic efficiency of rol gene integrated Vinca minor transgenic plant: correlating factors associated with morpho-anatomical changes, gene expression and alkaloid productivity - Verma, Priyanka; Khan, Shamshad Ahmad; Masood, Nusrat; Manika, N.; Sharma, Abhishek; Verma, Neha; Luqman, Suaib; Mathur, Ajay K. (Journal of Plant Physiology, 2017)
Transgenic plants obtained from a hairy root line (PVG) of Vinca minor were characterized in relation to terpenoid indole alkaloids (TIAs) pathway gene expression and vincamine production. The hairy roots formed callus with green nodular protuberances when transferred onto agar-gelled MS medium containing 3.0 mg/l zeatin. These meristematic zones developed into shoot buds on medium with 1.0 mg/l 2, 4-dichlorophenoxyacetic acid and 40 mg/l ascorbic acid. These shoot buds subsequently formed rooted plants when shifted onto a hormone-free MS medium with 6% sucrose. Transgenic nature of the plants was confirmed by the presence of rol genes of the Ri plasmid in them. The transgenic plants (TP) had elongated internodes and a highly proliferating root system. During glass house cultivation TP consistently exhibited slower growth rate, low chlorophyll content (1.02 +/- 0.08 mg/gm fr. wt.), reduced carbon exchange rate (2.67 +/- 0.16 mu mol m(-2) s(-1)), less transpiration rate (2.30 +/- 0.20 mmol m(-2) s(-1)) and poor stomatal conductance (2.21 +/- 0.04 mmol m-2 s(-1)) when compared with non-transgenic population. The activity of rubisco enzyme in the leaves of TP was nearly two folds less in comparison to non-transgenic controls (1.80 milliunits ml(-1) mg protein-1 against 3.61 milliunits ml(-1) mg protein-1, respectively). Anatomically, the TP had a distinct tetarch arrangement of vascular bundles in their stem and roots against a typical ployarched pattern in the non-transgenic plants. Significantly, the transgenic plants accumulated 35% higher amount of total TIAs (3.10 +/- 0.21% dry wt.) along with a 0.03% dry wt. content of its vasodilatory and nootropic alkaloid vincamine in their leaves. Higher productivity of alkaloids in TP was corroborated with more than four (RQ = 4.60 +/- 0.30) and five (RQ = 5.20 +/- 0.70) times over-expression of TIAs pathway genes tryptophan decarboxylase (TDC) and strictosidine synthase (STR) that are responsible for pushing the metabolic flux towards TIAs synthesis in this medicinal herb.

Digestive ripening: a fine chemical machining process on the nanoscale - Shimpi, Jayesh Ramesh; Sidhaye, Deepti S.; Prasad, Bhagavatula L V (Langmuir, 2017)
A comprehensive over view of the process named as 'digestive ripening' that is known to convert polydisperse nanocrystals to monodisperse ones is presented. Apart from highlighting the role of organic molecules (ligands) in achieving size control the role of other parameters like the nanocrystal-ligand binding strength and the temperature at which the reaction is carried out in accomplishing size control is also delineated. The generality of the procedure is illustrated by providing examples of how it is used to prepare monodispersed nanocrystals of different metals, alloy systems, ultra small nanocrystals and also to narrow the size distribution in complex binary and ternary nanocrystal systems. Finally, the current status as far as the theoretical understanding of how the size control is being achieved by digestive ripening is laid out, emphasizing at the same time the necessity to undertake more systematic studies to completely realize the full potential of this practically very useful procedure.

Digestive ripening of Au nanoparticles by multidentate ligands - Sahu, Puspanjali; Shimpi, Jayesh; Lee, Han Ju; Lee, T. Randall; Prasad, Bhagavatula L. V (Langmuir, 2017)
The efficiency of multidentate ligands as digestive ripening agents for the preparation of monodisperse Au nanoparticles was investigated. This systematic investigation was performed using ligands possessing one, two, or three thiol moieties as ligands/digestive ripening agents. Our results clearly establish that among the different ligands, those that are monodentate and the use of temperatures in the range of 60 °C and 120 °C offer the best conditions for digestive ripening. In addition, when digestive ripening was carried out at lower temperatures (e.g., 60 °C), the nanoparticle size increased as the number of thiol groups per ligand increased. However, in the case of ligands possessing two and three thiol moieties when they are heated with polydispersed particles at higher temperatures (120 °C or 180 °C), the etching process dominates, which affects the quality of the nanoparticles in terms of their monodispersity. We conclude that the temperature-dependent strength of the interaction between the ligand headgroup and the nanoparticle surface plays a vital role in controlling the final particle sizes.

Dihydropyrimidinone-isatin hybrids as novel non-nucleoside HIV-1 reverse transcriptase inhibitors - Devale, T. L.; Parikh, J.; Miniyar, P.; Sharma, P.; Shrivastava, B.; Murumkar, P. (Bioorganic Chemistry, 2017)
A novel series of substituted N-(2-( 2,3-dioxoindolin-1-yl) acetyl)-2-oxo-1,2,3,4-tetrahydropyrimidine-5carboxamide was designed, synthesized and evaluated for in vitro Reverse Transcriptase (RT) inhibitory activity. This series is a combination of peculiar structural features from leading scaffolds of [(2-hydroxye thoxy) methyl]-6-(phenylthio) thymine (HEPT) and oxyindole. In vitro screening led to identification of two hybrids (9c and 9d) possessing higher RT inhibitory activity than the standard rilpivirine. Docking study was performed to study the binding orientations of synthesized hybrids towards RT enzyme.

Direct C-N bond formation in an in situ ligand transformation reaction and formation of polymeric 1D cadmium(II) complexes with end-to-end bridging thiocyanate or selenocyanate ions: Synthesis, structures and theoretical studies - Sadhu, Mehul H.; Solanki, Ankita; Kundu, T.; Hingu, Vinayak; Ganguly, B.; Kumar, Sujit B. (Polyhedron, 2017)
Two new one-dimensional polymeric thiocyanato and selenocyanato bridged cadmium(II) complexes [Cd(dpip)(mu(1,3)-SCN)(2)](n) and [Cd(dpip)(mu(1,3)-SeCN)(2)](n), where dpip = 3,5-dimethy1-14(3-phenylimidazolidin-ly1)-methyl)-1H-pyrazole have been synthesized and characterized by elemental analysis, IR, 1H NMR and single crystal X-ray diffraction studies. The bidentate N-2-coordinated ligand dpip is formed from N-4-coor-dinated tetradentate ligand N,N-bis(3,5-dimethy1-1H-pyrazol-1-yOmethyl-N-2-phenylethane-1,2-diamine (bdpab) due to unusual transformation, removing one pyrazole group and formation of saturated imidazole ring during in situ complexation reaction. The 1D structures of the two complexes have been confirmed by single crystal X-ray diffraction studies and both NCS- and NCSe- act as end -to -end (-1,3) bridging ligands. The coordination environment around the cadmium center in the complexes are CdN4S2 and CdN4Se2, respectively and each cadmium(II) center has distorted octahedral geometry. The distortion in the molecules are due to two unequal Cd-N (organic ligand dpip) bond lengths and small bite angel of the unsymmetrical organic ligand. The DFT calculations performed with cadmium(II) complexes [Cd (dpip)(mu(1,3)-SCN)(2)](n) and [Cd(dpip)(mu(1,3)-SeCN)(2)](n) corroborated the observed crystal structures and the structural parameter were found to be in good agreement in both calculated and X-ray geometries. (C) 2017 Elsevier Ltd. All rights reserved.
Keywords: 1d Chain; Cd(Ii) Complexes; Cobalt(Ii); coordination polymers; Crystal-structure; Dft Pyrazole Based Ligand; Dinuclear; End-to-end Bridge; Infrared-spectra; Magnetic-properties; Metal; Ncs/Secn Ion; Nickel(Ii); Nitrogen Single Bond

