Bimetallic and plasmonic Ag-Au on TiO2 for solar water splitting : an active nanocomposite for entire visible light region absorption - Patra, Kshirodra K.; Gopinath, Chinnakonda S. (Chemcatchem, 2016)
The current study demonstrates a potential method for maximum utilization of the entire visible light region of the solar spectrum by designing a plasmonic-metals semiconductor composite. A combination of Ag+Au nanoclusters would broaden the visible-light absorption at least between 400 and 650nm. This hypothesis was evaluated through solar water splitting (SWS) activity of Au-TiO2, Ag-TiO2, and Ag on Au-TiO2 (AgAuT) composites. AgAuT bimetallic nanocomposite shows the maximum apparent quantum yield of 3.3% with hydrogen generation (718molh.g(-1)) from aqueous methanol, and overall water splitting activity (7molg.h(-1), AQY=0.04%) under one sun conditions. Enhanced photocatalytic activity of AgAuT is partly attributed to the formation of hot electrons. A thin layer of Ag coating on Au particles leads to a core-shell morphology with Au in the core. Fermi level equilibration between metal and titania, and Schottky junction formation are directly demonstrated. The strong electronic interaction between Ag and Au, and with TiO2 is evident from its electron rich character and confirmed by Raman spectroscopy, X-ray photoelectron spectroscopy, photoluminescence, and high-resolution TEM measurements. Electronic factors seem to be responsible for the high rate of hydrogen production.

Biosynthesis of anti-proliferative gold using endophytic fusarium oxysporum strain isolated from neem (A-indica) leaves - Siddiqui, Ejaz Ahmad; Ahmad, Absar; Julius, Anju; Syed, Asad; Khan, Shadab; Kharat, Mahesh; Pai, Kalpana; Kadoo, Narendra Y.; Gupta, Vidya (Current topics in medicinal chemistry, 2016)
Here we report a simple, rapid, environment friendly approach for the synthesis of gold nanoparticles using neem (Azadirachta indica A. Juss.) fungal endophyte, which based upon morphological and cultural characteristics was eventually identified as Fusarium oxysporum. The aqueous precursor (HAuCl4) solution when reacted with endophytic fungus resulted in the biosynthesis of abundant amounts of well dispersed gold nanoparticles of 10-40 nm with an average size of 22nm. These biosynthesized gold nanoparticles were then characterized by standard analytical techniques such as UV-Visible spectroscopy, X-ray diffraction, Transmission Electron Microscopy and Fourier Transform Infrared Spectroscopy. Cytotoxic activity of these nanoparticles was checked against three different cell types including breast cancer (ZR-75-1), Daudi (Human Burkitt's lymphoma cancer) and normal human peripheral blood mononuclear cells (PBMC), where it was found that our gold nanoparticles are anti-proliferative against cancer cells but completely safe toward normal cells. In addition to this, assessment of toxicity toward human RBC revealed less than 0.1 % hemolysis as compared to Triton X-100 suggesting safe nature of our biosynthesized gold nanoparticles on human cells. Also, our nanoparticles exhibited no anti-fungal (against Aspergillus niger) or anti-bacterial [against Gram positive (Bacillus subtilis & Staphylococcus aureus) and Gram negative (Escherichia coli & Pseudomonas aeruginosa) bacteria] activity thus suggesting their non-toxic, biocompatible nature. The present investigation opens up avenues for eco-friendly, biocompatible nanomaterials to be used in a wide variety of application such as drug delivery, therapeutics, theranostics and so on.

Biosynthesis of fluorescent Bi2S3 nanoparticles and their application as dual-functionSPECT-CT probe for animal imaging - Uddin, Imran; Ahmad, Absar; Siddiqui, Ejaz Ahmad; Rahaman, Sk. Hasanur; Gambhir, Sanjay (Current Topics In Medicinal Chemistry, 2016)
Bismuth sulphide (Bi2S3) is an excellent semiconductor and its nanoparticles have numerous significant applications including photovoltaic materials, photodiode arrays, bio-imaging, etc. Nevertheless, these nanoparticles when fabricated by chemical and physical routes tend to easily aggregate in colloidal solutions, are eco-unfriendly, cumbrous and very broad in size distribution. The aim of the present manuscript was to ecologically fabricate water dispersible, safe and stable Bi2S3 nanoparticles such that these may find use in animal imaging, diagnostics, cell labeling and other biomedical applications. Herein, we for the first time have biosynthesized highly fluorescent, natural protein capped Bi2S3 nanoparticles by subjecting the fungus Fusarium oxysporum to bismuth nitrate pentahydrate [Bi(NO3)(3).5H(2)O] alongwith sodium sulphite (Na2SO3) as precursor salts under ambient conditions of temperature, pressure and pH. The nanoparticles were completely characterized using recognized standard techniques. These natural protein capped Bi2S3 nanoparticles are quasi-spherical in shape with an average particle size of 15 nm, maintain long term stability and show semiconductor behavior having blue shift with a band gap of 3.04 eV. Semiconductor nanocrystals are fundamentally much more fluorescent than the toxic fluorescent chemical compounds (fluorophores) which are presently largely employed in imaging, immunohistochemistry, biochemistry, etc. Biologically fabricated fluorescent nanoparticles may replace organic fluorophores and aid in rapid development of biomedical nanotechnology. Thus, biodistribution study of the so-formed Bi2S3 nanoparticles in male Sprague Dawley rats was done by radiolabelling with Technitium-99m (Tc-99m) and clearance time from blood was calculated. The nanoparticles were then employed in SPECT-CT probe for animal imaging where these imparted iodine equivalent contrast.

Budding trends in integrated pest management using advanced micro- and nano-materials: challenges and perspectives - Khandelwal, Neha; Barbole, Ranjit S.; Banerjee, Shashwat S.; Chate, Govind P.; Biradar, Ankush V.; Khandare, Jayant J.; Giri, Ashok P. (Journal of Environmental Management, 2016)
One of the most vital supports to sustain human life on the planet earth is the agriculture system that has been constantly challenged in terms of yield. Crop losses due to insect pest attack even after excessive use of chemical pesticides, are major concerns for humanity and environment protection. By the virtue of unique properties possessed by micro and nano-structures, their implementation in Agri-biotechnology is largely anticipated. Hence, traditional pest management strategies are now forestalling the potential of micro and nanotechnology as an effective and viable approach to alleviate problems pertaining to pest control. These technological innovations hold promise to contribute enhanced productivity by providing novel agrochemical agents and delivery systems. Application of these systems engages to achieve: i) control release of agrochemicals, ii) site-targeted delivery of active ingredients to manage specific pests, iii) reduced pesticide use, iv) detection of chemical residues, v) pesticide degradation, vi) nucleic acid delivery and vii) to mitigate post-harvest damage. Applications of micro and nano-technology are still marginal owing to the perception of low economic returns, stringent regulatory issues involving safety assessment and public awareness over their uses. In this review, we highlight the potential application of micro and nano-materials with a major focus on effective pest management strategies including safe handling of pesticides. (C) 2016 Elsevier Ltd. All rights reserved.

Capsicum annuum proteinase inhibitor ingestion negatively impacts the growth of sorghum pest Chilo partellus and promotes differential protease expression - Jadhav, A. R.; War, A. R.; Nikam, A. N.; Adhav, A. S.; Gupta, V. S.; Sharma, H. C.; Giri, A. P.; Tamhane, V.A. (Biochemistry and Biophysics Reports, 2016)
Background Chilo partellus is an important insect pest infesting sorghum and maize. The larvae internalize in the stem, rendering difficulties in pest management. We investigated the effects of Capsicum annuum proteinase inhibitors (CanPIs) on C. partellus larvae by in-vitro and in-vivo experiments. Methods Recombinant CanPI-7 (with four-Inhibitory Repeat Domains, IRDs), -22 (two-IRDs) and insect proteinase activities were estimated by proteinase assays, dot blot assays and in gel activity assays. Feeding bioassays of lab reared C. partellus with CanPI-7 and -22 were performed. C. partellus proteinase gene expression was done by RT-PCR. In-silico structure prediction of proteinases and CanPI IRDs was carried out, their validation and molecular docking was done for estimating the interaction strength. Results Larval proteinases of C. partellus showed higher activity at alkaline pH and expressed few proteinase isoforms. Both CanPIs showed strong inhibition of C. partellus larval proteinases. Feeding bioassays of C. partellus with CanPIs revealed a dose dependent retardation of larval growth, reduction of pupal mass and fecundity, while larval and pupal periods increased significantly. Ingestion of CanPIs resulted in differential up-regulation of C. partellus proteinase isoforms, which were sensitive to CanPI-7 but were insensitive to CanPI-22. In-silico interaction studies indicated the strong interaction of IRD-9 (of CanPI-22) with Chilo proteinases tested. Conclusions Of the two PIs tested, CanPI-7 prevents induction of inhibitor insensitive proteinases in C. partellus so it can be explored for developing C. partellus tolerance in sorghum. General significance Ingestion of CanPIs, effectively retards C. partellus growth; while differentially regulating the proteinases.

Catalyst deactivation and regeneration - Satyanarayana, C. V.; Srikant, D.; Gurav, H. R. (Industrial catalytic processes for fine and specialty chemicals, 2016)
Catalysis plays a vital role in the manufacture of fuels, industrial chemicals, fine chemicals, and specialty chemicals. A catalyst is not only expected to be highly active, it should be stable for long hours on stream and should be recyclable, if required. However, in reality, all the catalysts have finite life. Hence, a most important goal of any catalyst development is to get a catalyst that is highly active for long periods without needing any regeneration. This chapter addresses various causes of catalyst deactivation with reference to different catalyst systems. It discusses various forms coke (carbon) forms on catalysts and the side reactions that drive their formation. The role of support on carbon formation as well as how carbon can be limited using bimetallic catalysts is discussed. Various mechanisms responsible for sintering of metals have been discussed while suggesting means to suppress the same. This chapter also discusses loss of catalyst activity due to strong chemisorption of impurities or byproducts. Typical poisons to different catalysts are listed. The effect of various poisons and how they can influence the course of a catalytic reaction are described. A catalyst may also lose its activity due to mechanical failures such as (i) crushing of catalyst pellets or granules, (ii) breakup of catalyst pellets followed by its attrition, and (iii) erosion of catalyst particles or monolith wash coats. Various solutions to prevent or delay catalyst deactivation as well as various catalyst regeneration methods are summarized.

Catalytic reaction engineering - Gunjal, P. R.; Ranade, V. V. (Industrial catalytic processes for fine and specialty chemicals, 2016)
hemical reaction engineering has contributed remarkably in bringing laboratory-developed chemistry into commercial practice. Reaction engineering is useful for analysis of reactions, identifying rate-limiting steps, determining overall rates, selection of reactor configuration and design and scale-up of reactors. Reaction engineering also provides useful insights into catalytic cycles and provides clues for improving catalyst systems. It essentially includes all the activities necessary to evolve best possible hardware and operating protocol for the reactor to carry out the desired transformation of raw materials (or reactants) into value-added products. This chapter provides an overview of reaction engineering aspects of catalytic processes.

Catecholase and phenoxazinone synthase activities of a ferromagnetically coupled tetranuclear Cu(II) complex - Mitra, Merry; Kundu, Tanay; Kaur, Gurpreet; Sharma, Gyaneswar; Choudhury, Angshuman Roy; Singh, Yogesh; Ghosh, Rajarshi (RSC Advances, 2016)
A crystallographically characterized tetranuclear Cu(II) complex [Cu-4(II)(L)(4)] (1) [H2L = N-(2-hydroxyethyl)-3-methoxysalicylaldimine] is found to show overall ferromagnetic exchange coupling. Complex (1) mimics the catalytic activity of the plant enzyme catechol oxidase by oxidising 3,5-di-tert-butylcatechol to its corresponding quinone in methanol and dichloromethane medium in the presence of aerial oxygen. The reaction follows Michaelis-Menten enzymatic reaction kinetics with turnover numbers (K-cat) 6.99 x 10(3) and 1.85 x 10(3) h(-1) in methanol and dichloromethane, respectively. 1 is also phenoxazinone synthase active in methanol medium with a turnover number of 1.21 x 10(5) h(-1).

C-H activation of methane to formaldehyde on Ce1-xZrxO2 thin films: a step to bridge the material gap - Dubey, Anjani; Kolekar, Sadhu K.; Gopinath, Chinnakonda S. (ChemCatChem, 2016)
Ce1−xZrxO2 (CZ) thin films were prepared by a combination of sol–gel and spin-coating methods and were evaluated for the C−H activation of methane by using a molecular beam set-up with the aim to bridge the material gap. The C−H activation of methane begins at 950 K, and a Ce-rich CZ composition displays a high selectivity (4–12 %) to the partially oxidised product, formaldehyde. A 10–12 % selectivity towards HCHO with 1.6 % methane conversion was observed with methane-rich CH4/O2 reactant compositions at 1050 K. Short contact times, prevalent under molecular beam conditions, could be a possible reason for HCHO formation. Although combustion products were observed instantly upon shining the mixture of reactants on CZ surfaces, up to 20 s delay was observed before formaldehyde generation, which indicates that the oxygen vacancy migration contributes to the rate-determining step and the diffusion-controlled nature of the reaction. A burst in HCHO generation at the point of molecular beam opening, after beam-closed conditions, suggests that the diffusion of oxygen vacancies to the surface is the reason for HCHO formation. Kinetics results also indicate the necessity of reduction sites for HCHO generation.

C-H activation of methane to syngas on MnxCe1-x-yZryO2 - a molecular beam study - Dubey, Anjani; Kolekar, Sadhu K.; Gopinath, Chinnakonda S. (Chemcatchem, 2016)
Mn-doped ceria zirconia thin films (MnxCe1-x-yZryO2, MCZ) were employed as flat model catalyst surfaces for CH4 activation. MCZ films exhibit characteristics of single crystal and powder materials, such as smooth surfaces and porosity. From molecular-beam studies, it has been identified that the oxygen storage capacity increases with Mn content. Mutually exclusive observation of H2O or a mixture of products (CO2+ CO + H-2) occurs, when the reactants was allowed to react directly on MCZ, underscoring their formation or prevention (and consumption), respectively. The results suggest that there is competition and cooperation among different elementary reactions under complementary conditions. From a significant partial oxidation of CH4 through C-H activation, it is found that formation of syngas begins at 700 K and the reaction rate increases with increasing temperature. Kinetic evidences indicate that the reaction proceeds through a combustion-reformation pathway.

Characterization of roseomonas and nocardioides spp. for arsenic transformation - Bagade, Aditi V.; Bachate, Sachin P.; Dholakia, Bhushan B.; Giri, Ashok P.; Kodam, Kisan M. (Journal of Hazardous Materials, 2016)
The metalloid arsenic predominantly exists in the arsenite [As(III)] and arsenate [As(V)]. These two forms are respectively oxidized and reduced by microbial redox processes. This study was designed to bioprospect arsenic tolerating bacteria from Lonar lake and to characterize their arsenic redoxing ability. Screening of sixty-nine bacterial species isolated from Lonar lake led to identification of three arsenic oxidizing and seven arsenic-reducing species. Arsenite oxidizing isolate Roseomonas sp. L-159a being closely related to Roseomonas cervicalis ATCC 49957 oxidized 2 mM As(III) in 60 h. Gene expression of large and small subunits of arsenite oxidase respectively showed 15- and 17-fold higher expression. Another isolate Nocardioides sp. L-37a formed a clade with Nocardioides ghangwensis JC2055, exhibited normal growth with different carbon sources and pH ranges. It reduced 2 mM As(V) in 36 h and showed constitutive expression of arsenate reductase which increased over 4-fold upon As(V) exposure. Genetic markers related to arsenic transformation were identified and characterized from the two isolates. Moderate resistance against the arsenicals was exhibited by the two isolates in the range of 1-5 mM for As(III) and 1-200 mM for As(V). Altogether we provide multiple evidences to indicate that Roseomonas sp. and Nocardioides sp. exhibited arsenic transformation ability. (C) 2016 Elsevier B.V. All rights reserved.