Direct steam generation for process heat applications in compound parabolic collector (CPC) - Sardeshpande, Madhavi V.; Sardeshpande, Vishal R. (11th ISES EuroSun Conference, 2017)
In recent years, CPC (Compound Parabolic Collector) is gaining its acceptance for temperature range higher than non-concentrating stationery solar collectors like flat plate collectors but lower end of temperature range of concentrating solar collectors like PTC (parabolic trough concentrators). Generally, pressurized hot water or thermal oil is used as a working fluid in the CPC. The elimination of solar tracking in CPC provides flexibility for installation and lower price point compared to other concentrating technologies with tracking. Steam is one of the universally accepted working fluid for process heat applications due to availability, nontoxic and high heat carrying capacity. Many industrial sectors such as food and beverages, textile, chemical processes etc utilize steam as a working fluid for process heat applications. Direct steam generation as a working fluid through a CPC has various operational, integration and cost advantages. The use of CPC for direct steam generation at saturation steam temperature range 105-145 degrees C (equivalent saturation pressure 0.5-3 bar (g)) can cater for low temperature process heat demand. Solar radiation intensity changes with the time of the day leading to change in heat flux for steam generation. There arc challenges for handling two phase flow (steam generation) in 'U' shaped metal tubes due to pressure drop, flow instabilities and control of steam dryness fraction under vatying solar heat flux. The focus of the present research work is to analyze a CPC system for direct steam generation. This paper discusses an experimental setup and challenges for direct steam generation. The experimental measurements will he focused on behavior of the thermal flow pattern inside the inclined metal tube at various heat flux conditions throughout the day, measurement of local heat transfer coefficients and corresponding vapor quality. Experimental data analysis and understanding will be useful to develop direct steam generation engineering schemes and its integration approach with various end-use applications.

Diverse profiles of N-acyl-homoserine lactones in biofilm forming isolates of Cronobacter sakazakii - Singh, Niharika; Patil, Amrita; Prabhune, Asmita Ashutosh; Raghav, Mamta; Goel, Gunjan (Virulence, 2017)
The present study investigates the role of quorum sensing (QS) molecules expressed by C. sakazakii in biofilm formation and extracellular polysaccharide expression. The QS signaling was detected using Chromobacterium violaceum 026 and Agrobacterium tumefaciens NTL4(pZLR4) based bioassay. Long chain N-acyl-homoserine lactones (AHLs) with C6- C18 chain length were identified using High Performance Liquid Chromatography and Liquid Chromatography-High Resolution Mass Spectrometry. A higher Specific Biofilm Formation (SBF) index (p < 0.05) with the presence of genes associated with cellulose biosynthesis (bcsA, bcsC and bcsG) was observed in the strains. AHLs and their mechanisms can serve as novel targets for developing technologies to eradicate and prevent biofilm formation by C. sakazakii.

Draft genome sequence of lactobacillus plantarum strains E2C2 and E2C5 isolated from human stool culture - Suryavanshi, Mangesh V.; Paul, Dhiraj; Doijad, Swapnil P.; Bhute, Shrikant S.; Hingamire, Tejashri B.; Gune, Rahul P.; Shouche, Yogesh S. (Standards in Genomic Sciences, 2017)
Probiotic Lactobacillus species offer various health benefits, thus have been employed in treatment and prevention of various diseases. Due to the differences in the isolation source and the site of action, most of the lactobacilli tested in-vitro for probiotics properties fail to extend similar effects in-vivo. Consequently, the search of autochthonous, efficacious and probably population specific probiotics is a high priority in the probiotics research. In this regards, whole genome sequencing of as many Lactobacillus as possible will help to deepen our understanding of biology and their health effects. Here, we provide the genomic insights of two coherent oxalic acid tolerant Lactobacillus species (E2C2 and E2C5) isolated from two different healthy human gut flora. These two isolates were found to have higher tolerance towards oxalic acid (300 mM sodium oxalate). The draft genome of strain E2C2 consists of 3,603,563 bp with 3289 protein-coding genes, 94 RNA genes, and 43.99% GC content, while E2C5 contained 3,615,168 bp, 3293 coding genes (93.4% of the total genes), 95 RNA genes and 43.97% GC content. Based on 16S rRNA gene sequence analysis followed by in silico DNA-DNA hybridization studies, both the strains were identified as Lactobacillus plantarum belonging to family Lactobacillaceae within the phylum Firmicutes. Both the strains were genomically identical, sharing 99.99% CDS that showed 112 SNPs. Both the strains also exhibited deconjugation activity for the bile salts while genome analysis revealed that the L. plantarum strains E2C2 and E2C5 also have the ability to produce vitamins, biotin, alpha-and beta-glucosidase suggesting potential probiotic activities of the isolates. The description presented here is based on the draft genomes of strains E2C2 and E2C5 which are submitted to GenBank under the accession numbers LSST00000000.1 and LTCD00000000.1, respectively.

Drug-triggered self-assembly of linear polymer into nanoparticles for simultaneous delivery of hydrophobic and hydrophilic drugs in breast cancer cells - Palvai, Sandeep; Anandi, Libi; Sarkar, Sujit; Augustus, Meera; Roy, Sudip; Lahiri, Mayurika; Basu, Sudipta (ACS Omega, 2017)
Breast cancer is the most devastating disease among females globally. Conventional chemotherapeutic regimen relies on the use of highly cytotoxic drugs as monotherapy and combination therapy leading to severe side effects to the patients as collateral damage. Moreover, combining hydrophobic and hydrophilic drugs create erratic biodistribution and suboptimal medicinal outcome. Hence, packaging multiple drugs of diverse mechanisms of action and biodistribution for safe delivery into tumor tissues with optimal dosages is indispensable for next-generation breast cancer therapy. To address these, in this report, we describe a unique cisplatin-triggered self-assembly of linear polymer into 3D-spherical sub 200 nm particles. These nano-particles comprise a hydrophobic (paclitaxel) and hydrophilic drug (cisplatin) simultaneously in a single particle. Molecular dynamics simulation revealed hydrophilic-hydrophilic interaction and interchain H-bonding as underlying mechanisms of self-assembly. Confocal microscopy studies evidently demonstrated that these novel nanoparticles can home into lysosomes in breast cancer cells, fragment subcellular nuclei, and prevent cell division, leading to improved breast cancer cell death compared to free drug combination. Moreover, 3D-breast tumor spheroids were reduced remarkably by the treatment of these nanoparticles within 24 h. These dual-drug-loaded self-assembled polymeric nanoparticles have prospective to be translated into a clinical strategy for breast cancer patients.

Dynamic metabolic reprogramming of steroidal glycol-alkaloid and phenylpropanoid biosynthesis may impart early blight resistance in wild tomato (Solanum arcanum Peralta) - Shinde, Balkrishna A.; Dholakia, Bhushan B.; Hussain, Khalid; Panda, Sayantan; Meir, Sagit; Rogachev, Ilana; Aharoni, Asaph; Giri, Ashok P.; Kamble, Avinash C. (Plant Molecular Biology, 2017)
Alternaria solani severely affects tomato (Solanum lycopersicum L.) yield causing early blight (EB) disease in tropical environment. Wild relative, Solanum arcanum Peralta could be a potential source of EB resistance; however, its underlying molecular mechanism largely remains unexplored. Hence, non-targeted metabolomics was applied on resistant and susceptible S. arcanum accessions upon A. solani inoculation to unravel metabolic dynamics during different stages of disease progression. Total 2047 potential metabolite peaks (mass signals) were detected of which 681 and 684 metabolites revealed significant modulation and clear differentiation in resistant and susceptible accessions, respectively. Majority of the EB-triggered metabolic changes were active from steroidal glycol-alkaloid (SGA), lignin and flavonoid biosynthetic pathways. Further, biochemical and gene expression analyses of key enzymes from these pathways positively correlated with phenotypic variation in the S. arcanum accessions indicating their potential role in EB. Additionally, transcription factors regulating lignin biosynthesis were also up-regulated in resistant plants and electrophoretic mobility shift assay revealed sequence-specific binding of rSaWRKY1 with MYB20 promoter. Moreover, transcript accumulation of key genes from phenylpropanoid and SGA pathways along with WRKY and MYB in WRKY1 transgenic tomato lines supported above findings. Overall, this study highlights vital roles of SGAs as phytoalexins and phenylpropanoids along with lignin accumulation unrevealing possible mechanistic basis of EB resistance in wild tomato.