Characterization of two coleopteran alpha-amylases and molecular insights into their differential inhibition by synthetic alpha-amylase inhibitor, acarbose - Channale, Sonal M.; Bhide, Amey J.; Yadav, Yashpal; Kashyap, Garima; Pawar, Pankaj K.; Maheshwari, V. L.; Ramasamy, Sureshkumar; Giri, Ashok P. (Insect Biochemistry and Molecular Biology, 2016)
Post-harvest insect infestation of stored grains makes them unfit for human consumption and leads to severe economic loss. Here, we report functional and structural characterization of two coleopteran alpha-amylases viz. Callosobruchus chinensis alpha-amylase (CcAmy) and Tribolium castaneum alpha-amylase (TcAmy) along with their interactions with proteinaceous and non-proteinaceous alpha-amylase inhibitors. Secondary structural alignment of CcAmy and TcAmy with other coleopteran alpha-amylases revealed conserved motifs, active sites, di-sulfide bonds and two point mutations at spatially conserved substrate or inhibitor binding sites. Homology modeling and molecular docking showed structural differences between these two enzymes. Both the enzymes had similar optimum pH values but differed in their optimum temperature. Overall, pattern of enzyme stabilities were similar under various temperature and pH conditions. Further, CcAmy and TcAmy differed in their substrate affinity and catalytic efficiency towards starch and amylopectin. HPLC analysis detected common amylolytic products like maltose and maltotriose while glucose and malto-tetrose were unique in CcAmy and TcAmy catalyzed reactions respectively. At very low concentrations, wheat alpha-amylase inhibitor was found to be superior over the acarbose as far as complete inhibition of amylolytic activities of CcAmy and TcAmy was concerned. Mechanism underlying differential amylolytic reaction inhibition by acarbose was discussed. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: Acarbose; alpha-amylase; alpha-amylase inhibitor; Callosobruchus chinensis; Coleoptera; Tribolium castaneum

Charge delocalization in the cascade band structure CdS/CdSe and CdS/CdTe core-shell sensitized with Re(I)-polypyridyl complex - Maity, Partha; Debnath, Tushar; Banerjee, Tanmay; Das, Amitava; Ghosh, Hirendra N. (Journal of Physical Chemistry C, 2016)
Charge-carrier dynamics of CdS quantum dot (QD) and CdS/CdSe type-I and CdS/CdTe type-II core shell nanocrystals (NCs) sensitized with a Re(I)-polypyridyl complex have been carried with special emphasis on studies on carrier delocalization and the role of Re-complex as a hole acceptor and sensitizer molecule. Our investigation confirmed photoexcited hole transfer from CdS and CdS/CdSe to the Re-complex, while no hole transfer was observed in the CdS/CdTe Re-complex system. This was rationalized by the evaluation of the relative energy levels, which revealed that such hole migration was not energetically favorable due to low-lying highest occupied molecular orbital (HOMO) of the Re-complex as compared with the valence band (VB) of CdTe shell; however, luminescence quenching from upper excited states of Re-complex was observed in the presence of all three QD and core shell systems, which has been attributed to electron injection from hot state (energetically higher than the LUMO state) of the Re-complex to the conduction band (CB) of the QDs. Transient absorption (lambda(pump) = 400 nm, lambda(probe) = 450-750 nm) spectra recorded for Re complex-sensitized CdS and CdS/CdSe composite in the femtosecond time domain revealed a broad transient absorption band in the 580-750 nm region with a peak around 595 nm, and this was attributed to the cation radical formation for Re-complex, either by capturing photoexcited hole from the NCs or by injecting electron to the CB of the NCs. As anticipated, no such spectrum was observed for the CdS/CdTe Re-complex composite system after 400 nm excitation. Electron injection from photoexcited Re-complex to CdS QD and CdS/CdSe core shell was found to be <100 fs, while the hole transfer from photoexcited CdS QD and CdS/CdSe core shell to Re-complex took place within the time scale of 900 fs and 2.5 ps, respectively.

"Click" polymerization: a convenient strategy to prepare designer fullerene materials - Krishnamurthy, Munusamy; Krishnamoorthy, Kothandam; Arulkashmir, Arulraj; Raghavendra, V.; Murali, Adhigan; Jaisankar, Sellamuthu N.; Murugan, P.; Gurusamy-Thangavelu, Senthil A.; Nasar, A. Sultan; Mandal, Asit Baran; Samanta, Debasis (Materials & Design, 2016)
"Click" polymeric assemblies of fullerenes, thiophenes and aryl compounds were prepared for the first time to study their spectroscopic/chemical/electronic characteristics and possible applications in photovoltaic cells. The GPC and NMR spectroscopic data confirmed a moderate to high degree of polymerization while microscopic pictures showed well-defined arrangements of fullerenes. The FTIR studies indicated that the product is free from starting azide materials, whereas thermogravimetric analysis data suggested a good stability. Band gap of the material was determined using UV-Vis spectroscopy, cyclic voltammetric techniques and compared with computational investigation. The fullerene copolymer was fabricated as acceptor material in a bulk heterojunction photovoltaic cell. (C) 2016 Elsevier Ltd. All rights reserved.

Comparative functional characterization of eugenol synthase from four different ocimum species: implications on eugenol accumulation - Anand, Atul; Jayaramaiah, Ramesha H.; Beedkar, Supriya D.; Singh, Priyanka A.; Joshi, Rakesh S.; Mulani, Fayaj A.; Dholakia, Bhushan B.; Punekar, Sachin A.; Gade, Wasudeo N.; Thulasiram, Hirekodathakallu V.; Giri, Ashok P. (Biochimica Et Biophysica Acta-Proteins and Proteomics, 2016)
Isoprenoids and phenylpropanoids are the major secondary metabolite constituents in Ocimum genus. Though enzymes from phenylpropanoid pathway have been characterized from few plants, limited information exists on how they modulate levels of secondary metabolites. Here, we performed phenylpropanoid profiling in different tissues from five Ocimum species, which revealed significant variations in secondary metabolites including eugenol, eugenol methyl ether, estragole and methyl cinnamate levels. Expression analysis of eugenol synthase (EGS) gene showed higher transcript levels especially in young leaves and inflorescence; and were positively correlated with eugenol contents. Additionally, transcript levels of coniferyl alcohol acyl transferase, a key enzyme diverting pool of substrate to phenylpropanoids, were in accordance with their abundance in respective species. In particular, eugenol methyl transferase expression positively correlated with higher levels of eugenol methyl ether in Ocimum tenuiflorum. Further, EGSs were functionally characterized from four Ocimum species varying in their eugenol contents. Kinetic and expression analyses indicated, higher enzyme turnover and transcripts levels, in species accumulating more eugenol. Moreover, biochemical and bioinformatics studies demonstrated that coniferyl acetate was the preferred substrate over coumaryl acetate when used, individually or together, in the enzyme assay. Overall, this study revealed the preliminary evidence for varied accumulation of eugenol and its abundance over chavicol in these Ocimum species. Current findings could potentially provide novel insights for metabolic modulations in medicinal and aromatic plants. (C) 2016 Elsevier B.V. All rights reserved.

Comparative study of dG affinity vs. DNA methylation modulating properties of side chain derivatives of procainamide: insight into its DNA hypomethylating effect - Gawade, Rupesh L.; Chakravarty, Debamitra K.; Debgupta, Joyashish; Sangtani, E.; Narwade, S.; Gonnade, Rajesh G.; Puranik, Vedavati G.; Deobagkar, D. D. (RSC Advances, 2016)
Procainamide derivatives have been synthesized to investigate the role of side chains in modulating the DNA methylation level in cancer cells and gain insight into its mechanism of action. The synthesized derivatives comprised of flexible (dimethyl), constrained (pyrrolidine, piperidine, morpholine) and planar aromatic (pyridine, phenyl) side chain motifs. The affinity of procainamide and its derivatives towards the deoxyguanosine (dG) base in neutral form has been assessed by performing Differential Pulse Voltammetry (DPV) under physiological conditions. Further, molecular docking with hemimethylated CpG rich DNA acquired from an active mDNMT-1-DNA (PDB ID-4DA4) crystal structure, reveals their preferential non-covalent interaction with dG nucleobase in the intercalation cavity of the minor groove. Differential affinity of the derivatives to dG base in neutral and bound forms (DNA) is correlated with their DNA methylation modulating properties at sub-lethal concentrations. Among all the derivatives, a compound with an aromatic phenyl side chain (1) has shown a highest binding affinity for dG nucleobase in neutral form as well as for partially denatured CpG rich DNA which is attributed to the formation of p/p stacking interaction in addition to N-H/O hydrogen bonding with the pyrimidine ring of dG base. It also shows the highest cytotoxicity and global hypomethylation at a sub-lethal level in the MCF-7 cancer cell line compared to other derivatives and procainamide. A docking study has also illustrated the plausible structural basis of DNA methylation modulating a property of procainamide. Strong association of procainamide with dG bases of partially denatured CpG rich DNA via H-bonding and other non-covalent interactions may alter the active topology of DNA required by the DNA-binding regulatory proteins (e. g. DNMT-1) which is validated by a DNMT-1 inhibition assay. This systematic investigation leads to a new potent alternative to procainamide being found and gives a plausible insight into the DNA hypomethylating effect of procainamide.

Controlled synthesis of end-functionalized mannose-6-phosphate glycopolypeptides for lysosome targeting - Das, Soumen; Parekh, Nimisha; Mondal, Basudeb; Sen Gupta, Sayam (ACS Macro Letters, 2016)
The ubiquitous expression of the mannose-6-phosphate receptor on the majority of human cells makes it a valid target in the quest to deliver therapeutics selectively to the lysosome. In this work end-functionalized polyvalent mannose-6-phosphate glycopolypeptides (M6P-GPs) with high molecular weights (up to 22 kDa) have been synthesized via NCA polymerization. These synthetic M6P-GPs were found to display minimal toxicity to cells in vitro and show exceptional selectivity for trafficking into lysosomes in various cell lines. Comparison of the cellular uptake behavior of M6P-GP and the corresponding mannose-GP polymer reveals that incorporation of the phosphate moiety at the 6-position of mannose completely alters its trafficking behavior and becomes exclusively lysosome specific. We also demonstrate that trafficking of M6P-GPs in mammalian cells is likely associated with the CI-MPR receptor pathway.

Coordination polymers of Fe(III) and Al(III) ions with TCA ligand: distinctive fluorescence, CO2 uptake, redox-activity and oxygen evolution reaction - Dhara, Barun; Sappati, Subrahmanyam; Singh, Santosh K.; Kurungot, Sreekumar; Ghosh, Prasenjit; Ballav, Nirmalya (Dalton Transactions, 2016)
Fe and Al belong to different groups in the periodic table, one from the p-block and the other from the d-block. In spite of their different groups, they have the similarity of exhibiting a stable 3+ oxidation state. Here we have prepared Fe(III) and Al(III) based coordination polymers in the form of metal-organic gels with the 4,4', 4 `'-tricarboxyltriphenylamine (TCA) ligand, namely Fe-TCA and Al-TCA, and evaluated some important physicochemical properties. Specifically, the electrical conductivity, redox-activity, porosity, and electrocatalytic activity (oxygen evolution reaction) of the Fe-TCA system were noted to be remarkably higher than those of the Al-TCA system. As for the photophysical properties, almost complete quenching of the fluorescence originating from TCA was observed in case of the Fe-TCA system, whereas for the Al-TCA system a significant retention of fluorescence with red-shifted emission was observed. Quantum mechanical calculations based on density functional theory (DFT) were performed to unravel the origin of such discriminative behaviour of these coordination polymer systems.

Correlating the role of hydrophilic/hydrophobic nature of Rh(I) and Ru(II) supported organosilica/silica catalysts in organotransformation reactions - Lazar, Anish; George, Shoy C.; Jithesh, P. R.; Vinod, C. P.; Singh, A. P. (Applied Catalysis A-General, 2016)
Highly reactive and hydrophobic triphenyl phosphine based rhodium(I) and ruthenium(II) organometallic complexes over benzene containing periodic mesoporous organosilica (PMOB) have been synthesized. This has been achieved by the immobilization of neat metal complexes like RhCl(PPh3)(3) [Wilkinson catalyst], RuHCl(CO)(PPh3)(3) and RuCl2(PPh3)(3) over aminofunctionalized PMOB to get RhCl(PPh3)(2)-PrNH2PMOB, RuHCl(CO)(PPh3)(2)-PrNH2PMOB and RuCl2(PPh3)(3)-PrNH2PMOB, respectively. The physico-chemical properties of the functionalized catalysts were analyzed by elemental analysis, ICP-OES, XRD, N-2 sorption analyses, FT-IR, solid state C-13 and Si-29 NMR spectra, XPS, SEM, TEM and contact angle measurements. The XRD and N-2 sorption analyses showed excellent textural properties with ordered mesoporous channel structure of all synthesized catalysts. The organic moieties anchored in PMOB were confirmed by C-13 CPMAS NMR and Fr-IR spectroscopy with Si-29 CPMAS NMR spectroscopy providing the information about the degree of functionalization of surface silanol groups with organic moiety. The Rh(I) and Ru(II) complexes supported on MCM-41/SBA-15/PMOE (ethane-PMO) were synthesized, and their catalytic activities in hydrogenation and sulfoxidation reactions were compared with Rh(I) and Ru(II) complexes supported on PMOB. The results show that PMOB based catalysts exhibit higher activities and selectivities than MCM-41/SBA-15/PMOB supported catalysts, neat homogeneous complexes and without catalyst. The better catalytic performance of PMOB based catalyst is attributed to the hydrophobic nature and high surface area of the PMOB support. The recycling studies of anchored catalysts show no major deactivation of the catalyst. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Heterogeneous catalysts; Hydrogenation and sulfoxidation; Hydrophobic; Periodic mesoporous organosilica

Counteranion driven homochiral assembly of a cationic C-3-symmetric gelator through ion-pair assisted hydrogen bond - Maity, Arunava; Gangopadhyay, Monalisa; Basu, Arghya; Aute, Sunil; Babu, Sukumaran Santhosh; Das, Amitava (Journal of the American Chemical Society, 2016)
The helical handedness in achiral self-assemblies is mostly complex due to spontaneous symmetry breaking or kinetically controlled random assembly formation. Here an attempt has been made to address this issue through chiral anion exchange. A new class of cationic achiral C-3-symmetric gelator devoid of any conventional gelation assisting functional units is found to form both right-and left-handed helical structures. A chiral counteranion exchange-assisted approach is successfully introduced to control the chirality sign and thereby to obtain preferred homochiral assemblies. Formation of anion-assisted chiral assembly was confirmed by circular dichroism (CD) spectroscopy, microscopic images, and crystal structure. The X-ray crystal structure reveals the construction of helical assemblies with opposite handedness for (+)- and (-)-chiral anion reformed gelators. The appropriate counteranion driven ion-pair-assisted hydrogen-bonding interactions are found responsible for the helical bias control in this C-3-symmetric gelator.

Crystal engineering of a zwitterionic drug to neutral cocrystals: a general solution for floxacins - Gunnam, Anilkumar; Suresh, Kuthuru; Ganduri, Ramesh; Nangia, Ashwini (Chemical Communications, 2016)
The transformation of zwitterionic Sparfloxacin (SPX) to the neutral form is achieved by cocrystallization. Neutral forms of drugs are important for higher membrane permeability, while zwitterions are more soluble in water. The twin advantages of higher solubility/dissolution rate and good stability of neutral SPX are achieved in a molecular cocrystal compared to its zwitterionic SPX hydrate. The amine-phenol supra-molecular synthon drives cocrystal formation, with the paraben ester acting as a "proton migrator'' for the ionic to neutral transformation.