Effect of ligand attachment on the C-I bond dissociation process on aluminum nanoclusters: a DFT investigation - Sengupta, Turbasu; Samanta, Bipasa; Pal, Sourav (Journal of Physical Chemistry C, 2017)
The influence of the ligand attachment on the activation process of carbon halogen bond on small sized aluminum nanoclusters are investigated using density functional theory. Attaching suitable ligand to metal clusters is among the widely popular techniques often used by experimentalists in order to stabilize metastable clusters. In depth theoretical investigations have shown that based on the jellium configuration of the cluster, attaching an electron withdrawing ligand can either make a cluster more reactive toward the C-I dissociation or may convert the cluster relatively inert. The alteration of the activation barriers and other associated parameters due to ligand attachment are included in this paper along with additional calculations and explanations. The study also shows that even the reaction parameters of specific magic clusters can be significantly altered via ligand attachment. The activation process of small molecules on metal clusters are of crucial importance for the development of material science and cluster chemistry. The present investigation will therefore be useful for better understanding of the properties of the ligated clusters as well as may also aid the experimentalists toward controlling the reactivity of a specific cluster as required.

Effect of phytase and FYM on soil enzyme activities, microbial population and nutrient availability of non-calcareous soil - Jadhav, A.B.; Suradkar, R.; Taggu, B.; Tamboli, B.D.; Priyanka, B. (Journal of the Indian Society of Soil Science, 2017)
A pot culture experiment was conducted to assess the effect of phytase and FYM levels on soil enzyme activities and nutrient availability of non-calcareous soil under soybean cultivation. The treatment consisted of four levels of phytase (0, 1200, 2400 and 3600 IU) and FYM (0, 2.5, 5.0 and 7.5 t ha-1). Enzyme activities and nutrient availability in soil was assessed at 50% flowering and harvest of soybean. It was observed that application of phytase @ 3600 IU recorded significantly higher acid and alkaline phosphatase and dehydrogenase activity at both the growth stages of soybean. Results revealed that significant interaction effect with combine application of phytase @ 3600IU and FYM @ 7.5 t ha-1 recorded higher bacterial, fungal and actinomycetes population. Combined application of phytase @ 3600 IU and FYM @ 7.5 t ha-1 recorded significantly higher available nitrogen (289.3 and 213.6 kg ha-1) and potassium (295.0 and 270.6 kg ha-1) at 50% flowering and at harvest of soybean, respectively. However, in case of phosphorus (P), at 50% flowering significantly higher available P was recorded with phytase @ 3600 IU + 7.5 t ha-1 (23.9 kg ha-1). Reduction trend obtained for calcium carbonate content from 4.24 to 3.68% at 50% flowering and from 4.20 to 3.60% at harvest stage was obtained with the application of phytase @ 3600 IU. This study suggest that application of phytase in combination with manure substantially improves soil biological activities as well as better nutrient supply to crop.

Effective degradation of organic water pollutants by atmospheric non-thermal plasma torch and analysis of degradation process - Bansode, Avinash H.; More, Supriya Eknath; Siddiqui, Ejaz Ahmad; Satpute, Shruti; Ahmad, Absar; Bhoraskar, Sudha V.; Mathe, Vikas L. (Chemosphere, 2017)
The paper reports the use of atmospheric non-thermal plasma torch as a catalyst for degradation of various organic pollutants dissolved in water. A flow of He mixed with air was used to produce the dielectric barrier discharge (DBD), at the tip of the torch, using pulsed electric excitation at 12 kV. The torch, operated at a power of 750 mW/mm², was seen to completely degrade the aqueous solutions of the pollutants namely methylene blue (MB), methyl orange (MO) and rhodamine-B (RB), at around 10⁻⁴ M concentrations, the concentration of polluants is one order higher than of routinely used heterogeneous photocatalytic reactions, within 10 min of irradiation time at room temperature. UV Visible spectra of the organic dye molecules, monitored after different intervals of plasma-irradiation, ranging between 1 and 10 min, have been used as tools to quantify their sequential degradation. Further, instead of using He, only air was used to form plasma plume and used for degradation of organic dye which follow similar trend as that of He plasma. Further, Liquid Chromatography Mass Spectroscopy (LCMS) technique has been used to understand degradation pathway of methylene blue (MB) as a representative case. Total organic carbon (TOC) measurements indicates significant decrease in its content as a function of duration of plasma exposure onto methylene blue as a representative case. Toxicity studies were carried out onto Gram negative Escherichia coli. This indicated that methylene blue, without plasma treatment, shows growth inhibition, whereas with plasma treatment no inhibition was observed.

Efficient and durable oxygen reduction electrocatalyst based on CoMn alloy oxide nanoparticles supported over N-doped porous graphene - Singh, Santosh K.; Kashyap, Varchaswal; Manna, Narugopal; Bhange, Siddheshwar N.; Soni, Roby; Boukherroub, Rabah; Szunerits, Sabine; Kurungot, Sreekurnar (ACS Catalysis, 2017)
Transition metal oxide derived materials are very important for various applications, such as electronics, magnetism, catalysis, electrochemical energy conversion, and storage. Development of efficient and durable catalysts for the oxygen reduction reaction (ORR), an important reaction in fuel cells and metal air batteries, is highly desirable. Moreover, the futuristic catalysts for these applications need to be costeffective in order to ensure a competitive edge for these devices in the energy market. This article describes the synthesis of a cost-effective and efficient electrocatalyst for ORR It is based on supporting CoMn alloy oxide nano particles on N-doped porous graphene through a simple and scalable microwave irradiation method. Microwave irradiation was found to be very crucial for the fast creation of pores in the graphene framework with a concomitant formation of the CoMn alloy oxide nanoparticles. A series of catalysts have been synthesized by varying the Co:Mn ratio, among which, the one with the Co:Mn ratio of 2:1 [designated as CoMn/pNGr(2:1)] displayed remarkably higher ORR activity in 0.1 M KOH solution. It showed a similar to 60 mV potential shift with a low Tafel slope of 74 mV/decade, which is comparable to that derived from the commercial Pt/C catalyst. This high activity of CoMn/pNGr(2:1) has been credited to the cooperative effect arising from the metal entities and the defects present in the N-doped porous graphene. Finally, real system-level validations of the use of CoMn/pNGr(2:1) as cathode catalyst could be performed by fabricating and testing single-cells of an anion-exchange membrane fuel cell (AEMFC) and a primary Zn-air battery, which successfully demonstrated the efficiency of the catalyst to facilitate ORR in real integrated systems of the single-cell assemblies.
Keywords: anion-exchange membrane fuel cell; cooperativity effect; microwave synthesis; oxygen reduction reaction; porous N-doped graphene; Zn-air battery

Efficient Sn(II)-catalyzed one-pot synthesis of a 3-substituted azetidine-2,4-dione framework - Chavan, Santosh S.; Supekar, Mrudul V.; Burate, Pralhad A.; Rupanwar, Bapurao D.; Shelke, Anil M.; Suryavanshi, Gurunath (Organic & Biomolecular Chemistry, 2017)
A novel Sn(II)-catalyzed tandem cyclization reaction of aromatic aldehydes with ethyl cyanoacetate has been achieved to afford a series of 3-substituted azetidine-2,4-diones in good to excellent yields. This protocol provides straightforward access to construct the azetidine core through sequential Knoevenagel condensation, hydration and the C-N cyclization reaction.

Efficient synthesis of the opioid analgesic (R)-phenampromide via an aziridinium ion - Mujahid, Mohammad; Mujumdar, Prashant; Sasikumar, Murugesan; Deshmukh, Shirish P.; Muthukrishnan, Murugan (Tetrahedron-Asymmetry, 2017)
A simple and efficient synthesis of the opioid analgesic agent (R)-phenampromide with high enantiopurity (> 99% ee) via the formation of an aziridinium ion as a key step using commercially available starting material is described. (C) 2017 Elsevier Ltd. All rights reserved.

Efficient trifluoromethylation of C(sp(2))-H functionalized alpha-oxoketene dithioacetals: a route to the regioselective synthesis of functionalized trifluoromethylated pyrazoles - Sharma, N.; Kumari, N.; Chundawat, T. S.; Kumar, S.; Bhagat, S. (RSC Advances, 2017)
An operationally simple approach for the regioselective construction of diversely substituted trifluoromethylated pyrazoles via nucleophilic trifluoromethylation of iodo-substituted alpha-oxoketene dithioacetals is described. X-ray crystallographic studies confirmed the trifluoromethylation as well as formation of a regioselective cyclized product. Furthermore, trifluoromethylated pyrazoles bearing thiomethyl groups may allow further functionalization and are of considerable interest in medicinal chemistry.

Efficient valorisation of palm shell powder to bio-sorbents for copper remediation from aqueous solutions - Kushwaha, Shilpi; Soni, Harnish; Bojja, Sreedhar; Padmaja, P. (Journal of Environmental Chemical Engineering, 2017)
Alternative bio-sorbents, prepared from cost effective pre-treatment of biomass have been used to remediate toxic heavy metals. Palm shell powder (PSP) and acid treated palm shell powder (APSP) provide an attractive approach for the removal of Cu(II) from aqueous solutions and further use of the copper loaded adsorbents as catalysts. PSP was charred with sulfuric acid (H2SO4) to oxidize ligno-cellulosic groups present in PSP, resulted in acid treated palm shell powder (APSP). Structure property relationship was explored with the help of sophisticated spectroscopic tools (¹³C nuclear magnetic resonance (¹³C NMR), X-Ray photoelectron spectroscopy (XPS), X-Ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy). Pretreatment lead to conversion of ligno-cellulosic content to more valuable and easily process-able polysaccharide content.APSP and PSP displayed a maximum adsorption capacity of 125 and 36 mg/g respectively for copper. Copper adsorption was found to be more in APSP due to presence of COOH groups which rendered the surface more hydrophilic and amenable to enhanced Cu²⁺ sorption. Furthermore the adsorbents loaded with copper could be used as catalysts for oxidation of styrene. The developed adsorbents promise advantages such as low cost, high adsorption capacity, environmental friendliness as well as zero sludge.

Electrical resistance tomography for gas holdup in a gas-liquid stirred tank reactor - Sardeshpande, Madhavi V.; Gupta, Suraj; Ranade, Vivek V. (Chemical Engineering Science, 2017)
Gas-Liquid flows in stirred tank reactors (STR) are used in many significant industrial operations such as hydrogenation, absorption, stripping, oxidation, hydrogenation, ozonation, chlorination, fermentation, etc. Gas-Liquid STRs are expected to perform several functions such as mixing, dispersing gas into liquid, mass and heat transfer and reactions. Gas hold up distribution and various flow regimes are the key parameters affecting performance of gas-liquid STRs. Various techniques such as visual analysis, photography, light attenuation, optical probe method are used to understand gas hold-up distribution within stirred tanks. Most of these techniques have some limitations with respect to measurement of gas hold up distribution. Electrical Resistance Tomography (ERT) is an upcoming technique for obtaining both qualitative and quantitative data on multiphase process units non-invasively and non-intrusively. In this work, an attempt was made to establish and validate the ERT technique for characterizing gas-liquid flows in a laboratory scale STR using the Rushton turbine impeller. ERT was used to study gas holdup and to identify flow regimes. The results were compared with the visual measurements as well as previously published correlations. The effect of gas flow rate, impeller speed on the mean gas holdup is discussed. The methodology and results presented in this work will be useful to effectively apply ERT for characterizing gas-liquid flows in stirred tanks. (C) 2017 Elsevier Ltd. All rights reserved.

Electrochemical formation of Fe-V (O) and mechanism of its reaction with water during O-O bond formation - Pattanayak, Santanu; Chowdhury, Debarati Roy; Garai, Bikash; Singh, Kundan K.; Paul, Amit; Dhar, Basab B.; Sen Gupta, Sayam (Chemistry-A European Journal, 2017)
A detailed electrochemical investigation of a series of iron complexes (biuret-modified tetraamido iron macrocycles FeIII-bTAML), including the first electrochemical generation of Fe-V(O), and demonstration of their efficacy as homogeneous catalysts for electrochemical water oxidation (WO) in aqueous medium are reported. Spectroelectrochemical and mass spectral studies indicated FeV(O) as the active oxidant, formed due to two redox transitions, which were assigned as Fe-IV(O)/Fe-III(OH2)and Fe-V(O)/Fe-IV(O). The spectral properties of both of these high-valent iron oxo species perfectly match those of their chemically synthesised versions, which were thoroughly characterised by several spectroscopic techniques. The O-O bond-formation step occurs by nucleophilic attack of H2O on FeV(O). A kinetic isotope effect of 3.2 indicates an atom-proton transfer (APT) mechanism. The reaction of chemically synthesised Fe-V(O) in CH3CN and water was directly probed by electrochemistry and was found to be first-order in water. The pK(a) value of the buffer base plays a critical role in the rate-determining step by increasing the reaction rate several-fold. The electronic effect on redox potential, WO rates, and onset overpotential was studied by employing a series of iron complexes. The catalytic activity was enhanced by the presence of electron-withdrawing groups on the bTAML framework. Changing the substituents from OMe to NO2 resulted in an eightfold increase in reaction rate, while the overpotential increased threefold.

Electrochemical synthesis of a ternary transition metal sulfide nanosheets on nickel foam and energy storage application - Sahoo, Surjit; Naik, Kusha Kumar; Late, Dattatray J.; Rout, Chandra Sekhar (Journal of Alloys and Compounds, 2017)
We report growth of nickel cobalt sulfide (NCS) ultrathin nanosheets directly on Ni foam substrate by a facile and novel electrodeposition method. The as-prepared NCS sample is used as an electrode material for supercapacitor application due to their large electrochemically active surface area and interconnected nanosheet channels for the facilitation of ion transportation. The NCS nanosheets possess enhanced electrochemical performance in terms of fast and high reversible faradaic reactions characterized by prominent oxidation and reduction peaks. NCS nanosheets showed an ultrahigh specific capacitance of 1712 Fg(-1) at a current density of 1 Ag-1 with excellent cyclic stability. The excellent supercapacitor performance of NCS nanosheets can be attributed to its rich redox reactions as well as high transport rate for both electrolyte ions and electrons. (C) 2016 Elsevier B.V. All rights reserved.

Electrodeposited nickel cobalt manganese based mixed sulfide nanosheets for high performance supercapacitor application - Sahoo, S.; Mondal, R.; Late, D. J.; Rout, C. S. (Microporous and Mesoporous Materials, 2017)
Porous multi component Nickel Cobalt Manganese Sulfide (NCMS) nanosheets have been grown on Ni foam by cathodic electrodeposition method. The as-prepared NCMS nanosheets sample is used as an electrode material for supercapacitor application due to its large electrochemically active surface and high porosity structure. Moreover, NCMS nanosheets have good electrical and mechanical connections to the conductive Ni foam to achieve enhanced reaction kinetics with improved electrode integrity. The NCMS nanosheets exhibit an ultrahigh specific capacitance of 2717 Fig at a current density of 1 Aug with excellent cyclic stability and energy density of 94.07 Wh/kg. The electrodeposited NCMS nanosheets with extraordinary electrochemical performance enable the novel electrodes to hold great potential for high efficient energy storage systems.

Electronic control on linear versus branched alkylation of 2-/3-aroylbenzofurans with acrylates: combined DFT and synthetic studies - Srinivas, Kolluru; Dangat, Yuvraj; Kommagalla, Yadagiri; Vanka, Kumar; Ramana, Chepuri V. (Chemistry-A European Journal, 2017)
Investigations on the factors that govern unusual branched alkylation of 2-aroylbenzofurans with acrylates by Ru-catalyzed carbonyl-directed C-H activation has been carried out by calculating the kinetics associated with the two key steps-the coordination of the acrylate with the intermediate ruthenacycle and the subsequent migratory insertion reaction-studied with the help of DFT calculations. Eight possible orientations for each mode of alkylation have been considered for the calculations. From these calculations, it has been understood that there is a synergistic operation of the steric and electronic effects favoring the branched alkylation. Further DFT investigations on the alkylation of the isomeric 3-aroylbenzofurans indicated a preference for the linear alkylation and this has been verified experimentally. Overall, the observed/calculated complementary selectivity in the alkylation of 2-/3-aroylbenzofurans with acrylates reveals that the substrate-dependent charge distribution of the Ru-C bond in the intermediate ruthenacycle is an important determining factor and thus the current work opens up a new domain of substrate design for controlling regioselectivity.
Keywords: acrylates; Alkylation; aroylbenzofuran; C-H activation; Density functional calculations