Culture conditions for the production of thermostable lipase by thermomyces lanuginosus - Sreelatha, B.; Vankudoth, Koteswara Rao; Kumar, R. Ranjith; Girisham, Sivadevuni; Reddy, S. M. (Journal of Basic and Applied Sciences, 2016)
In the present investigation lipase production by three strains of thermophilic Thermomyces lanuginosus (GSLMBKU-10, GSLMBKU-13 and GSLMBKU-14) was carried out in submerged fermentation process. Olive oil and triacetin (0.1%) were added to the basal medium, which stimulated the lipase production. The maximum lipase was produced by GSLMBKU-10 and GSLMBKU-13 in yeast extract starch medium supplemented with triacetin (0.1%). The optimum pH was recorded at 6.0, 6.5 and 7.0 by GSLMBKU-10, GSLMBKU-13 and GSLMBKU-14 respectively. T. lanuginosus GSLMBKU-10 strains failed to produce lipase at pH 8.0. The optimum temperature for lipase production was observed at 45 °C by GSLMBKU-14 and GSLMBKU-10, while that for GSLMBKU-13 was at 50 °C. The marginal temperature ranged from 45 °C to 50 °C for both lipase production and vegetative growth by the three strains of T. lanuginosus under study. In conclusion, the GSLMBKU-13 strain was comparatively superior in the production of lipase than the other two strains under investigation.

Cutaneous exposure to clinically-relevant pigeon pea (Cajanus cajan) proteins promote T(H)2-dependent sensitization and IgE-mediated anaphylaxis in Balb/c mice - Gupta, Rinkesh Kumar; Kumar, Sandeep; Gupta, Kriti; Sharma, Akanksha; Roy, Ruchi; Verma, Alok Kumar; Chaudhari, Bhushan P.; Das, Mukul; Ansari, Irfan Ahmad; Dwivedi, Premendra D. (Journal of Immunotoxicology, 2016)
Epicutaneous (EC) sensitization to food allergens may occur when the skin has been lightly damaged. The study here tested whether cutaneous exposure to pigeon pea protein(s) may cause allergic sensitization. BALB/c mice were either orally gavaged or epicutaneously sensitized by repeated application of pigeon pea crude protein extract (CPE) on undamaged areas of skin without any adjuvant; afterwards, both groups were orally challenged with the pigeon pea CPE. Anaphylactic symptoms along with measures of body temperature, MCPT-1, TSLP, pigeon pea-specific IgE and IgG(1), myeloperoxidase (MPO) activity, T(H)2 cytokines, T(H)2 transcription factors (TFs) and filaggrin expression were determined. Mast cell staining, eosinophil levels and histopathological analysis of the skin and intestines were also performed. In the epicutaneously-sensitized mice, elevated levels of specific IgE and IgG(1), as well as of MCPT-1, TSLP, T(H)2 cytokines and TFs, higher anaphylactic scores and histological changes in the skin and intestine were indicative of sensitization ability via both routes in the pigeon pea CPE-treated hosts. Elevated levels of mast cells were observed in both the skin and intestine; increased levels of eosinophils and MPO activity were noted only in the skin. Decreased levels of filaggrin in skin may have played a key role in the skin barrier dysfunction, increasing the chances of sensitization. Therefore, the experimental data support the hypothesis that in addition to oral exposure, skin exposure to food allergens can promote T(H)2-dependent sensitization, IgE-mediated anaphylaxis and intestinal changes after oral challenge. Based on this, an avoidance of cutaneous exposures to allergens might prevent development of food anaphylaxis.

Data of in vitro synthesized dsRNAs on growth and development of helicoverpa armigera - Chikate, Y. R.; Dawkar, V. V.; Barbole, R. S.; Tilak, P. V.; Gupta, V. S.; Giri, A. P. (Data in Brief, 2016)
The data presented in this article is related to the research article "RNAi of selected candidate genes interrupts growth and development of Helicoverpa armigera" (Chikate et al., 2016) [1]. RNA interference (RNAi) is emerging as a potent insect pest control strategy over current methods and their resistance by pest. In this study we tested 15 different in vitro synthesized dsRNAs for gene silencing in Helicoverpa armigera. These dsRNAs were specific against H. armigera enzymes/proteins such as proteases like trypsins (HaTry2, 3, 4 and 6), chymotrypsin (HaChy4) and cysteine proteases such as cathepsin (HaCATHL); glutathione S-transferases (HaGST1a, 6 and 8); esterases (HaAce4, HaJHE); catalase (HaCAT); super-oxide-dismutase (HaCu/ZnSOD); fatty acid binding protein (HaFabp) and chitin deacetylase (HaCda5b). These dsRNAs were fed to second instar larvae at an optimized dose (60 μg/day) for 3 days separately. Effects of dsRNA feeding were observed in terms of larval mass gain, percentage mortality and phenotypic abnormalities in later developmental stages of H. armigera. These findings might provide potential new candidates for designing sequence-specific dsRNA as pesticide in crop protection.

Data on changes in the fatty acid composition during fruit development and ripening of three mango cultivars (Alphonso, Pairi and Kent) varying in lactone content - Deshpande, A. B.; Chidley, H. G.; Oak, P. S.; Pujari, K. H.; Giri, A. P.; Gupta, V. S. (Data in Brief, 2016)
Data in this article presents fatty acid composition of three mango cultivars; Alphonso, Pairi and Kent through fruit development and ripening. Change in the ω-6 and ω-3 fatty acids level during mango fruit development and ripening is depicted. Also, data on aroma volatile ‘lactones’ composition from pulp and skin tissues of these cultivars at their ripe stage, respectively is provided. Statistical data is also shown, which correlates modulation in lactone content with that of fatty acid composition and content during fruit development and ripening in all the three mango cultivars.

Design and fabrication of mechanically strong nano-matrices of linseed oil based polyesteramide blends - Killi, Naresh; Dhakare, Runali Arjun; Singam, Amarnath; Lokanadham, Metta; Chitikeshi, Harshavardhan; Gundloori, Rathna Venkata Naga (Medchemcomm, 2016)
New nanomaterials of bio-origin with improved mechanical properties are in demand for biomedical application. Therefore, we propose to design and fabricate bioactive nano-matrices with good mechanical strength using polyesteramides derived from linseed oil. Polyesteramide was synthesized from linseed oil and blended with poly(L-lactide) and human serum albumin to enhance the mechanical strength, biodegradation, biocompatibility and hydrophilicity. The various blend solutions with and without drugs (triclosan and metronidazole) were electrospun into non-woven nano-matrices. The morphology of the nano-matrices represented smooth and fine nanofibers with the diameter ranging from 300 to 400 nm. Drug binding efficiency, cytotoxicity, hydrophilicity, thermal and mechanical studies indicated their suitability as biomaterials. To demonstrate their utility, the drug release kinetics and antibacterial properties were evaluated. The metronidazole loaded nano-matrices showed drug release up to 8 h, beyond which no release was observed until 72 h. Antibacterial studies were done using the drugs triclosan and metronidazole. The antibacterial activity of the drug loaded nanofiber mats increased with the increase in drug concentration. The uniqueness of the developed nano-matrices of polyesteramide blends is that their mechanical strength is 3-fold higher than that of the nano-matrices of poly(L-lactide), which is one of the essential features of these nano-matrices to be used as a biomaterial for biomedical applications.

Design, synthesis and biological evaluation of novel azaspiro analogs of linezolid as antibacterial and antitubercular agents - Gadekar, Pradip K.; Roychowdhury, Abhijit; Kharkar, Prashant S.; Khedkar, Vijay M.; Arkile, Manisha A.; Manek, Hardik; Sarkar, Dhiman; Sharma, Rajiv; Vijayakumar, V.; Sarveswari, S. (European Journal of Medicinal Chemistry, 2016)
The design, synthesis and antimicrobial evaluation of a novel series of azaspiro analogues of linezolid (1) have been described. Linezolid comprises of a morpholine ring which is known for its metabolism related liabilities. Therefore, the key modification made in the linezolid structure was the replacement of morpholine moiety with its bioisostere, 2-oxa-6-azaspiro[3.3]heptane. Furthermore, the replacement of N-acetyl terminal of 1 with various aromatic or aliphatic functionalities was carried out. The title compounds were evaluated against a panel of Gram-positive and Gram-negative bacteria and Mycobacterium tuberculosis. Subsequent structure-activity relationship (SAR) studies identified several compounds with mixed antibacterial and antitubercular profiles. Compound 22 (IC50 0.72, 0.51, 0.88, 0.49 mu g/mL for Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus subtilis, respectively) exhibited similar antibacterial profile as I. The N-acetyl derivative 18 was similar to 1 in antitubercular profile. Thus, the present study successfully demonstrated the use of azaspiro substructure in the medicinal chemistry of antibacterial and antitubercular agents. (C) 2016 Elsevier Masson SAS. All rights reserved.

Detection of clostridium tetani in human clinical samples using tetX specific primers targeting the neurotoxin - Ganesh, Madhu; Sheikh, Nasira K.; Shah, Pooja; Mehetre, Gajanan T.; Dharne, Mahesh S.; Nagoba, Basavraj S. (Journal of Infection and Public Health, 2016)
Tetanus resulting from ear injury remains an important health problem, particularly in the developing world. We report the successful detection of Clostridium tetani using tetX specific primers targeting the Cl. tetani neurotoxin. The sample was obtained from an ear discharge of a case of otogenic tetanus in a 2-year-old male child. Based on the culture results of the ear discharge, Gram staining and virulence testing by genotyping, a diagnosis of tetanus was confirmed. This is the first report from India on the successful detection of Cl. tetani in a human clinical sample using tetX specific primers targeting the Cl. tetani neurotoxin. (C) 2015 King Saud Bin Abdulaziz University for Health Sciences. Published by Elsevier Limited. All rights reserved.
Keywords: Cl. tetani; Neurotoxin; Otogenic tetanus; Trismus

Development of genetic programming based softsensor model for styrene polymerization process and its application in model based control - Ghugare, Suhas B.; Tambe, Sanjeev S. (2016 Indian Control Conference (ICC), 2016)
In recent years, soft sensors have been established as a valuable alternative to the traditional hardware sensors for the acquisition of critical information regarding ``difficult-to-measure'' process variables and/or parameters in chemical process monitoring and control. Soft sensors can also be modified as a novel process identification tool for process monitoring and model based control. Often, in polymer industries the main polymerization reaction is highly nonlinear and complex to model accurately by the conventional ``first principles'' approach. In such cases, genetic programming (GP)-a novel artificial intelligence-based exclusively data driven modeling technique-can be employed for process identification. In this work GP-based soft sensors have been developed for a continuous styrene polymerization reactor. The resulting GP-based models (soft sensor) showed high prediction and generalization performances. The best performing model was successfully utilized in designing a model predictive control (MPC) scheme for the polymerization reactor.
2nd Indian Control Conference (ICC), Indian Inst Technol, Hyderabad, INDIA, JAN 04-06, 2016
Keywords: Artificial intelligence; genetic programming; Model Predictive Control; process identification; Styrene Polymerization

Disinfection of water using vortex diode as hydrodynamic cavitation reactor - Gaikwad, V.; Ranade, V. (Asian Journal of Chemistry, 2016)
Hydrodynamic cavitation offers distinct advantages for water disinfection and wastewater treatment particularly at large scales of operations. Vortex Diode is a fluidic device, which is conventionally used as a leaky non-return valve in nuclear industry. Recently this device was shown to be effective hydrodynamic cavitation device. In the present study, we have investigated use of cavitation in vortex diode for water disinfection application. Escherichia coli contaminated water is treated successfully using vortex diode. The operating parameters desirable for the disinfection are investigated. The performance is evaluated based on the reduction in the colony forming unit (CFU/mL) of E. coli count estimated by standard spread plate method. The presented results will be useful for identifying appropriate operating conditions for using vortex diode to effectively reduce the bacterial load and disinfect water.

Disruption of native beta-turns: consequence of folding competition between native and orthanilic acid proline-based pseudo beta-turn - Ingole, Tukaram S.; Vijayadas, Kuruppanthara N.; Chaitanya, K. N.; Kotmale, Amol S.; Gawade, Rupesh L.; Gonnade, Rajesh G.; Rajamohanan, P. R.; Sanjayan, Gangadhar J. (European Journal of Organic Chemistry, 2016)
Five tetrapeptides comprising beta-turn-forming elements and a pseudo beta-turn (C9 H-bonding) based on an SAntPro (orthanilic acid - proline) motif were designed and synthesized. Their extensive conformational investigation by single-crystal X-ray crystallography, solution-state 2D NMR spectroscopic, and nOe-restrained MD simulation studies revealed the formation of C14 or C9 folding and disruption of the native beta-turn (C10 H-bonding) architecture. The striking difference between the psi(psi(2)) angle of ``i + 2'' residues of native beta-turn and designed peptides suggest that formation of the native beta-turn is not favored. The results suggest that other turn-forming motifs can dramatically modulate the stability of the native beta-turn structure.
Keywords: Conformation analysis; hydrogen bonds; Peptidomimetics; structure elucidation

Diversity of arsenic resistant bacteria from Lonar lake: A meteorite impact alkaline crater lake in Indi - Bagade, A. V.; Paul, D.; Rikame, T.; Giri, A. P.; Dhotre, D.; Pawar, S.; Kodam, K. (Arsenic Research and Global Sustainability - Proceedings of the 6th International Congress on Arsenic in the Environment, AS 2016, 2016)
Lonar lake known for its meteorite impact origin and highly alkaline environment harbors a plethora of diverse organisms. Arsenic transforming microbe diversity from Lonar remains unexplored. We attempted to explore the microorganisms causing arsenic transformation using culture-dependent and independent approaches. Amongst the 67 microbes isolated, Bacillus infantis L4-18 and Bacillus solimangrovi L4-7b could oxidise 15 mM arsenite in 8 days. None of the cultures could reduce arsenate. All the other isolates resisted 2 mM arsenic. In the culture independent approach, microbial diversity revealed Bacteroides (41.9%), followed by Proteobacteria (17.9%), Firmicutes (14.2%), Actinobacteria (13.9%), occurring in the Lonar sediment sample. This study provides foundation to study microbial arsenic biogeochemical cycle along with other biochemical cycles and microbial function in Lonar lake eco system.

Does the position of the electron-donating nitrogen atom in the ring system influence the efficiency of a dye-sensitized solar cell? A computational study - Biswas, Abul Kalam; Barik, Sunirmal; Das, Amitava; Ganguly, Bishwajit (Journal of Molecular Modeling, 2016)
We have reported a number of new metal-free organic dyes (2-6) that have cyclic asymmetric benzotripyrrole derivatives as donor groups with peripheral nitrogen atoms in the ring, fluorine and thiophene groups as pi-spacers, and a cyanoacrylic acid acceptor group. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were employed to examine the influence of the position of the donor nitrogen atom and pi-conjugation on solar cell performance. The calculated electron-injection driving force (Delta G(inject)), electron-regeneration driving force (Delta G(regen)), light-harvesting efficiency (LHE), dipole moment (mu(normal)), and number of electrons transferred (Delta q) indicate that dyes 3, 4, and 6 have significantly higher efficiencies than reference dye 1, which exhibits high efficiency. We also extended our comparison to some other reported dyes, 7-9, which have a donor nitrogen atom in the middle of the ring system. The computed results suggest that dye 6 possesses a higher incident photon to current conversion efficiency (IPCE) than reported dyes 7-9. Thus, the use of donor groups with peripheral nitrogen atoms appears to lead to more efficient dyes than those in which the nitrogen atom is present in the middle of the donor ring system.
Keywords: DFT; Dye-sensitized solar cells; Organic dyes; Position effect; TD-DFT

Dynamics of colonization and expression of pathogenicity related genes in fusarium oxysporum f.sp ciceri during chickpea vascular wilt disease progression - Upasani, Medha L.; Gurjar, Gayatri S.; Kadoo, Narendra Y.; Gupta, Vidya S. (Plos One, 2016)
Fusarium wilt caused by Fusarium oxysporum f.sp. ciceri (Foc) is a constant threat to chickpea productivity in several parts of the world. Understanding the molecular basis of chickpea-Foc interaction is necessary to improve chickpea resistance to Foc and thereby the productivity of chickpea. We transformed Foc race 2 using green fluorescent protein (GFP) gene and used it to characterize pathogen progression and colonization in wilt-susceptible (JG62) and wilt-resistant (Digvijay) chickpea cultivars using confocal microscopy. We also employed quantitative PCR (qPCR) to estimate the pathogen load and progression across various tissues of both the chickpea cultivars during the course of the disease. Additionally, the expression of several candidate pathogen virulence genes was analyzed using quantitative reverse transcriptase PCR (qRT-PCR), which showed their characteristic expression in wilt-susceptible and resistant chickpea cultivars. Our results suggest that the pathogen colonizes the susceptible cultivar defeating its defense; however, albeit its entry in the resistant plant, further proliferation is severely restricted providing an evidence of efficient defense mechanism in the resistant chickpea cultivar.