Electron–nucleus scalar–pseudoscalar interaction in PbF: Z-vector study in the relativistic coupled-cluster framework - Sasmal, S.; Talukdar, K.; Nayak, M.K.; Vaval, N.; Pal, S. (Molecular Physics, 2017)
The scalar–pseudoscalar interaction constant of PbF in its ground state electronic configuration is calculated using the Z-vector method in the relativistic coupled-cluster framework. The precise calculated value is very important to set upper bound limit on (Formula presented.)-odd scalar–pseudoscalar interaction constant, ks, from the experimentally observed (Formula presented.)-odd frequency shift. Further, the ratio of the effective electric field to the scalar–pseudoscalar interaction constant is also calculated which is required to get an independent upper bound limit of electric dipole moment of electron, de, and ks and how these (de and ks) are interrelated is also presented here. © 2017 Informa UK Limited, trading as Taylor & Francis Group

Elucidation of molecular mechanism of stability of the heme-regulated eIF2α kinase upon binding of its ligand, hemin in its catalytic kinase domain - Bhavnani, V. (Journal of Biomolecular Structure and Dynamics, 2017)
The eIF2α kinase activity of the heme-regulated inhibitor (HRI) is regulated by heme which makes it a unique member of the family of eIF2α kinases. Since heme concentrations create an equilibrium for the kinase to be active/inactive, it becomes important to study the heme binding effects upon the kinase and understanding its mechanism of functionality. In the present study, we report the thermostability achieved by the catalytic kinase domain of HRI (HRI.CKD) upon ligand (heme) binding. Our CD data demonstrates that the HRI.CKD retains its secondary structure at higher temperatures when it is in ligand bound state. HRI.CKD when incubated with hemin loses its monomeric state and attains a higher order oligomeric form resulting in its stability. The HRI.CKD fails to refold into its native conformation upon mutation of H377A/H381A, thereby confirming the necessity of these His residues for correct folding, stability, and activity of the kinase. Though our in silico study demonstrated these His being the ligand binding sites in the kinase insert region, the spectra-based study did not show significant difference in heme affinity for the wild type and His mutant HRI.CKD.
Keywords: Heme Regulated Inhibitor (HRI); HRI-eIF2α Complex; Protein–Ligand Modeling; Thermostability

Engineering molecular topology: A pseudopeptidic macrocyclic figure-eight motif - Sharma, Sakshi; Thorat, Shridhar H.; Gonnade, Rajesh G.; Jasinski, Jerry P.; Butcher, Ray; Haridas, V. (European Journal of Organic Chemistry, 2017)
We herein present a rational-design strategy for the synthesis of molecules with figure-eight topology. The design concept is based on the incorporation of turn units in the back-bone of the macrocycle. The molecular structures and the folding are studied by X-ray crystallography and NMR, FT-IR, and CD spectroscopy.
Keywords: Macrocycles; noncovalent interactions; Pi interactions; topology; X-ray diffraction

Enhanced field emission characteristics of a 3D hierarchical Hfo2-Zno heteroarchitecture - Shisode, Raju T.; Suryawanshi, Sachin R.; Mistari, Chetan D.; Late, Dattatray J.; More, Mahendra A. (ChemistrySelect, 2017)
Three dimensional (3D) HfO2-ZnO heteroarchitecture comprised of thin coating of HfO2 on self assembled 3D ZnO urchins with pointed apex has been synthesized using hydrothermal route followed by Pulsed Laser Deposition (PLD). The as-synthesized HfO2-ZnO heteroarchitecture was characterized using XRD, SEM, EDS, and (HR) TEM, in order to reveal its structural, morphological, and chemical properties. The HfO2-ZnO heteroarchitecture emitter exhibits superior field emission (FE) behaviour in contrast to the pristine ZnO urchins, demonstrated by delivery of high emission current density of similar to 885 mA/cm2 at an applied field of similar to 3.35 V/mm, against similar to 383 mA/cm(2) at an applied field of similar to 4.32 V/mu m for the pristine ZnO urchins emitter. Interestingly, the HfO2-ZnO heteroarchitecture emitter exhibits excellent emission current stability characterized with fewer fluctuations, owing to very good ion-bombardment resistance offered by the HfO2 coating. Furthermore, the heteroarchitecture thus obtained facilitates tailoring of the morphology with high aspect ratio and modulation of electronic properties as well, thereby enhancing the FE behaviour. Despite HfO2 being wide band gap and high-k material, the HfO2-ZnO heteroarchitecture exhibits potential as promising candidate for fabrication of high current density cold cathode
Keywords: 3D heteroarchitecture; Field Emission (FE); hydrothermal; PLD; TEM

Enhanced proton conduction by post-synthetic covalent modification in a porous covalent framework - Samanta, Partha; Desai, Aamod V.; Anothumakkool, Bihag; Shirolkar, Mandar M.; Karmakar, Avishek; Kurungot, Sreekumar; Ghosh, Sujit K. (Journal of Materials Chemistry A, 2017)
A highly chemically stable porous covalent framework (PCF-1) based on ether linkages has been synthesized, which exhibits no loss up to similar to 500 degrees C along with retention of integrity under acidic, basic and oxidative reagent conditions. Owing to its thermal and chemical stability, post-synthetic covalent modification was executed for the introduction of pendant sulphonic acid (-SO3H) groups. The covalently modified compound (PCF-1-SO3H) presents a remarkably high conductivity (ca. 0.026 S cm(-1)), with an similar to 130 fold enhancement in proton conductivity over the parent compound. This value is comparable with those of commercially used Nafion-based proton conducting materials and stands as the highest known value in the regime of post-synthetically modified porous organic frameworks. It is noteworthy to mention that PCF-1 is stable in both acidic and alkaline media, which is not commonly observed for most of the porous materials trialed as proton conducting materials, including metal organic frameworks.

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.

Exploration of amination reactions on highly extendable active sites of Pd(II)-3-allylsalicylaldiminophenol (ASIP) complex over thiofunctionalized SBA-15 - Lazar, Anish; Vinod, C. P.; Singh, A. P. (Microporous and Mesoporous Materials, 2017)
An effective and impressive heterogeneous catalyst, Pd(II)-3-allylsalicylaldiminophenol-SBA-15, dubbed as Pd(II)ASIP@SBA-15, for amination reactions of aryl halides to synthesize secondary amines (2), has been synthesized and characterized. Pd(II)ASIP@SBA-15 has been synthesized by the covalent anchoring of 3-allylsalicylaldehyde over thiofunctionalized SBA-15, then further reaction with 2-aminophenol, followed by metallation process by using Pd(11)(OAc)(2). A specifically designed cheap and easily available organic ligand, 3-allylsalicylaldiminophenol (ASIP), was synthesized from 3-allylsalicylaldehyde and 2-aminophenol. Using this, the synthesis of Pd(II)ASIP@SBA-15 was carried out whereby the ligand providing an active co-ordination or chelating sites for palladium metal. This strategy helped in exposing the Pd(11)ASIP active sites from surface to channels of SBA-15 support during the reactions. The synthesized catalyst were characterized by CHN analysis, PXRD, Nitrogen sorption analyses, TG & DTA, FTIR, C-13 and Si-29 CPMASS NMR spectra, XPS, UV-Visible, SEM, EDAX and TEM. Pd(II)ASIP@SBA-15 catalyst was screened in heterogeneous amination reactions of aryl halides to produce N-aryl derivatives or secondary amines with high catalytic activity as revealed by turn over frequency (TOF) calculations. To explore the heterogeneous nature of catalysts, amination reactions were carried with neat Pd(II)ASIP complex and Pd(11)(OAc)(2) catalysts. The catalyst was recycled several times without much loss of activity and Sheldon hot filtration test has been performed. (C) 2017 Elsevier Inc. All rights reserved.
Keywords: Amination Reactions; heterogeneous catalysis; Reusable; Supported catalysis

Exploring the gem-dimethyl effect in the formation of imine-based macrocycles and cages - Madhu, Suresh; Rashmi, E. V.; Gonnade, Rajesh Ghanshyam; Sanjayan, Gangadhar J. (New Journal of Chemistry, 2017)
Using the gem-dimethyl effect as a platform, a variety of organic [2+2] macrocycles and [2+3] cofacial cages was obtained in high yields. Imine-based macrocyclization could be performed even at high concentrations (0.5 to 1.0 M), via instant mixing of aldehydes and amines.