Effect of donors on the activation mechanism in ziegler-natta catalysis: a computational study - Kumawat, Jugal; Gupta, Virendra Kumar; Vanka, Kumar (Chemcatchem, 2016)
Full quantum chemical calculations, using density functional theory (DFT), have been conducted to explain the effect of donors on the ``activation mechanism'' in the Ziegler-Natta (Z-N) catalyst system. In the activation mechanism, the inactive (TiCl4)-Cl-IV catalyst converts into the active (TiCl2Et)-Cl-III catalyst with the help of the AlEt3 present in the system. The donors that have been considered in this study are: ethyl benzoate (eb), two representative diether cases, a phthalate donor, and a silyl ester donor. The results indicate that eb and the diether donor cases donor have a negative effect on the barriers for the activation mechanism. However, the eb donor can be displaced from the MgCl2 surface by AlEt3, which matches experimental observations. For the phthalate, silyl ester and TiCl3-OC4H8Cl cases, the results indicate that a significant induction period would be present in Z-N systems employing such donors or having such a catalytic center, before catalysis could commence.
Keywords: Alkylation; aluminum; Density functional calculations; surface chemistry; titanium

Effect of orifice shape on water disinfection efficacy - Gaikwad, V.; Gaikwad, S.; Ranade, V. (Pollution Research, 2016)
Hydrodynamic cavitation offers distinct advantages for water disinfection and waste watei treatment particularly at large scales of operations. For applying hydrodynamic cavitation foi water disinfection/treatment, water stream to be treated is passed through a fluidic device ir which there exists a low pressure region. Cavities are generated in this region when the pressurt falls below vapour pressure (in absence of any dissolved gases). These cavities are then collapsec when they travel to regions of higher pressure and lead to very high shear, temperatures anc pressures in localized regions. These high pressure/temperature as well as high shear facilitati disinfection as well as reduction in chemical oxygen demand, colour and amonical nitrogen in the water. In this work, we have investigated hydrodynamic cavitation generated by five difieren orifices have been studied which have different shapes with same fractional open area and have tested their effectiveness for water disinfection. The efficacy of generated cavitation on wate disinfection was quantified based on measurements of non-pathogenic E. coli colony forminj units (CFU/mL). The presented results and analysis will be useful for designing hydrodynamii cavitation based systems for water disinfection

Effect of plasma treatment on multilayer graphene: X-ray photoelectron spectroscopy, surface morphology investigations and work function measurements - Patil, Urmila V.; Pawbake, Amit S.; Machuno, Luis G. B.; Gelamo, Rogerio V.; Jadkar, Sandesh R.; Rout, Chandra Sekhar; Late, Dattatray J. (RSC Advances, 2016)
We report here the effect of plasma treatment on multilayer graphene samples as determined by X-ray photoelectron spectroscopy and surface morphology studies with atomic force microscopy, scanning electron microscopy and transmission electron microscopy. The plasma treatment was modified to introduce controlled levels of defects and functionalities to the graphene samples to give tunable properties. The elemental composition and structure were investigated by XPS and micro Raman spectroscopy. The XPS study showed that there was a slight variation in the sp(2)/sp(3) hybridization ratio between the plasma-treated samples and the pristine sample. Kelvin probe measurements were carried out on all the multilayer graphene samples and indicated a slight variation in the work function of the graphene samples after plasma treatment.

Effect of plug temperature on the strain and thickness distribution ofcomponents made by plug assist thermoforming - Marathe, D.; Rokade, D.; Azad, Lal Busher; Jadhav, Kishor; Mahajan, Sunil; Ahmad, Zubair; Gupta, S.; Kulkarni, S.; Juvekar, Vinay A.; Lele, Ashish K. (International Polymer Processing, 2016)
Plug temperature is a key parameter affecting the thickness distribution of thermoplastic components made by plug assist thermoforming. For a specified pair of plug and plastic sheet, the variation in plug temperature can alter the coefficient of friction (COF) between the pair. We show here how the temperature dependence of COF influences the nature and extent of biaxial stretching of the sheet and consequently the thickness distribution of the thermoformed component. In the present study, high impact polystyrene (HIPS) sheets were thermoformed into axisymmetric cups using a plug-assist process in which the aluminum plug temperature (T-plug) was varied from ambient to above the glass transition temperature of HIPS (similar to 100 degrees C). Biaxial strain maps on the surfaces of the formed cups were measured and quantified using Grid Strain Analysis (GSA). Thickness distributions of the cups were also measured. Temperature dependent COF between HIPS and aluminum was determined independently using a rotational rheometer. The measured COF was low for T < 100 degrees C, whereas it increased appreciably at and above 100 degrees C. We conclude that when T-plug < 100 degrees C the HIPS sheet slips on the plug during forming, and this results in biaxial stretching of the base and walls of the formed cup. In contrast for T-plug > 100 degrees C, a significant reduction in the magnitude of slip is expected. Here the sheet is gripped at the clamp and by the plug during forming which causes reduced biaxial stretching of the base and increased uniaxial stretching of the walls of the cup. Simulations of plug-assist thermoforming using a temperature dependent COF showed qualitative agreement with the GSA data thereby supporting our inferences.

Effect of sequence on the ionization of guanine in DNA - Chakraborty, Rahul; Ghosh, Debashree (Physical Chemistry Chemical Physics, 2016)
The accurate estimation of the ionization energies and understanding the nature of the ionized states of the nucleic acid bases (NABs) are crucial to the understanding of the DNA damage mechanism. The vertical ionization energy (VIE) of guanine is the lowest among the NABs and the ionization energies are strongly affected by the environment, such as solvation and characteristics of nearby NABs. Therefore, we investigate the sequence dependence of the VIEs of guanine in B-DNA. We use the equation of motion coupled cluster method for the estimation of ionization potential with single and double excitations (EOM-IP-CCSD) and density functional theory with dispersion corrected omega B97x-D for the estimation of VIEs. A significant amount of non-additivity or cooperativity, directly proportional to charge delocalization, is noticed in the change in VIE due to the interaction with the nearby NABs. While the change in VIE due to base pairing originates predominantly from charge-dipole interactions, stacking between base pairs is a more complicated balance of dispersion and charge-dipole interactions as well as stabilization due to the delocalization of the positive charge. The long range interactions are however dominated by 1/r(3) distance dependence which shows the major role played by charge-dipole interactions. The extent of localization of positive holes on guanine is also estimated for various sequences.

Effect of solvation on electron detachment and excitation energies of a green fluorescent protein chromophore variant - Bose, Samik; Chakrabarty, Suman; Ghosh, Debashree (Journal of Physical Chemistry B, 2016)
Hybrid quantum mechanics/molecular mechanics (QM/MM) is applied to the fluorinated green fluorescent protein (GFP) chromophore (DFHBDI) in its deprotonated form to understand the solvatochromic shifts in its vertical detachment energy (VDE) and vertical excitation energy (VEE). This variant of the GFP chromophore becomes fluorescent in an RNA environment and has a wide range of applications in biomedical and biochemical fields. From microsolvation studies, we benchmark (with respect to full QM) the accuracy of our QM/MM calculations with effective fragment potential (EFP) as the MM method of choice. We show that while the solvatochromic shift in the VEE is minimal (0.1 eV blue shift) and its polarization component is only 0.03 eV, the effect of the solvent on the VDE is quite large (3.85 eV). We also show by accurate calculations on the solvatochromic shift of the VDE that polarization accounts for similar to 0.23 eV and therefore cannot be neglected. The effect of the counterions on the VDE of the deprotonated chromophore in solvation is studied in detail, and a charge-smearing scheme is suggested for charged chromophores.

Effective and selective oxidation of 2-butanol over Mn supported catalyst systems - Prabu, Kandasamy; Prabu, Marimuthu; Venugopal, Ashok Kumar; Venugopalan, Aswathy Thareparambil; Sandilya, W. V. Y. Sai; Gopinath, Chinnakonda S.; Raja, Thirumalaiswamy (Applied Catalysis A-General, 2016)
Oxidation of alcohols to their corresponding aldehydes/ketones is an important reaction in industries as well as in academic perspective. Selective oxidation (Selox) of alcohols like methanol, ethanol and propanol are well studied in literature; however, alcohols like butanol, pentanol, octanol is a challenging task. Selective oxidation of 2-butanol to methyl ethyl ketone (MEK) is an important reaction due to its wide range of applications. Herein, we demonstrated the selective oxidation of 2-butanol to MEK over Mn supported on different oxide supports. A series of MnxOy-Al2O3 (MA), MnxOy-CeO2 (MC), MnxOy-ZrO2 (MZ) and MnxOy-SiO2 (MS) catalysts were prepared by co-precipitation followed by hydrothermal method. As synthesised catalysts were characterised by various physico-chemical characterisation techniques. It was found that the presence of Mn3O4 species in MA and MZ catalysts is responsible for maximum catalytic activity towards 2-butanol oxidation. MA catalyst conferred a maximum 2-butanol conversion of 51% and 88% selectivity towards MEK. XPS analysis revealed that Mn in MA catalyst exists in +2 and +3 oxidation states and responsible for 2-butanol oxidation. Moreover it was found that the acidity of the catalyst also plays an important role in catalytic activity. (C) 2016 Published by Elsevier B.V.

Effective noncovalent functionalization of poly(ethylene glycol) to reduced graphene oxidenanosheets through gamma-radiolysis for enhanced lubrication - Gupta, Bhavana; Kumar, Niranjan; Panda, Kalpataru; Melvin, Ambrose A.; Joshi, Shailesh; Dash, Sitaram; Tyagi, Ashok Kumar (Journal of Physical Chemistry C, 2016)
High-quality reduced graphene oxide (rGO) nanosheets (NSs) were synthesized by the oxidation of graphite followed by hydrazine treatment for the reduction of the oxygen functionalities. gamma-Radiolysis was then used for the functionalization of the rGO-NSs with poly(ethylene glycol) 200 (PEG200). The functionalization resulted in the intercalation of PEG200 molecules in rGO through hydrogen bonding between the hydroxyl groups of rGO and the oxygen atoms of PEG200 molecules. This resulted in an increase in the d spacing of the graphene sheets and a decrease in the defect density of the carbon network in the rGO. The friction coefficient and wear of sliding steel surfaces were reduced by 38% and 55%, respectively, when 0.03 mg mL(-1) PEG200-functionalized rGO dispersed in PEG200 was used. The lubrication properties can be described by bipolar interactions between PEG200 and rGO, leading to effective dispersion. Chemical analysis of wear particles showed decomposition of rGO into nanosized graphite domains, as exhibited by mechanical energy produced in tribo-contact. Moreover, these domains formed effective and stable tribofilms on the steel wear tracks that easily sheared under the action of contact stress. This significantly enhanced the antifriction and antiwear properties, resulting in improved oxidation resistance of PEG200 under the tribo-contact. It was found that, at high rGO concentrations, the lubrication efficiency decreased as a result of graphene-graphene intersheet collisions, producing mechanical energy and chemical defects at contact interfaces.

Effects of the benzoxazole group on green fluorescent protein chromophore crystal structure and solid state photophysics - Ghodbane, Abdelhamid; Fellows, W. Brett; Bright, John R.; Ghosh, Debashree; Saffon, Nathalie; Tolbert, Laren M.; Fery-Forgues, Suzanne; Solntsev, Kyril M. (Journal of Materials Chemistry C, 2016)
Four benzoxazole-substituted GFP chromophores that differ by the length of their alkyl chain (from C1 to C12) were synthesized. In solution, the four compounds showed identical spectroscopic behavior, emitting blue light with moderate quantum yield. In the solid state, the butyl, pentyl and dodecyl derivatives strongly emitted orange light, while the methyl derivative was only weakly emissive. Based on the X-ray data and DFT calculations, emission in the solid state was explained by the formation of excimers. A very unusual ``hot-dog''-type excimer was found for the dodecyl derivative, in which two overlapping chromophores are separated by an alkyl chain.

Efficient cellular entry of (r-x-r)-type carbamate-plasmid DNA complexes and its implication for noninvasive topical DNA delivery to skin - Vij, Manika; Natarajan, Poornemaa; Yadav, Amit K.; Patil, Kiran M.; Pandey, Tanuja; Gupta, Nidhi; Santhiya, Deenan; Kumar, Vaijayanti A.; Fernandes, Moneesha; Ganguli, Munia (Molecular Pharmaceutics, 2016)
Arginine-rich cell penetrating peptides are powerful tools for in vitro as well as in vivo delivery of a wide plethora of biomolecules. However, presence of consecutive arginine residues leads to enhanced amenability for proteolytic degradation as well as steric hindrances for membrane interactions which compromise its bioavailability. In order to overcome these limitations we previously reported a safe and stable octaarginine based oligomer, i.e., (r-x-r)4-carbamate, where the backbone amide linkages were replaced by carbamate linkages and 6-aminohexanoic acid based spacer moieties were incorporated for better flexibility, hydrophobicity, optimal spacing of guanidinium groups, and protection against proteolytic cleavage; resulting in improved transfection efficiency over its amide counterpart. In the present work we have investigated the mechanism behind this enhanced transfection efficiency and, based on our observations, demonstrate how the synergistic effect of rationalized oligomer designing, complex characteristics, and cell type contributes to overall effective intracellular delivery. Our results indicate that the (r-x-r)4-carbamate plasmid DNA complexes primarily utilize lipid raft dependent pathway of cellular entry more than other pathways, and this possibly facilitates their increased entry in the lipid raft rich milieu of skin cells. We also emphasize the utility of oligomer (r-x-r)4-carbamate as an efficient carrier for topical delivery of nucleic acids in skin tissue. This carrier can be utilized for safe, efficient, and noninvasive delivery of therapeutically relevant macromolecular hydrophilic cargo like nucleic acids to skin.
Keywords: Cell penetrating peptides; endocytosis; nucleic acid delivery; skin penetration; transfection

Efficient synthesis of potent anti-tubercular drug candidate BM212 - More, N. A.; Patil, M. D.; Garud, D. R.; Gajbhiye, J. M. (Rasayan Journal of Chemistry, 2016)
A novel five step total synthesis route for an anti-tubercular drug BM212 starting from 4-chlorophenacyl bromide was developed with 48% overall yield. The synthesis is amiable for the synthesis of biologically active derivatives of BM 212.

Electrocatalytic water oxidation by a molecular cobalt complex through a high valent cobalt oxo intermediate - Das, Debasree; Pattanayak, Santanu; Singh, Kundan K.; Garai, Bikash; Sen Gupta, Sayam (Chemical Communications, 2016)
Biuret-modified tetraamidomacrocyclic cobalt complex [Co-III-bTAML]- is shown to catalyze electrochemical water oxidation at basic pH leading to the formation of O-2. Electrochemical and spectroscopic studies indicate a high valent cobalt oxo intermediate isoelectronic to Co-V(O) as the active oxidant. The kinetic isotope effect of 8.63 indicates an atom proton transfer mechanism.

Electronic structure and properties of layered gallium telluride - Shenoy, U. Sandhya; Gupta, Uttam; Narang, Deepa S.; Late, Dattatray J.; Waghmare, Umesh V.; Rao, C. N. R. (Chemical Physics Letters, 2016)
Layer-dependent electronic structure and properties of gallium monochalcogenides, GaX where X=S, Se, Te, have been investigated using first-principles calculations based on various functionals, with a motivation to assess their use in photocatalytic water splitting. Since hydrogen evolution by water splitting using visible light provides a promising way for solar energy conversion, both theoretical and experimental studies have been carried out on the photochemical hydrogen evolution by GaTe. We also present the Raman spectra of GaTe examined by both theory and experiment. (C) 2016 Elsevier B.V. All rights reserved.

Employing carboxylic acids in aryne multicomponent coupling triggered by aziridines/azetidines - Roy, Tony; Bhojgude, Sachin Suresh; Kaicharla, Trinadh; Thangaraj, Manikandan; Garai, Bikash; Biju, Akkattu T. (Organic Chemistry Frontiers, 2016)
The transition-metal-free aryne multicomponent coupling (MCC) involving carboxylic acids initiated by aziridines/azetidines has been reported. The use of aziridines as nucleophiles afforded N-aryl beta-amino alcohol derivatives and the application of azetidines as nucleophilic triggers furnished N-aryl gamma-amino alcohol derivatives in moderate to good yields. These reactions proceed under mild conditions and result in the formation of a new carbon-nitrogen bond and a new carbon-oxygen bond. The utility of carboxylic acids in aryne MCCs has been demonstrated, and the synthetic potential of phenols as acid surrogates in the present aryne MCCs has been realized.

Enantioselective modular total synthesis of macrolides Sch725674 and C-4-epi-Sch725674 - Sharma, Brijesh M.; Gontala, Arjun; Kumar, Pradeep (European Journal of Organic Chemistry, 2016)
The convergent total synthesis of Sch725674 has been accomplished by starting from (R)-1,2-epoxyheptane and assembling five modules in a highly stereoselective manner to give the final product in 6.6% overall yield. The same strategy was extended to the synthesis of its C-4 epimer. Key reactions of the synthetic pathway include a Jacobsen hydrolytic kinetic resolution of an epoxide followed by its regioselective opening through a Yamaguchi-Hirao alkynylation, and ring-closing metathesis reaction to furnish the unique 14-membered ring macrolactone. In addition, the influence of protecting groups on the efficiency of the ring-closing metathesis (RCM) macrocyclization has been studied to maximize its yields.
Keywords: Asymmetric synthesis; Hydrolytic kinetic resolution; Macrocycles; Metathesis; Natural products

Enantioselective synthesis of spirocyclohexadienones by NHC-catalyzed formal [3+3] annulation reaction of enals - Yetra, Santhivardhana Reddy; Mondal, Santigopal; Mukherjee, Subrata; Gonnade, Rajesh G.; Biju, Akkattu T. (Angewandte Chemie-International Edition, 2016)
The enantioselective synthesis of pyrazolone-fused spirocyclohexadienones was demonstrated by the reaction of alpha,beta-unsaturated aldehydes with alpha-arylidene pyrazolinones under oxidative N-heterocyclic carbene (NHC) catalysis. This atom-economic and formal [3+3] annulation reaction proceeds through a vinylogous Michael addition/spiroannulation/dehydrogenation cascade to afford spirocyclic compounds with an all-carbon quaternary stereocenter in moderate to good yields and excellent ee values. Key to the success of the reaction is the cooperative NHC-catalyzed generation of chiral alpha,beta-unsaturated acyl azoliums from enals, and base-mediated tandem generation of dienolate/enolate intermediates from pyrazolinones.
Keywords: annulation reactions; asymmetric catalysis; N-heterocyclic carbenes; organocatalysis; spiro compounds

Encapsulation of yeast (Saccharomyces cereviciae) by spray drying for extension of shelf life - Chandralekha, A.; Tavanandi, A. Hrishikesh; Amrutha, N.; Hebbar, H. Umesh; Raghavarao, K. S. M. S.; Gadre, Ramchandra V. (Drying Technology, 2016)
The objective of the present work was to encapsulate yeast using different carrier materials and examine their efficacy in retaining viability of cells after spray drying. Slurry containing yeast cells along with known amount of carrier material (maltodextrin, corn starch, gum arabic, acacia gum, polyethylene glycol 8000, -cyclodextrin, and skimmed milk powder, one at a time) was added and served as feed. Among these carrier materials attempted, corn starch and maltodextrin showed the best results with respect to powder yield (59%, w/w) and cell survival (80.5%), respectively. However, considering both survival and powder yield (67 and 59% w/w, respectively), corn starch was observed to be the most suitable carrier material.
Keywords: Cell viability; Encapsulation; freeze-drying; spray drying; Yeast

Engineering and in vitro evaluation of acid labile cholesterol tethered MG132 nanoparticle fortargeting ubiquitin-proteasome system in cancer - Ghosh, Chandramouli; Gupta, Neha; More, Piyush; Sengupta, Poulomi; Mallick, Abhik; Santra, Manas Kumar; Basu, Sudipta (Chemistryselect, 2016)
In recent years, proteasome has evolved as one of the important alternative targets in cancer chemotherapy. However, selective targeting of proteasome system in cancer cells still remains a major challenge. To address this, a potent peptide based proteasome inhibitor MG132 was chemically conjugated with biocompatible-biodegradable cholesterol by acid cleavable hydrazone linkage. Spherical nanoparticles (MG132-NPs) were engineered from cholesterol-MG132 conjugate. Increased amount of free MG132 was released from these nanoparticles in acidic environment compared to physiological milieu in a slow and controlled manner. These MG132-NPs were taken up by breast cancer MCF7 cells into lysosomes within 6 h. Proteasome system was inhibited by these MG132-NPs leading to stabilization of beta-catenin, cyclin A and cyclin B in HEK-293T cells. Interestingly, MG132-NPs induced much improved cell death in drug resistant MDA-MB-231 cells with insignificant toxicity in healthy cells (HEK293 and L929) even in higher concentration.

Engineering crystals that facilitate the acyl-transfer reaction: insight from a comparison of the crystal structures of myo-inositol-1,3,5-orthoformate-derived benzoates and carbonates - Tamboli, Majid I.; Krishanaswamy, Shobhana; Gonnade, Rajesh G.; Shashidhar, Mysore S. (ACTA Crystallographica Section C-Structural Chemistry, 2016)
Minor variations in the molecular structure of constituent molecules of reactive crystals often yield crystals with significantly different properties due to altered modes of molecular association in the solid state. Hence, these studies could provide a better understanding of the complex chemical processes occurring in the crystalline state. However, reactions that proceed efficiently in molecular crystals are only a small fraction of the reactions that are known to proceed (with comparable efficiency) in the solution state. Hence, for consistent progress in this area of research, investigation of newer reactive molecular crystals which support different kinds of reactions and their related systems is essential. The crystal structures and acyl-transfer reactivity of a myo-inositol-1,3,5-orthoformate-derived dibenzoate and its carbonate (4-O-benzoyl-2-O-phenoxycarbonyl-myo-inositol 1,3,5-orthoformate, C21H18O9) and thiocarbonate (4-O-benzoyl-2-O-phenoxythiocarbonyl-myo-inositol 1,3,5-orthoformate, C21H18O8S) analogs are compared with the aim of understanding the relationship between crystal structure and acyl-transfer reactivity. Insertion of an O atom in the acyl (or thioacyl) group of an ester gives the corresponding carbonate (or thiocarbonate). This seemingly minor change in molecular structure results in a considerable change in the packing of the molecules in the crystals of myoinositol-1,3,5-orthoformate-derived benzoates and the corresponding carbonates. These differences result in a lack of intermolecular acyl-transfer reactivity in crystals of myo-inositol-1,3,5-orthoformate-derived carbonates. Hence, this study illustrates the sensitivity of the relative orientation of molecules, their packing and ensuing changes in the reactivity of resulting crystals to minor changes in molecular structure.

Enhanced electrochemical performance of polypyrrole coated MoS2 nanocomposites as electrode material for supercapacitor application - Thakur, Anukul K.; Choudhary, Ram Bilash; Majumder, Mandira; Gupta, Govind; Shelke, Manjusha V. (Journal of Electroanalytical Chemistry, 2016)
Binary nanocomposites of polypyrrole (PPY) and Molybdenum disulfide (MoS2), with varying weight% of MoS2 viz. MP1, MP2, and MP3 corresponding to 12.5, 25, and 50% of MoS2 respectively, were prepared via. in-situ polymerization method. X-ray diffraction (XRD), field emission scanning microscopy (FESEM), and transmission electron microscopy (TEM) were employed to study the structure and morphology of the prepared nanocomposites. The electrochemical properties were studied by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) techniques. The nanocomposite electrode material MP2 reached a specific capacitance of 400 F/g at the current density 1 A/g which was higher than that of pure PPY and the other two nanocomposites viz. MP1 and MP3 having different compositions of MoS2 and PPY than that of MP2. It was noteworthy that the maximum capacitance value was obtained only for an optimum dose of MoS2 (MP2 in this case with 25% of MoS2) and any deviation from which ultimately degraded the capacitive performance of the nanocomposite electrode material. This could be attributed to the occurrence of maximum interaction between MoS2 and PPY in the nanocomposite only at a particular concentration of its host materials. The results showed that the specific capacitance of MP2 nanocomposite declined by 7.2% after 5000 cycles. Further, MP2 nanocomposite electrode showed much higher energy density (8.88 Wh/kg) as well as power density (2286 W/kg) which were higher than that shown by PPY electrode. (C) 2016 Elsevier B.V. All rights reserved.

Enhancement in rate of photocatalysis upon catalyst recycling - Sorathiya, Kalpesh; Mishra, Biswajit; Kalarikkal, Abhishek; Reddy, Kasala Prabhakar; Gopinath, Chinnakonda S.; Khushalani, Deepa (Scientific Reports, 2016)
Recyclability is an important aspect for heterogeneous photo-catalysts. Ease of recovery and stability of the photo-catalyst in terms of efficiency over the number of cycles are highly desired and in fact it is ideal if the efficiency is constant and it should not decrease marginally with each cycle. Presented here is a seminal observation in which the photocatalytic activity is shown to improve with increasing number of catalytic cycles (it is 1.7 times better after the 1st cycle and 3.1 times better after the 2nd cycle). Specifically, nanorods of pure TiO2 and TiO2 doped with controlled amount of tungsten have been used to degrade two model pollutants: Phenol and Rhodamine B under exclusive visible light illumination. It was found that, in case of 1 mol.% W incorporation, rate of photocatalysis and also the range of visible light absorption of the photocatalyst increased after the photocatalysis as compared to before photocatalysis. This aspect is unique for doped TiO2 and hence provides an intriguing way to mitigate low photoactivity.

Evaluation of uttroside B, a saponin from Solanum nigrum Linn, as a promising chemotherapeutic agent against hepatocellular carcinoma - Nath, Lekshmi R.; Gorantla, Jaggaiah N.; Thulasidasan, Arun Kumar T.; Vijayakurup, Vinod; Shah, Shabna; Anwer, Shabna; Joseph, Sophia M.; Antony, Jayesh; Veena, Kollery Suresh; Sundaram, Sankar; Marelli, Udaya K.; Lankalapalli, Ravi S.; et al. (Scientific Reports, 2016)
We report, for the first time, the remarkable efficacy of uttroside B, a potent saponin from Solanum nigrum Linn, against liver cancer. The compound has been isolated and characterized from the leaves of Solanum nigrum Linn, a plant widely used in traditional medicine and is a rich resource of several anticancer molecules. Uttroside B, that comprises of beta-D-glucopyranosyl unit at C-26 of the furostanol and beta-lycotetraosyl unit at C-3, is ten times more cytotoxic to the liver cancer cell line, HepG2 (IC50: 0.5 mu M) than sorafenib (IC50: 5.8 mu M), the only FDA-approved drug for liver cancer. Moreover, it induces cytotoxicity in all liver cancer cell lines, irrespective of their HBV status, while being non-toxic to normal immortalized hepatocytes. It induces apoptosis in HepG2 cells by down-regulating mainly the activation of MAPK and mTOR pathways. The drastic reduction in HepG2-xenograft tumor size achieved by uttroside B in NOD-SCID mice and substantiation of its biological safety through both acute and chronic toxicity studies in Swiss albino mice warrants clinical validation of the molecule against hepatic cancer, for which, the chemotherapeutic armamentarium currently has limited weapons.

Experimental and computational analysis of supramolecular motifs involving C-sp2(aromatic)-F and CF3 groups in organic solids - Panini, Piyush; Gonnade, Rajesh G.; Chopra, Deepak (New Journal of Chemistry, 2016)
A detailed experimental (SCXRD) and theoretical (PIXEL and QTAIM) investigation of the evolution of different supramolecular motifs formed via the presence of both C(sp(2))/(sp(3))-F groups in the crystal packing has been performed in a series of newly synthesized substituted benzanilides (containing ``both'' the fluorine and the trifluoromethyl group in the same molecule) along with previously reported similarly related crystal structures [CrystEngComm, 2008, 10, 54-67; CrystEngComm, 2012, 14, 1972-1989, CrystEngComm, 2013, 15, 3711-3733]. It was observed that the highest stabilized molecular motifs primarily consist of C(sp(2))-H center dot center dot center dot F-C(sp(2)) H-bonds in preference to C(sp(2))-H center dot center dot center dot F-C(sp(3)) H-bonds in the crystal. The motifs involving C(sp(2))-H center dot center dot center dot F-C(sp(2))/(sp(3)) H bonds were observed to be present over the entire distance range between 2.2 and 2.7 angstrom, albeit the difference in energies of stabilization involving fluorine atoms attached to sp(2) and sp(3) carbon is not significant in molecular crystals. From QTAIM analysis, the C(sp(2))/(sp(3))-F center dot center dot center dot F-C(sp(2))/(sp(3)) interactions were observed to be a closed shell in nature and provide local stabilization, indicating the formation of bonds, similar to weak hydrogen bonds observed in crystals.

Exploration of magnetically separable Ag@AgxNiy core/graded-alloy-shell nanostructures - Kumar, Mukesh; Soni, Kiran; Satpati, Biswarup; Gopinath, Chinnakonda S.; Deka, Sasanka (Chemical Communications, 2016)
We report novel bimetallic Ag@AgxNiy core@graded-alloy-shell nanoparticles (CGAS NPs), i.e. single Ag core NPs shelled by an AgxNiy graded alloy and stabilized by the CTAB surfactant employing a novel synthesis method. These Ag@AgxNiy CGAS NPs demonstrated superior catalytic performance in the synthesis of biologically active 3-amino alkylated indoles under green conditions.