Exploring the influence of shapes and heterogeneity of glyco-gold nanoparticles on bacterial binding for preventing infections - Toraskar, Suraj; Gade, Madhuri; Sangabathuni, Sivakoti; Thulasiram, Hirekodathakallu V.; Kikkeri, Raghavendra (Chemmedchem, 2017)
To investigate the effects of the heterogeneity and shape of glyco-nanoprobes on carbohydrate-protein interactions (CPIs), alpha-d-mannose-and beta-d-galactose-linked homo-and heterogeneous glycodendrons were synthesized and immobilized on spherical and rod-shaped gold nanoparticles (AuNPs). Lectin and bacterial binding studies of these glyco-AuNPs clearly illustrate that multivalency and shape of AuNPs contribute significantly to CPIs than the heterogeneity of glycodendrons. Finally, bacterial infection of HeLa cells was effectively inhibited by the homogeneous glycodendron-conjugated rod-shaped AuNPs relative to their heterogeneous counterparts. Overall, these results provide insight into the role of AuNP shape and multivalency as potential factors to regulate CPIs.

Exploring the role of GS-GOGAT cycle in microcystin synthesis and regulation - a model based analysis - Banerjee, Swarnendu; Subramanian, Abhishek; Chattopadhyay, Joydev; Sarkar, Ram Rup (Molecular Biosystems, 2017)
Toxic cyanobacteria blooms populate water bodies by consuming external nutrients and releasing cyanotoxins that are detrimental for other aquatic species, producing a significant impact on the plankton ecosystem and food web. To exercise population-level control of toxin production, understanding the biochemical mechanisms that explain cyanotoxin regulation within a bacterial cell is of utmost importance. In this study, we explore the mechanistic events to investigate the dependence of toxin microcystin on external nitrogen, a known regulator of the toxin, and for the first time, propose a kinetic model that analyzes the intracellular conditions required to ensure nitrogen dependence on microcystin. We hypothesize that the GS-GOGAT cycle is manipulated by variable influx of different intracellular metabolites that can either disturb or promote the balance between the enzyme microcystin synthetase and substrate glutamate to produce variable microcystin levels. As opposed to the popular notion that nitrogen starvation increases microcystin synthesis, our analyses suggest that under certain intracellular metabolite regimes, this relationship can either be completely lost or reversed. External nitrogen can only complement the conditions fixed by intracellular glutamate, glutamine and 2-oxoglutarate. This mechanistic understanding can provide an experimentally testable hypothesis for exploring the less-known biology of microcystin synthesis and designing specific interventions.

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

Fabrication, characterization and comparison of DSSC using anatase TiO 2 synthesized by various methods - Umale, Sanjivani V.; Tambat, Sneha N.; Vediappan, Sudhakar; Sontakke, Sharad M.; Krishnamoorthy, Kothandam (Advanced Powder Technology, 2017)
In this study, anatase TiO2 nanoparticles were synthesized by three techniques, namely, sol-gel, acid-base co-catalyst and room temperature colloidal methods. The synthesized materials were characterized by X-ray diffraction, scanning electron microscopy, pore diameter, pore volume and surface area. The dye-sensitized solar cells were fabricated using the synthesized materials and characterized for incident photon to current conversion efficiency, photocurrent density to photo voltage measurement and electrochemical impedance analysis. Among the studied materials, TiO2 synthesized by sol-gel method displayed highest photon to current conversion of 76.8% and a maximum solar cell efficiency of 7.85% with Jsc of 14.75mA/cm², Voc of 0.76V and FF of 0.7. This is the first study to report a high power conversion efficiency of DSSC using a sol-gel synthesized titania and its comparison with other two synthesized materials. The high power conversion efficiency of the solar cell using TiO2 synthesized by sol-gel method is attributed to its characteristic properties such high surface area, larger pore diameter and larger pore volume and highest dye loading capacity.

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 one-pot synthesis of aliphatic bridged diaryloxy compounds, cyclic and crown ethers under mild conditions - Sakate, Sachin; Kamble, Sumit; Chikate, Rajiv; Rode, Chandrashekhar (Supramolecular Chemistry, 2017)
We report here the facile, room temperature, catalyst free, one pot synthesis of aliphatic bridged diaryloxy compounds, cyclic and crown ethers. Anhydrous potassium carbonate (K2CO3) as a mild base along with dimethyl sulfoxide generates the phenoxide ion which facilitates the nucleophilic substitution of bromoalkanes to yield the corresponding crown ethers.

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

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

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

Facile synthesis of unique cellulose triacetate based flexible and high performance gel polymer electrolyte for lithium ion batteries - Nirmale, Trupti C.; Karbhal, Indrapal; Kalubarme, Ramchandra S.; Shelke, Manjusha V.; Varma, Anjani J.; Kale, Bharat B. (ACS Applied Materials & Interfaces, 2017)
Lithium ion batteries (LIBs) with polymer based electrolytes have attracted enormous attention due to the possibility of fabricating intrinsically safer and flexible devices. However, economical and eco-friendly sustainable technology is an oncoming challenge to fulfill the ever increasing demand. To circumvent this issue, we have developed a gel polymer electrolyte (GPE) based on renewable polymers like cellulose triacetate and poly (polyethylene glycol methacrylate) p(PEGMA) using a photo polymerization technique. Cellulose triacetate offers good mechanical strength with improved ionic conductivity, owing to its ether and carbonyl functional groups. It is observed that the presence of an open network has a critical impact on lithium ion transport. At room temperature, GPE PC exhibits an optimal ionic conductivity of 1.8 x 10(-3) S cm(-1) and transference number of 0.7. Interestingly, it affords an excellent electrochemical stability window up to 5.0 V vs Li/Li+. GPE PC shows a discharge capacity of 164 mAhg(-1) after the first cycle when evaluated in a Li/GPE/LiFePO4 cell at 0.5 C-rate. Interfacial compatibility of GPE PC with lithium metal improves the overall cycling performance. This system provides a guiding principle toward a future renewable and flexible electrolyte design for flexible LIBs (FLIBs).

Facile synthesis of ZnO-Ag nanocomposite and its photocatalytic activity - Sardar, Debasmita; Maity, Jayeta; Ghosalya, Manoj Kumar; Gopinath, Chinnakonda S.; Bala, Tanushree (Materials Research Express, 2017)
The evolution of photoactive hybrid materials (e.g. noble metal-semiconductor) has resulted in heterogeneous photocatalysis. We report a facile route for the synthesis of ZnO-Ag nanocomposites with varying percentage of loading of the noble metal, expecting a great boost in the photocatalytic behavior of ZnO. The as prepared material was thoroughly characterized by UV-Vis, FTIR, TEM, FESEM, XRD, XPS analyses. The photocatalytic activities of the nanocomposites have been assessed from the ability to degrade methylene blue dye in aqueous solution. The results suggest that incorporation of Ag nanoparticles on the surface of ZnO particles can enhance catalytic activity in comparison to pure ZnO particles under visible light by minimizing the recombination of photogenerated electron-hole pairs.

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

Fire-retardant, self-extinguishing inorganic/polymer composite memory foams - Chatterjee, Soumyajyoti; Shanmuganathan, Kadhiravan; Kumaraswamy, Guruswamy (ACS Applied Materials & Interfaces, 2017)
Polymeric foams used in furniture and automotive and aircraft seating applications rely on the incorporation of environmentally hazardous fire-retardant additives to meet fire safety norms. This has occasioned significant interest in novel approaches to the elimination of fire-retardant additives. Foams based on polymer nano composites or based on fire-retardant coatings show compromised mechanical performance and require additional processing steps. Here, we demonstrate a one-step preparation of a fire-retardant ice-templated inorganic/polymer hybrid that does not incorporate fire-retardant additives. The hybrid foams exhibit excellent mechanical properties. They are elastic to large compressional strain, despite the high inorganic content. They also exhibit tunable mechanical recovery, including viscoelastic "memory". These hybrid foams are prepared using ice-templating that relies on a green solvent, water, porogen. Because these foams are predominantly comprised of inorganic components, they exhibit exceptional fire retardance in torch burn tests and are self-extinguishing. After being subjected to a flame, the foam retains its porous structure and does not drip or collapse. In micro-combustion calorimetry, the hybrid foams show a peak heat release rate that is only 25% that of a commercial fire-retardant polyurethanes. Finally, we demonstrate that we can use ice-templating to prepare hybrid foams with different inorganic colloids, including cheap commercial materials. We also demonstrate that ice-templating is amenable to scale up, without loss of mechanical performance or fire-retardant properties.

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

Genome-wide identification and tissue-specific expression analysis of nucleotide binding site-leucine rich repeat gene family in Cicer arietinum (kabuli chickpea) - Sharma, R.; ,Rawat, V.; Suresh, C.G. (Genomics Data, 2017)
The nucleotide binding site-leucine rich repeat (NBS-LRR) proteins play an important role in the defense mechanisms against pathogens. Using bioinformatics approach, we identified and annotated 104 NBS-LRR genes in chickpea. Phylogenetic analysis points to their diversification into two families namely TIR-NBS-LRR and non-TIR-NBS-LRR. Gene architecture revealed intron gain/loss events in this resistance gene family during their independent evolution into two families. Comparative genomics analysis elucidated its evolutionary relationship with other fabaceae species. Around 50% NBS-LRRs reside in macro-syntenic blocks underlining positional conservation along with sequence conservation of NBS-LRR genes in chickpea. Transcriptome sequencing data provided evidence for their transcription and tissue-specific expression. Four cis-regulatory elements namely WBOX, DRE, CBF, and GCC boxes, that commonly occur in resistance genes, were present in the promoter regions of these genes. Further, the findings will provide a strong background to use candidate disease resistance NBS-encoding genes and identify their specific roles in chickpea.

Glucosylation of smoke-derived volatiles in grapevine (vitis vinifera) is catalyzed by a promiscuous resveratrol/guaiacol glucosyltransferase - Haratl, Katja; Huang, Fong-Chin; Giri, Ashok P.; Franz-Oberdorf, Katrin; Frotscher, Johanna; Shao, Yang; Hoffmann, Thomas; Schwab, Wilfried (Journal of Agricultural and Food Chemistry, 2017)
Vinification of grapes (Vitis vinifera) exposed to forest fire smoke can yield unpalatable wine due to the presence of taint compounds from smoke and the release of smoke derived volatiles from their respective glycosides during the fermentation process or in-mouth during consumption. To identify glycosyltransferases (GTs) involved in the formation of glycosidically bound smoke-derived volatiles we performed gene expression analysis of candidate GTs in different grapevine tissues. Second, substrates derived from bushfire smoke or naturally occurring in grapes were screened with the candidate recombinant GTs. A resveratrol GT (UGT72B27) gene, highly expressed in grapevine leaves and berries was identified to be responsible for the production of the phenolic glucosides. UGT72B27 converted the stilbene trans-resveratrol mainly to the 3-O-glucoside. Kinetic analyses yielded specificity constants (k(cat)/K-m) of 114, 17, 9, 8, and 2 mM(-1) s(-1) for guaiacol, trans-resveratrol, syringol, methylsyringol, and methylguaiacol, respectively. This knowledge will help to design strategies for managing the risk of producing smoke-affected wines.

Gold nanoconjugates reinforce the potency of conjugated cisplatin and doxorubicin - Iram, S. (Colloids and Surfaces B: Biointerfaces, 2017)
Osteosarcoma or osteogenic sarcoma is the most common and prevalent cancerous tumor of bone and occurs especially in children and teens. Recent treatment strategy includes a combination of both chemotherapy and surgeries. Although, the use of single drug-based chemotherapy treatment remains unsatisfactory. Therefore, combinatorial therapy has emerged as a potential strategy for treatment with limited side- effects. Here, we evaluated the combinatorial anticancerous effect of cisplatin (CIS) and doxorubicin (DOX) bioconjugated bromelain encapsulated gold nanoparticles (B-AuNPs conjugated CIS and DOX) in the treatment of osteosarcoma. The synthesized B-AuNPs conjugated CIS and DOX were characterized by various characterization techniques like UV–vis spectroscopy, TEM, DLS and zeta potential to ensure the synthesis, size, shape, size distribution and stability. Drug loading efficiency bioconjugation of CIS and DOX was ensured by UV–vis spectroscopy. Bioconjugation of CIS and DOX was further confirmed using UV–vis spectroscopy, TEM, DLS, Zeta potential and FT-IR analysis. The combinatorial effect of CIS and DOX in B-AuNPs conjugated CIS and DOX showed highly improved potency against MG-63 and Saos-2 cells at a very low concentration where primary osteoblasts didn't show any cytotoxic effect. The apoptotic effect of B-AuNPs conjugated CIS and DOX on osteosarcoma and primary osteoblasts cells were analyzed by increased permeability of the cell membrane, condensed chromatin and deep blue fluorescent condensed nucleus. The results clearly showed that B-AuNPs conjugated CIS and DOX significantly improved the potency of both the chemotherapeutic drugs by delivering them specifically into the nucleus of cancer cells through caveolae-dependent endocytosis. Thus, the greater inhibitory effect of combinatorial drugs (B-AuNPs conjugated CIS and DOX) over single drug based chemotherapy would be of great advantage during osteosarcoma treatment.
Keywords: cells; chemotherapy; Cytology; Cytotoxicity; Drug interactions; dynamic light scattering; Gold; Molecular Biology; Platinum Compounds

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.

Grafoil-scotch tape-derived highly conducting flexible substrate and its application as a supercapacitor electrode - Soni, Roby; Raveendran, Alka; Kurungot, Sreekumar (Nanoscale, 2017)
Development of flexible supercapacitors is limited by the availability of flexible and durable conducting substrates; a conducting and cheap substrate for the active material deposition is essential for breakthrough progress in this direction. In this report, a highly flexible, conducting, and cheap substrate is prepared by simple stick and peel-off method involving Scotch tape and Grafoil. A Grafoil-Scotch tape derived flexible substrate exhibits a sheet resistance of 7 Omega square(-1) along with a high degree of flexibility and durability. Moreover, its properties are further enhanced by the anodization in order to increase the hydrophilicity and surface area. The substrate is highly thin with a thickness of just 74 mu m. Its practical utility has been demonstrated by electrodepositing MnO2 as an active material and, thereafter, fabricating a solid-state flexible supercapacitor. The fabricated device exhibits high capacitance retention under bent (99%) and twisted (98%) conditions along with a low ESR of 7 Omega.

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.

Helical preorganization of molecules drives solid-state intermolecular acyl-transfer reactivity in crystals: structures and reactivity studies of solvates of racemic 2,6-Di-O-(4-fluorobenzoyl)-myo-inositol 1,3,5-orthoformate - Krishnaswamy, Shobhana; Shashidhar, Mysore S.; Bhadbhade, Mohan M. (Crystal Growth & Design, 2017)
Racemic 2,6-di-O-(4-fluorobenzoyl)-myo-inositol 1,3,5-orthoformate yielded structurally dissimilar solvent-free and solvated crystals depending upon the solvent of crystallization. The solvated crystals exhibited helical assembly of host molecules, due to the interaction of the guest molecules with the orthoformate moiety of the host. Some of the solvates showed specific but incomplete benzoyl group transfer reactivity below the phase transition temperature, whereas the reaction in solvent-free crystals led to a mixture of several products. These results reveal the necessity of helical molecular packing of the reacting molecules in their crystals to facilitate specific intermolecular acyl transfer reactivity. The crystal, structures of the fluorobenzoate solvates were similar to those of the solvates of the analogous chloro and bromobenzoates. The latter could be thermally :transformed into their solvent-free form via melt crystallization, resulting in the conversion of a helical molecular packing into a nonhelical molecular packing.

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

Hexaphosphate-derived phosphorus-functionalized carbon for lithium-ion battery anode - Gawli, Yogesh; Wahid, Malik; Fernandez, Rohan; Kothari, Dushyant; Shelke, Manjusha; Ogale, Satishchandra B. (Chemistryselect, 2017)
We show that high-temperature annealing of a dried hexaphosphate, namely phytic acid, renders activated (micro-porous) and phosphorus-functionalized graphene like carbon in a one-step process. At high enough temperature few volatile phosphates serve as porogen-forming entities while other groups reactively functionalize the carbon surface. The optimized material has high effective surface area due to the presence of defect states. As an anode material for Li-ion battery, it exhibits a reversible capacity that is double that of the graphite and is stable for 1000 cycles even at a high current of 5 A g(-1). This result is attributed to the concurrent presence of micropores and phosphorus containing groups in the carbon matrix.