Expression of proteins involved in digestion and detoxification are regulated in helicoverpa armigera to cope up with chlorpyrifos insecticide - Dawkar, Vishal V.; Chikate, Yojana R.; More, Tushar H.; Gupta, Vidya S.; Giri, Ashok P. (Insect Science, 2016)
Helicoverpa armigera is a key pest in many vital crops, which is mainly controlled by chemical strategies. To manage this pest is becoming challenging due to its ability and evolution of resistance against insecticides. Further, its subsequent spread on nonhost plant is remarkable in recent times. Hence, decoding resistance mechanism against phytochemicals and synthetic insecticides is a major challenge. The present work describes that the digestion, defense and immunity related enzymes are associated with chlorpyrifos resistance in H. armigera. Proteomic analysis of H. armigera gut tissue upon feeding on chlorpyrifos containing diet (CH) and artificial diet (AD) using nano-liquid chromatography-mass spectrometry identified upregulated 23-proteins in CH fed larvae. Database searches combined with gene ontology analysis revealed that the identified gut proteins engrossed in digestion, proteins crucial for immunity, adaptive responses to stress, and detoxification. Biochemical and quantitative real-time polymerase chain reaction analysis of candidate proteins indicated that insects were struggling to get nutrients and energy in presence of CH, while at the same time endeavoring to metabolize chlorpyrifos. Moreover, we proposed a potential processing pathway of chlorpyrifos in H. armigera gut by examining the metabolites using gas chromatography-mass spectrometry. H. armigera exhibit a range of intriguing behavioral, morphological adaptations and resistance to insecticides by regulating expression of proteins involved in digestion and detoxification mechanisms to cope up with chlorpyrifos. In these contexts, as gut is a rich repository of biological information; profound analysis of gut tissues can give clues of detoxification and resistance mechanism in insects.
Keywords: chlorpyrifos; Helicoverpa armigera; insecticide resistance; proteomics; real-time PCR

Extension of the effective fragment potential method to macromolecules - Gurunathan, Pradeep Kumar; Acharya, Atanu; Ghosh, Debashree; Kosenkov, Dmytro; Kaliman, Ilya; Shao, Yihan; Krylov, Anna I.; Slipchenko, Lyudmila V. (Journal of Physical Chemistry B, 2016)
The effective fragment potential (EFP) approach, which can be described as a nonempirical polarizable force field, affords an accurate first-principles treatment of noncovalent interactions in extended systems. EFP can also describe the effect of the environment on the electronic properties (e.g., electronic excitation energies and ionization and electron-attachment energies) of a subsystem via the QM/EFP (quantum mechanics/EFP) polarizable embedding scheme. The original formulation of the method assumes that the system can be separated, without breaking covalent bonds, into closed-shell fragments, such as solvent and solute molecules. Here, we present an extension of the EFP method to macromolecules (mEFP). Several schemes for breaking a large molecule into small fragments described by EFP are presented and benchmarked. We focus on the electronic properties of molecules embedded into a protein environment and consider ionization, electron-attachment, and excitation energies (single-point calculations only). The model systems include chromophores of green and red fluorescent proteins surrounded by several nearby amino acid residues and phenolate bound to the T4 lysozyme. All mEFP schemes show robust performance and accurately reproduce the reference full QM calculations. For further applications of mEFP, we recommend either the scheme in which the peptide is cut along the C-alpha-C bond, giving rise to one fragment per amino acid, or the scheme with two cuts per amino acid, along the C-alpha-C and C-alpha-N bonds. While using these fragmentation schemes, the errors in solvatochromic shifts in electronic energy differences (excitation, ionization, electron detachment, or electron-attachment) do not exceed 0.1 eV. The largest error of QM/mEFP against QM/EFP (no fragmentation of the EFP part) is 0.06 eV (in most cases, the errors are 0.01-0.02 eV). The errors in the QM/molecular mechanics calculations with standard point charges can be as large as 0.3 eV.

Field emission properties of highly ordered low-aspect ratio carbon nanocup arrays - Gupta, Bipin Kumar; Kedawat, Garima; Kumar, Pawan; Singh, Satbir; Suryawanshi, Sachin R.; Agrawal, Neetu; Gupta, Govind; Kim, Ah Ra; Gupta, R. K.; More, Mahendra A.; Late, Dattatray J.; Hahm, Myung Gwan (RSC Advances, 2016)
Herein, we design and develop a field emission device utilizing highly porous carbon nanocup (CNC) films. These three-dimensional (3D) low-aspect ratio CNC structures were fabricated by a combination of anodization and chemical vapor deposition techniques. The low turn-on fields of 2.30 V mu m(-1) were observed to draw an emission current density of 1 mu A cm(-2) and a maximum emission current density of similar to 1.802 mA cm(-2) drawn at an applied field of similar to 4.20 V mu m(-1). The enhanced field emission behavior observed from the CNC films is attributed to an excellent field enhancement factor of 1645. The observed field emission properties of CNC arrays are attributed to a synergistic combination of high aspect ratio, nano-sized radius of curvature, highly organized distribution of the emitters over the whole area of specimen and lower screening effect of the CNC arrays. These observations shed light on the effect of the stacking carbon layers of CNC on their electronic properties and open up possibilities to integrate new morphologies of graphitic carbon in nanotechnology applications. Thus, the low turn on field, high emission current density and better emission current stability enable CNC based future field emission applications.

Fine tuning the composition and nanostructure of Fe-based core-shell nanocatalyst for efficient CO2 hydrogenation - Gupta, Sharad; Jain, Vivek K.; Jagadeesan, Dinesh (Chemnanomat, 2016)
Hydrogenation of CO2 to hydrocarbons is one of the crucial technologies to address the energy deficit and increasing environmental pollution. In this work, we have synthesized and systematically studied the influence of composition and nanostructure of a Fe-based, carbon-coated core shell nanocatalyst. The synthesis method offered good control over the thickness of the carbon coating in the core shell catalyst, which in turn controlled the chemical composition of the core. The results emphasized an optimal amount of Fe3O4, Fe5C2 in the core and partially graphitized carbon in the shell for a high catalytic activity in the conversion of CO2 at atmospheric pressure with higher selectivity to C-2-C-4 olefins.

Formal total synthesis of anti-helicobacter pylori agent (+)-spirolaxine methyl ether - Gadakh, Sunita K.; Sudalai, Arumugam (Tetrahedron Letters, 2016)
A convergent, formal enantioselective synthesis of anti-Helicobacter pylori agent, (+)-spirolaxine methyl ether 2 has been achieved in high enantiomeric purity starting from commercially available 1,5-pentanediol. The strategy mainly comprises of the Noyori's asymmetric reduction and Brown allylation/Cu-catalyzed lactonization as the key step for the construction of key chiral intermediates, spiroketal 3 and phthalide fragment 4. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Brown allylation; Cu-catalyzed lactonization; Noyori's asymmetric reduction; Phthalide; Spiroketal

Functional and conformational transitions of mevalonate diphosphate decarboxylase from Bacopa monniera - Shakeel, Abbassi; Patel, Krunal; Khan, Bashir Mohammad; Bhosale, Siddharth H.; Gaikwad, Sushama M. (International Journal of Biological Macromolecules, 2016)
Functional and conformational transitions of mevalonate diphosphate decarboxylase (MDD), a key enzyme of mevalonate pathway in isoprenoid biosynthesis, from Bacopa monniera (BmMDD), cloned and overexpressed in Escherichia coli were studied under thermal, chemical and pH-mediated denaturation conditions using fluorescence and Circular dichroism spectroscopy. Native BmMDD is a helix dominant structure with 45% helix and 11% sheets and possesses seven tryptophan residues with two residues exposed on surface, three residues partially exposed and two situated in the interior of the protein. Thermal denaturation of BmMDD causes rapid structural transitions at and above 40 degrees C and transient exposure of hydrophobic residues at 50 degrees C, leading to aggregation of the protein. An acid induced molten globule like structure was observed at pH 4, exhibiting altered but compact secondary structure, distorted tertiary structure and exposed hydrophobic residues. The molten globule displayed different response at higher temperature and similar response to chemical denaturation as compared to the native protein. The surface tryptophans have predominantly positively charged amino acids around them, as indicated by higher K-SV for IC as compared to that for CsCl. The native enzyme displayed two different lifetimes, vi (1.203 +/- 0.036 ns) and tau 2 (3.473 +/- 0.12 ns) indicating two populations of tryptophan. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Aggregation; CD spectroscopy; Fluorescence quenching; Mevalonate diphosphate decarboxylase; Unfolding

Functional characterization and transient expression manipulation of a new sesquiterpene synthase involved in beta-caryophyllene accumulation in Ocimum - Jayaramaiah, Ramesha H.; Anand, Atul; Beedkar, Supriya D.; Dholakia, Shushan B.; Punekar, Sachin A.; Kalunke, Raviraj M.; Gade, Wasudeo N.; Thulasiram, Hirekodathakallu V.; Giri, Ashok P. (Biochemical And Biophysical Research Communications, 2016)
The genus Ocimum has a unique blend of diverse secondary metabolites, with major proportion of terpenoids including mono- and sesquiterpenes. Although, beta-Caryophyllene, bicyclic sesquiterpene, is one of the major terpene found in Ocimum species and known to possess several biological activities, not much is known about its biosynthesis in Ocimum. Here, we describe isolation and characterization of beta-caryophyllene synthase gene from Ocimum kilimandscharicum Gurke (OkBCS- GenBank accession no. KP226502). The open reading frame of 1629 bp encoded a protein of 542 amino acids with molecular mass of 63.6 kDa and pl value of 5.66. The deduced amino acid sequence revealed 50-70% similarity with known sesquiterpene synthases from angiosperms. Recombinant OkBCS converted farnesyl diphosphate to beta-caryophyllene as a major product (94%) and 6% alpha-humulene. Expression variation of OkBCS well corroborated with beta-caryophyllene levels in different tissues from five Ocimum species. OkBCS transcript revealed higher expression in leaves and flowers. Further, agro-infiltration based transient expression manipulation with OkBCS over-expression and silencing confirmed its role in beta-caryophyllene biosynthesis. These findings may potentially be further utilized to improve plant defense against insect pests. (C) 2016 Elsevier Inc. All rights reserved.
Keywords: beta-Caryophyllene; Natural product biosynthesis; Ocimum; Terpene synthase; Transient expression

Functionalization and isoreticulation in a series of metal-organic frameworks derived from pyridinecarboxylates - Pachfule, Pradip; Garai, Bikash; Banerjee, Rahul (Inorganic Chemistry, 2016)
The partially fluorinated metal-organic frameworks (F-MOFs) have been constructed from 3-fltoro-4-pyridinecarboxylic acid and trans-3-fluoro-4-pyridineacrylic acid linkers using Mn2+, Co2+, and, Cd2+ metals via the solvothetrnal method, which show isostructural isomerism with their nonfluorinated counterparts synthesized using 4-pyridinecarboxylic acid and trans-4-pyridineacrylic acid, respectively. The simultaneous effect of partial fluorination and isoreticulation on structure and H-2 adsorption has been studied systematically in isostructural nonfluorinated and partially fluorinated MOFs, which shows that the increment in the hydrogen uptake properties in F-MOFs is not a universal phenomenon but is rather system-specific and changes from one system to another.

Fusarium oxysporum mediates systems metabolic reprogramming of chickpea roots as revealed by a combination of proteomics and metabolomics - Kumar, Yashwant; Zhang, Limin; Panigrahi, Priyabrata; Dholakia, Bhushan B.; Dewangan, Veena; Chavan, Sachin G.; Kunjir, Shrikant M.; Wu, Xiangyu; Li, Ning; Rajmohanan, Pattuparambil R.; Kadoo, Narendra Y.; Giri, Ashok P.; et al. (Plant Biotechnology Journal, 2016)
Molecular changes elicited by plants in response to fungal attack and how this affects plant-pathogen interaction, including susceptibility or resistance, remain elusive. We studied the dynamics in root metabolism during compatible and incompatible interactions between chickpea and Fusarium oxysporum f. sp. ciceri (Foc), using quantitative label-free proteomics and NMR-based metabolomics. Results demonstrated differential expression of proteins and metabolites upon Foc inoculations in the resistant plants compared with the susceptible ones. Additionally, expression analysis of candidate genes supported the proteomic and metabolic variations in the chickpea roots upon Foc inoculation. In particular, we found that the resistant plants revealed significant increase in the carbon and nitrogen metabolism; generation of reactive oxygen species (ROS), lignification and phytoalexins. The levels of some of the pathogenesis-related proteins were significantly higher upon Foc inoculation in the resistant plant. Interestingly, results also exhibited the crucial role of altered Yang cycle, which contributed in different methylation reactions and unfolded protein response in the chickpea roots against Foc. Overall, the observed modulations in the metabolic flux as outcome of several orchestrated molecular events are determinant of plant's role in chickpea-Foc interactions.
Keywords: Chickpea; fusarium oxysporum; Metabolomics; NMR; plant-pathogen interaction; proteomics

GAME9 regulates the biosynthesis of steroidal alkaloids and upstream isoprenoids in the plant mevalonate pathway - Cardenas, Pablo D.; Sonawane, Prashant D.; Pollier, Jacob; Vanden Bossche, Robin; Dewangan, Veena; Weithorn, Efrat; Tal, Lior; Meir, Sagit; Rogachev, Ilana; Malitsky, Sergey; Giri, Ashok P.; Goossens, Alain; et al. (Nature Communications, 2016)
Steroidal glycoalkaloids (SGAs) are cholesterol-derived molecules produced by solanaceous species. They contribute to pathogen defence but are toxic to humans and considered as anti-nutritional compounds. Here we show that GLYCOALKALOID METABOLISM 9 (GAME9), an APETALA2/Ethylene Response Factor, related to regulators of alkaloid production in tobacco and Catharanthus roseus, controls SGA biosynthesis. GAME9 knockdown and overexpression in tomato and potato alters expression of SGAs and upstream mevalonate pathway genes including the cholesterol biosynthesis gene STEROL SIDE CHAIN REDUCTASE 2 (SSR2). Levels of SGAs, C24-alkylsterols and the upstream mevalonate and cholesterol pathways intermediates are modified in these plants. Delta(7)-STEROL-C5(6)-DESATURASE (C5-SD) in the hitherto unresolved cholesterol pathway is a direct target of GAME9. Transactivation and promoter-binding assays show that GAME9 exerts its activity either directly or cooperatively with the SlMYC2 transcription factor as in the case of the C5-SD gene promoter. Our findings provide insight into the regulation of SGA biosynthesis and means for manipulating these metabolites in crops.

Gas-solid interaction of H-2-Ce0.95Zr0.05O2: new insights into surface participation in heterogeneous catalysis - Jain, Ruchi; Dubey, Anjani; Ghosalya, Manoj Kumar; Gopinath, Chinnakonda S. (Catalysis Science & Technology, 2016)
A direct interaction between a reduction medium (H-2) and a Ce0.95Zr0.05O2 (CZ) solid surface was explored through ambient pressure photoelectron spectroscopy (APPES), with conventional X-ray and He-I photon sources, in H-2 atmosphere up to 0.1 mbar pressure and 773 K. A porous CZ thin film was prepared by a combination of sol-gel and spin-coating methods, and was employed to understand the redox nature of ceria under reduction conditions. The maximum of 45% Ce3+ along with the corresponding oxygen vacancy was observed due to reduction. An unprecedented decrease in the valence band (VB) energy up to 1.4 eV was observed on reduction along with a narrowing of VB. The highest occupied energy band derived from Ce 4f also shifts closer to E-F. H-2 molecular vibration observed in VB-APPES was employed as a probe to explore the surface potential changes along with the dynamic change in the nature of the surface under reduction conditions. The surface potential decreases by 0.27 eV up to 673 K, and then it reverts by 0.24 eV on further reduction at 773 K for different reasons. Further, an enhancement in the Ce 5d-O 2p interaction occurs at the expense of the Ce 4f-O 2p interaction under the above reduction conditions. Vacuum annealing and H-2 reduction after that show significantly more VB shift and enhanced reduction than H-2 reduction alone. Although Ce reduction occurs on high temperature vacuum annealing of CZ, a significantly lower amount of oxygen vacancies appears. This study shows the dynamic changes in the nature of the surface due to a gas (H-2)-solid (CZ) interaction and ensuing electronic structure changes that influence heterogeneous catalysis. It also underscores the necessity to study the catalytic materials under in situ conditions or closer to that.

Glycopolypeptide-grafted bioactive polyionic complex vesicles (PICsomes) and their specific polyvalent interactions - Pandey, Bhawana; Mahato, Jaladhar; Cotta, Karishma Berta; Das, Soumen; Sharma, Dharmendar Kumar; Sen Gupta, Sayam; Chowdhury, Arindam (ACS Omega, 2016)
Glycopolypeptide-based self-assembled nano-/microstructures with surface-tethered carbohydrates are excellent mimics of glycoproteins on the cell surface. To expand the broad repertoire of glycopolypeptide-based supramolecular soft structures such as polymersomes formed via self-assembly of amphiphilic polymers, we have developed a new class of polyionic complex vesicles (PICsomes) with glycopolypeptides grafted on the external surface. Oppositely charged hydrophilic block copolymers of glycopolypeptide(20)-b-poly-L-lysine(100) and PEG(2k)-b-poly-L-glutamate(100) [PEG = poly(ethylene glycol)] were synthesized using a combination of ring-opening polymerization of N-carboxyanhydrides and ``click'' chemistry. Under physiological conditions, the catiomer and aniomer self-assemble to form glycopolypeptide-conjugated PICsomes (GP-PICsomes) of micrometer dimensions. Electron and atomic force microscopy suggests a hollow morphology of the PICsomes, with inner aqueous pool (core) and peripheral PIC (shell) regions. Owing to their relatively large (similar to micrometers) size, the hollowness of the supramolecular structure could be established via fluorescence microscopy of single GP-PICsomes, both in solution and under dry conditions, using spatially distributed fluorescent probes. Furthermore, the dynamics of single PICsomes in solution could be imaged in real time, which also allowed us to test for multivalent interactions between PICsomes mediated by a carbohydrate (mannose)-binding protein (lectin, Con-A). The immediate association of several GP-PICsomes in the presence of Con-A and their eventual aggregation to form large insoluble aggregate clusters reveal that upon self-assembly carbohydrate moieties protrude on the outer surface which retains their biochemical activity. Challenge experiments with excess mannose reveal fast deaggregation of GP-PICsomes as opposed to that in the presence of excess galactose, which further establishes the specificity of lectin-mediated polyvalent interactions of the GP-PICsomes.

Gold(I)-catalyzed hydroaminaloxylation and petasis-ferrier rearrangement cascade of aminaloalkynes - Gade, Amol B.; Patil, Nitin T. (Organic Letters, 2016)
An efficient method has been developed to generate a diverse array of indolizidines and quinolizidines from readily available aminaloalkynes via a gold(I)-catalyzed hydroaminaloxylation and Petasis-Ferrier rearrangement cascade. The method enabled a formal synthesis of (+/-)-antofine.

Graphene based nanocomposites for alloy (SnO2), and conversion (Fe3O4) type efficient anodes for Li-ion battery applications - Mhamane, Dattakumar; Aravindan, Vanchiappan; Taneja, Divya; Suryawanshi, Anil; Game, Onkar; Srinivasan, Madhavi; Ogale, Satishchandra B. (Composites Science and Technology, 2016)
Two types of trigol reduced one pot synthesized graphene (TRG) based nanocomposites (SnO2-TRG, and Fe3O4-TRG) are examined as potential anodes for Lithium ion battery (LIB) applications. The two specific systems represent different electrode reaction mechanisms, namely alloying, and conversion respectively. The high resolution transmission electron microscopy (HR-TEM) analysis confirms the uniform distribution of SnO2 (similar to 2 nm), and Fe3O4 (similar to 8 nm) particulates on ultrathin TRG nanosheets and highlights the importance of surfactant free synthesis. The SnO2-TRG, and Fe3O4-TRG exhibited the maximum reversible capacity of similar to 947, and similar to 1024 mA h g(-1), respectively. The results show that such graphene based composite materials can be effectively used as prospective anodes for LIB applications. (C) 2016 Elsevier Ltd. All rights reserved.

Green leaf to inorganic leaf: a case study of ZnO - Sathu, Naveen K.; Devaraji, Perumal; Gopinath, Chinnakonda S. (Journal of Nanoscienceand Nanotechnology, 2016)
Can we use green leaves, available freely in our gardens, as a template for making inorganic leaf, while retaining the nanospace available within the leaf architecture. The answer is 'yes', and it is demonstrated with inorganic leaf made up of ZnO, by intercalating Zn2+ ions into the porous channels of the champa (Plumeria, Magnolia champaca) tree leaves. TEM studies reveal a variety of macro-micro-nanospace available in the inorganic leaf ZnO (IL-ZnO), and suggest the possibility of exploiting the same to produce natural nano-architecture for various applications. A speciality of the present work is the maximum suppression of defects in photoluminescence of IL-ZnO leaf, compared to the commercial ZnO, which is exploited for light harvesting through chemical conversion. Benzene to phenol conversion was studied in UV light and IL-ZnO show significant conversion and yield demonstrating C-H activation at ambient temperature.

Green synthesis of stable Cu(0) nanoparticles onto reduced graphene oxide nanosheets: a reusable catalyst for the synthesis of symmetrical biaryls from arylboronic acids under base-free conditions (vol 5, pg 1251, 2015) - Hussain, Najrul; Gogoi, Pranjal; Azhagan, Muniraj Vedi Kuyil; Shelke, Manjusha V.; Das, Manash R. (Catalysis Science & Technology, 2016)
Correction for ‘Green synthesis of stable Cu(0) nanoparticles onto reduced graphene oxide nanosheets: a reusable catalyst for the synthesis of symmetrical biaryls from arylboronic acids under base-free conditions’ by Najrul Hussain et al., Catal. Sci. Technol., 2015, 5, 1251–1260.

High hydroxide conductivity in a chemically stable crystalline metal-organic framework containing a water-hydroxide supramolecular chain - Nagarkar, Sanjog S.; Anothumakkool, Bihag; Desai, Aamod V.; Shirolkar, Mandar M.; Kurungot, Sreekumar; Ghosh, Sujit K. (Chemical Communications, 2016)
A chemically stable cationic MOF encapsulating an in situ formed water-hydroxide supramolecular anionic chain is realized for high hydroxide (OH-) ion conductivity in the solid-state (Type A). High OH- ion conductivity and low activation energy of the MOF demonstrate the advantage of the in situ incorporation of OH- ions to achieve efficient OH- ion conduction in the solid-state.

High loading of pd nanoparticles by interior functionalization of mofs for heterogeneous catalysis - Gole, Bappaditya; Sanyal, Udishnu; Banerjee, Rahul; Mukherjee, Partha Sarathi (Inorganic Chemistry, 2016)
In this report, the issue related to nanoparticle (NP) agglomeration upon increasing their loading amount into metal-organic frameworks (MOFs) has been addressed by functionalization of MOFs with alkyne groups. The alkynophilicity of the Pd2+ (or other noble metals) ions has been utilized successfully for significant loading of Pd NPs into alkyne functionalized MOFs. It has been shown here that the size and loading amount of Pd NPs are highly dependent on the surface area and pore width of the MOFs. The loading amount of Pd NPs was increased monotonically without altering their size distribution on a particular MOF. Importantly, the distinct role of alkyne groups for Pe(2+) stabilization has also been demonstrated by performing a control experiment considering a MOF without an alkyne moiety. The preparation of NPs involved two distinct steps viz. adsorption of metal ions inside MOFs and reduction of metal ions. Both of these steps were monitored by microscopic techniques. This report also demonstrates the applicability of Pd@MOF NPs as extremely efficient heterogeneous catalysts for Heck-coupling and hydrogenation reactions of aryl bromides or iodides and alkenes, respectively.

High-index faceted Au nanocrystals with highly controllable optical properties and electro-catalytic activity - Rajendra, Ranguwar; Gangadharan, Pranav K.; Tripathi, Shalini; Kurungot, Sreekumar; Ballav, Nirmalya (Nanoscale, 2016)
We introduce a new and naturally abundant mild reducing agent, tannic acid, to improve the seed-mediated growth method for the synthesis of elongated tetrahexahedral Au nanocrystals enclosed with high-index (730) planes, at room-temperature. The control of the dimensions, plasmonics and electro-catalysis of such high-index faceted nanocrystals is remarkable.

Highly efficient nitrogen-doped hierarchically porous carbon supported Ni nanoparticles for the selective hydrogenation of furfural to furfuryl alcohol - Kotbagi, Trupti V.; Gurav, Hanmant R.; Nagpure, Atul S.; Chilukuri, Satyanarayana V.; Bakker, Martin G. (RSC Advances, 2016)
Nickel nanoparticles supported on nitrogen doped hierarchically porous carbon (Ni/CN) are found to be highly efficient and reusable catalysts for the selective hydrogenation of biomass-derived furfural to furfuryl alcohol (FA). Various characterization methods were used to study the structural and morphological features of the catalysts. Furfural conversion of 96% and 95% FA selectivity was obtained using a 5 wt% Ni/CN catalyst. This catalyst showed excellent recyclability without any loss in activity and FA selectivity when it was reused four times. The higher catalytic performance is attributed to the nitrogen incorporated hierarchical porous 3D carbon network.

Highly stable laser-scribed flexible planar microsupercapacitor using mushroom derived carbon electrodes - Yadav, Poonam; Basu, Aniruddha; Suryawanshi, Anil; Game, Onkar S.; Ogale, Satishchandra (Advanced Materials Interfaces, 2016)
A report is presented on the fabrication of all solid-state interdigitated flexible microsupercapacitor using ultrafast and highly scalable laser scribing technique, using highly mesoporous carbon synthesized from biomass (mushroom) with hydrothermal preprocessing. The specific protocol used for carbon synthesis renders some unique property features to the material (surface area of 2604 m(2) g(-1) with hierarchical pore size distribution) in the context of supercapacitor electrode application. A polyvinyl alcohol (PVA)-H2SO4 gel electrolyte is used for electrochemical measurements. The microsupercapacitor shows high cyclic stability up to 15000 cycles. Moreover it shows nearly 90% stability after 1000 bending cycles at 60 degrees angle. It also retains its performance even under 120 degrees bending condition. This work represents a facile and fast technique for microscaled device fabrication that can be easily commercialized. Moreover, the mushroom-derived carbon used to make the electrodes holds great promise in context of the stability and flexibility of flexible supercapacitors.

Hydralazine inhibits amyloid beta (Aβ) aggregation and glycation and ameliorates Aβ1–42 induced neurotoxicity - Batkulwar, Kedar B.; Jana, Asis K.; Godbole, Rashmi K.; Khandelwal, Puneet; Sengupta, Neelanjana; Kulkarni, Mahesh J. (RSC Advances, 2016)

Hydrogel-derived soft materials for biomimetic and energy-related functions - Goudappagouda,; Wakchaure, V. C.; Ranjeesh, K. C.; Babu, S. S. (Australian Journal of Chemistry, 2016)
Supramolecular assembly of molecules leading to gelation of large amount of solvents is always a fascinating topic of research. In the very recent past, the exciting developments have marked hydrogels as intriguing materials with excellent features. Hydrogel scaffolds enable the accommodation of organic and/or inorganic guest materials to deliver diverse applications. Hydrogels have been exploited to generate soft materials with mechanical anisotropy, tunable rigidity, self-healing properties, as well as photocatalytic capabilities towards H2 production. Remarkably, the combination of a photocatalyst and a light-harvesting system in the gel matrix provides a unique means to photocatalytic H2 production. The biomimetic applications of hydrogels have also generated much attraction due to their potential demonstrations. The diverse applications underline the significance of such a soft gel medium to reach the final goal. Herein, important reports pertaining to the use of hydrogels as an effective way to generate advanced materials for biomimetic and energy-related issues are discussed.

Hydrogenation of cinnamaldehyde to hydrocinnamaldehyde over Pd nanoparticles deposited on nitrogen-doped mesoporous carbon - Nagpure, Atul S.; Gurrala, Lakshmiprasad; Gogoi, Pranjal; Chilukuri, Satyanarayana V. (RSC Advances, 2016)
Palladium nanoparticles deposited on nitrogen-doped mesoporous carbon (NMC) were synthesized by simple ultrasonic-assisted method. This novel Pd-NMC catalyst was highly active and selective for the hydrogenation of cinnamaldehyde (CA) to hydrocinnamaldehyde (HCA) at room temperature (30 degrees C) under low H-2 pressure. The nitrogen-free mesoporous carbon (MC) and activated carbon (AC) were also employed as the support for Pd in the liquid-phase hydrogenation of CA. The incorporation of nitrogen into carbon matrix remarkably enhanced the catalytic activity and C=C bond hydrogenation selectivity (HCA selectivity of 93% with 100% CA conversion for Pd-NMC) in CA hydrogenation compared to the catalysts with no nitrogen (HCA selectivity of 66 and 47% for Pd-MC and Pd-AC, respectively). Moreover, Pd-NMC catalyst demonstrated an excellent recyclability without any loss in activity and HCA selectivity when it was reused for six times. The superior catalytic performance of Pd-NMC catalyst in CA hydrogenation is attributed to the small size of Pd nanoparticles due to presence of high nitrogen content (11.6 wt%) and mesoporous nature of NMC support.

Hydrogen-bonded organic frameworks (HOFs): a new class of porous crystalline proton-conducting materials - Karmakar, Avishek; Illathvalappil, Rajith; Anothumakkool, Bihag; Sen, Arunabha; Samanta, Partha; Desai, Aamod V.; Kurungot, Sreekumar; Ghosh, Sujit K. (Angewandte Chemie-International Edition, 2016)
Two porous hydrogen-bonded organic frameworks (HOFs) based on arene sulfonates and guanidinium ions are reported. As a result of the presence of ionic backbones appended with protonic source, the compounds exhibit ultra-high proton conduction values (sigma) 0.75x 10(-2)Scm(-1) and 1.8x10(-2)Scm(-1) under humidified conditions. Also, they have very low activation energy values and the highest proton conductivity at ambient conditions (low humidity and at moderate temperature) among porous crystalline materials, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). These values are not only comparable to the conventionally used proton exchange membranes, such as Nafion used in fuel cell technologies, but is also the highest value reported in organic-based porous architectures. Notably, this report inaugurates the usage of crystalline hydrogen-bonded porous organic frameworks as solid-state proton conducting materials.
Keywords: guanidinium; hydrogen-bonded organic frameworks; porous crystalline frameworks; proton conduction; sulfonates

Identification of unintuitive features of sumoylation through mathematical modeling - Puntambekar, Shraddha S.; Nyayanit, Dimpal; Saxena, Priyanka; Gadgil, Chetan J. (Journal of Biological Chemistry, 2016)
Sumoylation is a multistep, multienzymatic post-translational modification in which a small ubiquitin-like modifier protein (SUMO) is attached to the target. We present the first mathematical model for sumoylation including enzyme mechanism details such as autosumoylation of E2 and multifunctional nature of SENP. Simulations and analysis reveal three nonobvious properties for the long term response, modeled as an open system: (i) the steady state sumoylation level is robust to variation in several enzyme properties; (ii) even when autosumoylation of E2 results in equal or higher activity, the target sumoylation levels are lower; and (iii) there is an optimal SENP concentration at which steady state target sumoylation level is maximum. These results are qualitatively different for a short term response modeled as a closed system, where e.g. sumoylation always decreases with increasing SENP levels. Simulations with multiple targets suggest that the available SUMO is limiting, indicating a possible explanation for the experimentally observed low fractional sumoylation. We predict qualitative differences in system responses at short post-translational and longer transcriptional time scales. We thus use this mechanism-based model to explain system properties and generate testable hypotheses for existence and mechanism of unexpected responses.

Immobilization of multivalent glycoprobes on gold surfaces for sensing proteins and macrophages - Gade, Madhuri; Khandelwal, Puneet; Sangabathuni, Sivakoti; Bavireddi, Harikrishna; Murthy, Raghavendra Vasudeva; Poddar, Pankaj; Kikkeri, Raghavendra (Analyst, 2016)
The multivalent display of carbohydrates on the cell surface provides cooperative binding to improve the specific biological events. In addition to multivalency, the spatial arrangement and orientation of sugars with respect to external stimuli also trigger carbohydrate-protein interactions. Herein, we report a non-covalent host-guest strategy to immobilize heptavalent glyco-beta-cyclodextrin on gold-coated glass slides to study multivalent carbohydrate-protein interactions. We have found that the localization of sugar entities on surfaces using beta-cyclodextrin (beta-CD) chemistry increased the avidity of carbohydrate-protein and carbohydrate-macrophage interactions compared to monovalent-beta-CD sugar coated surfaces. This platform is expected to be a promising tool to amplify the avidity of sugar-mediated interactions on surfaces and contribute to the development of next generation bio-medical products.