High quality hybrid perovskite semiconductor thin films with remarkably enhanced luminescence and defect suppression via quaternary alkyl ammonium salt based treatment - Naphade, Rounak A.; Zhao, Baodan; Richter, Johannes M.; Booker, Edward; Krishnamurthy, Shrreya; Friend, Richard H.; Sadhanala, Aditya; Ogale, Satishchandra B. (Advanced Materials Interfaces, 2017)
Significant enhancement in the luminescence and superior photophysical properties of CH3NH3PbBr3 thin films prepared via simple single step spin coating process involving a novel additive mediated solvent extraction step is reported. This process results in significantly lower disorder in CH3NH3PbBr3 perovskites with Urbach energies reducing from ≈35 to ≈17 meV, which is the lowest reported value to date. The additive mediated process also results in a remarkable improvement in the photoluminescence quantum yields (PLQYs) from 1% to 30%. Coupled with the overall increase in surface roughness, a significant increase in the internal PLQY from 7% to 77% is estimated, indicating the superior quality of the treated thin films. The resultant high quality CH3NH3PbBr3 perovskites with remarkable photophysical properties can be used in realizing highly efficient optoelectronic devices. Highly efficient light emitting diodes using these perovskites are demonstrated here.

High-level supercapacitive performance of chemically reduced graphene oxide - Jha, Plawan Kumar; Singh, Santosh Kumar; Kumar, Vikash; Rana, Shammi; Kurungot, Sreekumar; Ballav, Nirmalya (Chem, 2017)
Reduction of graphene oxide (GO) is an important process because it holds promise for the production of reduced graphene oxide (rGO) with physicochemical properties similar to those of pristine graphene. In conventional chemical reduction, strong reducing agents, such as sodium borohydride and hydrazine, cannot be recycled. Also, fast reaction kinetics bring an imbalance in the desirable properties of rGO. Here, we present one-pot chemical reduction of GO in aqueous medium by an unconventional mild reducing agent (FeCl2/HCl) where rGOis isolated as the precipitate and the reducing agent is recycled upon simple treatment of the filtrate with HCl. The fabricated all-solid-state supercapacitors of as-synthesized rGO exhibited significantly higher specific capacitance than those obtained with rGO derived from conventional reducing agents. The cycling stability of the all-solid-state supercapacitor (> 80% retention of capacitance beyond 100,000 continued cycles) and its flexibility (> 500 bending cycles) were remarkable. Use of commercially available organic electrolyte further boosted the supercapacitor performance.

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.

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.

Hydrogen bonding in molecular crystals - Thakuria, R.; Sarma, B.; Nangia, A. (Comprehensive Supramolecular Chemistry II, 2017)
The hydrogen bond is an important intermolecular interaction in chemical, biological, and materials systems. A proper understanding of noncovalent interactions, notably hydrogen bonds between molecules in supramolecular aggregates, is essential for the design of crystalline materials and new supramolecular systems with desired physical and chemical properties. The International Union of Pure and Applied Chemistry provided a broadly acceptable and yet fairly precise definition of the hydrogen bond in 2011. Knowledge of weak intermolecular interactions and hydrogen bonding has immediate applications in the discovery of new medicines and in the development of novel and biocompatible pharmaceutical products and implants for the next wave of innovations. In this article, we summarize a tutorial background of the hydrogen-bond interaction and then present examples of molecular crystals sustained by this interaction and the role of hydrogen bonding in directing the structural organization. The examples are meant to illustrate the different facets of hydrogen bonding in crystal structures, their design, and properties. We close with some of the new techniques for structure determination for very small or weakly diffracting crystals, as is often the case for supramolecular materials and pharmaceutical products.

Hydrogenolysis of sorbitol over Ni, Pt and Ru supported on SBA-15 - Banu, M.; Sankaranarayanan, T. M.; Venuvanalingam, P.; Magesh, G.; Sivasanker, S. (Indian Journal of Chemistry. Section A: Inorganic, Physical, Theoretical & Analytical Chemistry, 2017)
Hydrogenolysis of sorbitol (15% aqueous solution) has been carried out in a batch reactor over Ni (6 wt%), Pt (1 wt%) and Ru (1 wt%) supported on SBA-15 and carbon coated SBA-15 (SBA-15(C)). For comparison, the three metals have also been supported on activated carbon (AC). The catalysts are characterized by XRD, N-2 and H-2 adsorption measurements. Addition of Ca(OH)(2) to the reaction mixture increases conversion and selectivity for the dihydroxy compounds, 1,2-propanediol (PD) and ethylene glycol (EG). Based on yield of dihydric alcohols (PD+EG), the performance of the catalysts at 220 degrees C and 60 bar in the presence of Ca(OH)(2) is in the order: Ru-AC similar to Ru-SBA-15(C) > Ru-SBA-15 similar to Ni-SBA-15, the yields being 40, 39, 31 and 29 wt%, respectively.

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

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.

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

Influence of hyperglycemic conditions on self-association of the alzheimer's amyloid beta (a beta(1-42)) peptide - Menon, Sneha; Sengupta, Neelanjana (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-5/acsomega.7b00018/20170517/images/medium/ao-2017-00018p_0003.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;">Clinical studies have identified a correlation between type-2 diabetes mellitus and cognitive decrements en route to the onset of Alzheimer’s disease (AD). Recent studies have established that post-translational modifications of the amyloid β (Aβ) peptide occur under hyperglycemic conditions; particularly, the process of glycation exacerbates its neurotoxicity and accelerates AD progression. In view of the assertion that macromolecular crowding has an altering effect on protein self-assembly, it is crucial to characterize the effects of hyperglycemic conditions via crowding on Aβ self-assembly. Toward this purpose, fully atomistic molecular dynamics simulations were performed to study the effects of glucose crowding on Aβ dimerization, which is the smallest known neurotoxic species. The dimers formed in the glucose-crowded environment were found to have weaker associations as compared to that of those formed in water. Binding free energy calculations show that the reduced binding strength of the dimers can be mainly attributed to the overall weakening of the dispersion interactions correlated with substantial loss of interpeptide contacts in the hydrophobic patches of the Aβ units. Analysis to discern the differential solvation pattern in the glucose-crowded and pure water systems revealed that glucose molecules cluster around the protein, at a distance of 5–7 Å, which traps the water molecules in close association with the protein surface. This preferential exclusion of glucose molecules and resulting hydration of the Aβ peptides has a screening effect on the hydrophobic interactions, which in turn diminishes the binding strength of the resulting dimers. Our results imply that physical effects attributed to crowded hyperglycemic environments are incapable of solely promoting Aβ self-assembly, indicating that further mechanistic studies are required to provide insights into the self-assembly of post-translationally modified Aβ peptides, known to possess aggravated toxicity, under these conditions.
Keywords: Conformation; Drug discovery and Drug delivery systems; Free energy; Glycoproteins; Molecular association; Molecular dynamics simulation

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

Integrative machine learning strategy for improved prediction of essential genes in Escherichia coli metabolism using flux-coupled features - Nandi, Sutanu; Subramanian, Abhishek; Sarkar, Ram Rup (Molecular Biosystems, 2017)
Prediction of essential genes helps to identify a minimal set of genes that are absolutely required for the appropriate functioning and survival of a cell. The available machine learning techniques for essential gene prediction have inherent problems, like imbalanced provision of training datasets, biased choice of the best model for a given balanced dataset, choice of a complex machine learning algorithm, and data-based automated selection of biologically relevant features for classification. Here, we propose a simple support vector machine-based learning strategy for the prediction of essential genes in Escherichia coli K-12 MG1655 metabolism that integrates a non-conventional combination of an appropriate sample balanced training set, a unique organism-specific genotype, phenotype attributes that characterize essential genes, and optimal parameters of the learning algorithm to generate the best machine learning model (the model with the highest accuracy among all the models trained for different sample training sets). For the first time, we also introduce flux-coupled metabolic subnetwork-based features for enhancing the classification performance. Our strategy proves to be superior as compared to previous SVM-based strategies in obtaining a biologically relevant classification of genes with high sensitivity and specificity. This methodology was also trained with datasets of other recent supervised classification techniques for essential gene classification and tested using reported test datasets. The testing accuracy was always high as compared to the known techniques, proving that our method outperforms known methods. Observations from our study indicate that essential genes are conserved among homologous bacterial species, demonstrate high codon usage bias, GC content and gene expression, and predominantly possess a tendency to form physiological flux modules in metabolism.