Impact of modular substitution on crystal packing: the tale of two ureas - Koshti, Vijay S.; Thorat, Shridhar H.; Gote, Ravindra P.; Chikkali, Samir H.; Gonnade, Rajesh G. (CrystEngComm, 2016)

Improved all-polymer solar cell performance of n-type naphthalene diimide-bithiophene P(NDI2OD-T2) copolymer by incorporation of perylene diimide as coacceptor - Sharma, Sandeep; Kolhe, Nagesh B.; Gupta, Vinay; Bharti, Vishal; Sharma, Abhishek; Datt, Ram; Chand, Suresh; Asha, S. K. (Macromolecules, 2016)
Naphthalene diimide-bithiophene P(NDI2OD-T2) is a well-known donor-acceptor polymer, previously explored as n-type material in all-polymer solar cells (all-PSCs) and organic field effect transistor (OFETs) applications. The optical, bulk, electrochemical, and semiconducting properties of P(NDI2OD-T2) polymer were tuned via random incorporation of perylene diimide (PDI) as coacceptor with naphthalene diimide (NDI). Three random copolymers containing 2,2'-bithiophene as donor unit and varying compositions of naphthalene diimide (NDI) and perylene diimide (xPDI, x = 15, 30, and 50 mol % of PDI) as two mixed acceptors were synthesized by Stille coupling copolymerization. Proton NMR spectra recorded in CD Cl-3 showed that the pi-pi stacking induced aggregation among the naphthalene units could be successfully disrupted by the random incorporation of bulky PDI units. The newly synthesized random copolymers were investigated as electron acceptors in BHJ all-PSCs, and their performance was compared with P(NDI2OD-T2) as reference polymer. An enhanced PCE of 5.03% was observed for BHJ all-PSCs (all-polymer solar cells) fabricated using NDI-Th-PDI30 as acceptor and PTB7-Th as donor, while the reference polymer blend with the same donor polymer exhibited PCE of 2.97% efficiency under similar conditions. SCLC bulk carrier mobility measured for blend devices showed improved charge mobility compared to reference polymer, with PTB7-Th:NDI-Th-PDI30 blend device exhibiting the high hole and electron mobility of 4.2 x 10(-4) and 1.5 x 10(-4) cm(2)/(V s), respectively. This work demonstrates the importance of molecular design via random copolymer strategy to control the bulk crystallinity, compatibility, blend morphology, and solar cell performance of n-type copolymers.

In 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.

Inhibition of quorum-sensing-mediated biofilm formation in Cronobacter sakazakii strains - Singh, Niharika; Patil, Amrita; Prabhune, Asmita; Goel, Gunjan (Microbiology-SGM, 2016)
The present study investigated plant extracts for their anti-quorum-sensing (QS) potential to inhibit the biofilm formation in Cronobacter sakazakii strains. The bioassay based on loss of pigment production by Chromobacterium violaceum 026 and Agrobacterium tumefaciens NTL4 (pZLR4) was used for initial screening of the extracts. Further, the effect of extracts on the inhibition of QS-mediated biofilm in C. sakazakii isolates was evaluated using standard crystal violet assay. The effect on biofilm texture was studied using SYTO9 staining and light and scanning electron microscopy. Among the tested extracts, Piper nigrum and Cinnamomum verum at 100 ppm resulted in 78 and 68% reduction in the production of violacein as well as blue-green colour in both biosensor strains. A higher inhibitory activity (>50 %) on biofilm formation in C. sakazakii was observed for Pip. nigrum and Cin. verum, whereas the other extracts possessed moderate (25-50 %) and minimal (<25 %) inhibitory activities. Further, the fluorescent and scanning electron microscopic images indicated a major disruption in the architecture of biofilms of tested strains by Pip. nigrum. This study points to the possibility of using Pip. nigrum and Cin. verum as inhibitor of QS-mediated biofilm formation by C. sakazakii that could be further explored for novel bioactive molecules to limit the emerging infections of C. sakazakii

Intramolecular dehydrogenative coupling of 2,3-diaryl acrylic compounds: access to substituted phenanthrenes - Gupta, Vijay; Rao, V. U. Bhaskara; Das, Tamal; Vanka, Kumar; Singh, Ravi P. (Journal of Organic Chemistry, 2016)
A simple, facile, and environmentally benign intramolecular dehydrogenative coupling of various 1,2-diarylethylenes for the synthesis of phenanthrenes in excellent yield has been described. This new methodology uses ceric ammonium nitrate (CAN) as a promoter at room temperature and has been extended to intermolecular synthesis of biaryl compounds. The electron transfer from methoxyarene to cerium leads to cationic radical formation, which further proceeds to intramolecular coupling. Preliminary mechanistic investigation by EPR spectroscopy and density functional theory calculation suggested a similar view.

Inverse high internal phase emulsion polymerization (i-HIPE) of GMMA, HEMA and GDMA for the preparation of superporous hydrogels as a tissue engineering scaffold - Nalawade, Archana C.; Ghorpade, Ravindra V.; Shadbar, Sadiqua; Qureshi, Mohammed Shadbar; Chavan, Nayaku; Khan, Ayesha A.; Ponrathnam, S. (Journal of Materials Chemistry B, 2016)
A series of novel superporous hydrogels for regenerative medicine were prepared by oil-in-water (o/w) or inverse high internal phase emulsion (i-HIPE) copolymerization of glycerol monomethacrylate (GMMA), 2-hydroxy ethyl methacrylate (HEMA) and glycerol dimethacrylate (GDMA) as a cross-linker using a non toxic solvent and a redox initiator system at the physiological temperature (37 degrees C). The monomer GMMA was synthesized from glycidyl methacrylate (GMA) by an alternative facile method using Amberlyst-15. The described i-HIPEs showed a significantly wider stability window. The polyHIPE hydrogels were characterized by FTIR, BET method for surface area, mercury porosimetry, SEM, DSC, TGA, XRD, compressive strain and strain recovery. The swelling ratio of the hydrogels and their degradation in 0.007 M NaOH and lipase B (Candida antarctica) solutions were determined gravimetrically and the rate of degradation was explained in terms of the molecular structure of the hydrogels. The morphological studies showed that the pore diameter varied between 20 and 30 mu m and the pore throats (interconnecting windows) diameter was in the range of 4-8 mu m. The described polyHIPE hydrogels were found to have an open cell morphology and interconnected pore architecture, which are important characteristics for scaffold applications. The initial cytotoxicity study performed according to ISO-10993-5 indicated cytocompatibility (97% cell viability) and the subsequent cell seeding and proliferation study exhibited 55-88% cell viability (increased monotonously from GHG-1 to GHG-5), which could be attributed to modulation of the physical and chemical properties of the hydrogels. The described super porous hydrogels are considered as potential candidates for scaffold materials in tissue engineering applications.

Kinetic studies on an algal biofilm reactor for raw sewage water treatment - Gera, Gayatri S.; Yewalkar, Swati N.; Nene, Sanjay; Kulkarni, Bhaskar D.; Kamble, Sanjay P. (Chemical Engineering & Technology, 2016)
A packed-bed algae biofilm reactor was developed using porous and nonporous dual packings. The biofilm was cultivated on reticulated polyurethane foam cubes. The nonporous glass Raschig rings were taken as bed support that helps to remove generated gas from the system. The effect of variables such as column length-to-diameter ratio, catalyst cube dimension, and feed flow rate on the treatment of sewage water was studied. The reaction kinetics indicates that the nutrients uptake rate is dependent on both pore and film diffusion. The kinetics of uptake of nutrients follows a pseudo first-order reaction. From the pseudo reaction rate constant, Thiele modulus and effectiveness factor were calculated and a kinetic model equation for fractional nutrient uptake was developed in terms of operating variables. The model can predict the reaction rate with low deviation. The results obtained may be valuable for large-scale treatment of sewage water.

Laser shielding and thermal ablation characteristics of resorcinol formaldehyde/boronnitride composites for thermal protection systems - Daniel, Alex; Badhe, Yutika; Srikanth, Ivaturi; Gokhale, Suresh; Balasubramanian, Kandasubramanian (Industrial & Engineering Chemistry Research, 2016)
Resorcinol formaldehyde (RF) composites were modified by incorporating different weight ratios of hexagonal boron nitride (h-BN) through a novel in situ polymerization technique. Temperature modulated SAXS was used to understand the changes in polymer network due to h-BN addition. The ablation performance of RF BN composites was evaluated by pulsed laser and oxyacetylene torch tests. Linear ablation resistance under oxyacetylene conditions improved by 18%. Laser ablation resistance increased by 44%. The reasons for improved ablation resistance for RF BN composites were studied using XRD, FTIR, and XPS methods which indicated that h-BN undergoes phase transformation at higher temperatures and also displays typical floral assimilation leading to significant energy consumption. This results in improved ablation resistance. These findings could lead to fabrication of RF BN based thermal protection systems (TPS) having better protection capabilities.

Lewis acid catalyzed selective reactions of donor-acceptor cyclopropanes with 2-naphthols - Kaicharla, Trinadh; Roy, Tony; Thangaraj, Manikandan; Gonnade, Rajesh G.; Biju, Akkattu T. (Angewandte Chemie-International Edition, 2016)
Lewis acid-catalyzed reactions of 2-substituted cyclopropane 1,1-dicarboxylates with 2-naphthols is reported. The reaction exhibits tunable selectivity depending on the nature of Lewis acid employed and proceed as a dearomatization/rearomatization sequence. With Bi(OTf)(3) as the Lewis acid, a highly selective dehydrative [3+2] cyclopentannulation takes place leading to the formation of naphthalene-fused cyclopentanes. Interestingly, engaging Sc(OTf)(3) as the Lewis acid, a Friedel-Crafts-type addition of 2-naphthols to cyclo-propanes takes place, thus affording functionalized 2-naphthols. Both reactions furnished the target products in high regioselectivity and moderate to high yields.
Keywords: annulations; arenes; Lewis acids; reaction mechanisms; small ring systems

Low band gap benzimidazole COF supported Ni3N as highly active OER catalyst - Nandi, Shyamapada; Singh, Santosh Kumar; Mullangi, Dinesh; Illathvalappil, Rajith; George, Leena; Vinod, Chathakudath P.; Kurungot, Sreekumar; Vaidhyanathan, Ramanathan (Advanced Energy Materials, 2016)
Covalent organic frameworks (COFs) have structures and morphologies closely resembling graphenes, whose modular construction permits atomiclevel manipulations. This, combined with their porous structure, makes them excellent catalyst supports. Here, the high electrocatalytic activity of a composite, formed by supporting Ni3N nanoparticles on a benzimidazole COF, for oxygen evolution reaction is shown. The composite oxidizes alkaline water with a near-record low overpotential of 230 mV @ 10 mA cm(-2) (eta(10)). This high activity is attributed to the ability of the COF to confine the Ni3N nanoparticles to size regimes otherwise difficult to obtain and to its low band gap character (1.49 eV) arising from the synergy between the conducting Ni3N nanoparticles and the pi-conjugated COF. The COF itself, as a metalfree self-standing framework, has an oxygen evolution reaction activity with 10 of 400 mV. The periodic structure of the COF makes it serve as a matrix to disperse the catalytically active Ni3N nanoparticles favoring their high accessibility and thereby good charge-transport within the composite. This is evident from the amount of O-2 evolved (230 mmol h(-1) g(-1)), which, to the best of our knowledge, is the highest reported. The work reveals the emergence of COF as supports for electrocatalysts.

Low frequency noise and photo-enhanced field emission from ultrathin PbBi2Se4 nanosheets - Suryawanshi, Sachin R.; Guin, Satya N.; Chatterjee, Arindom; Kashid, Vikas; More, Mahendra A.; Late, Dattatray J.; Biswas, Kanishka (Journal of Materials Chemistry C, 2016)
Atomically thin two-dimensional layered materials have gained wide interest owing to their novel properties and potential for applications in nanoelectronic and optoelectronic devices. Here, we present the spectral analysis and photo-enhanced field emission studies of a layered intergrowth PbBi2Se4 nanosheet emitter, performed at the base pressure of similar to 1 x 10(-8) mbar. The emitter shows a turn-on field value of similar to 4.80 V mu m(-1), corresponding to an emission current density of similar to 1 mu A cm(-2). Interestingly, when the cathode was illuminated with visible light, it exhibited a lower turn-on field of B3.90 V mm(-1), and a maximum emission current density of similar to 893 mu A cm(-2) has been drawn at an applied electric field of similar to 8.40 V mu m(-1). Furthermore, the photo-enhanced emission current showed reproducible, step-like switching behavior in synchronous with ON-OFF switching of the illumination source. The emission current-time plots reveal excellent stability over a duration of similar to 6 h. Low-frequency noise is a significant limitation for the performance of nanoscale electronic devices. The spectral analysis performed on a Fast Fourier Transform (FFT) analyzer revealed that the observed noise is of 1/f(alpha) type, with the value of alpha similar to 0.99. The low frequency noise, photo-enhanced field emission, and reproducible switching behavior characterized with very fast rise and fall times propose the layered PbBi2Se4 nanosheet emitter as a new promising candidate for novel vacuum nano-optoelectronic devices.

Mechanistic insights into pincer-ligated palladium-catalyzed arylation of azoles with aryl Iodides: evidence of a Pd-II-Pd-IV-Pd-II pathway - Khake, Shrikant M.; Jagtap, Rahul A.; Dangat, Yuvraj B.; Gonnade, Rajesh G.; Vanka, Kumar; Punji, Benudhar (Organometallics, 2016)
Pincer-based (R2POCNR′2)PdCl complexes along with CuI cocatalyst catalyze the arylation of azoles with aryl iodides to give the 2-arylated azole products. Herein, we report an extensive mechanistic investigation for the direct arylation of azoles involving a well-defined and highly efficient (iPr2POCNEt2)PdCl (2a) catalyst, which emphasizes a rare PdII–PdIV–PdII redox catalytic pathway. Kinetic studies and deuterium labeling experiments indicate that the C–H bond cleavage on azoles occurs via two distinct routes in a reversible manner. Controlled reactivity of the catalyst 2a underlines the iodo derivative (iPr2POCNEt2)PdI (3a) to be the resting state of the catalyst. The intermediate species (iPr2POCNEt2)Pd-benzothiazolyl (4a) has been isolated and structurally characterized. A determination of reaction rates of compound 4a with electronically different aryl iodides has revealed the kinetic significance of the oxidative addition of the C(sp2)–X electrophile, aryl iodide, to complex 4a. Furthermore, the reactivity behavior of 4a suggests that the arylation of benzothiazole proceeds via an oxidative addition/reductive elimination pathway involving a (iPr2POCNEt2)PdIV(benzothiazolyl)(Ar)I species, which is strongly supported by DFT calculations.

Mechanochemically synthesized covalent organic framework as a proton-conducting solid electrolyte - Shinde, Digambar Balaji; Aiyappa, Harshitha Barike; Bhadra, Mohitosh; Biswal, Bishnu P.; Wadge, Pritish; Kandambeth, Sharath; Garai, Bikash; Kundu, Tanay; Kurungot, Sreekumar; Banerjee, Rahul (Journal of Materials Chemistry A, 2016)
Mechanochemistry has become an increasingly important synthetic tool for a waste-free environment. However, the poor quality of the so-derived materials in terms of their crystallinity and porosity has been their major drawback for any practical applications. In this report, we have for the first time successfully leveraged such characteristics to show that the mechanochemically synthesized bipyridine based covalent organic framework (COF) outperforms its conventional solvothermal counterpart as an efficient solid-state electrolyte in PEM fuel cells. Marking the first such attempt in COFs, a Membrane Electrode Assembly (MEA) fabricated using the mechanochemically synthesized COF was observed to inhibit the fuel crossover and build up a stable Open Circuit Voltage (OCV = 0.93 V at 50 degrees C), thereby establishing itself as an effective solid electrolyte material (with a proton conductivity of 1.4 x 10(-2) S cm(-1)), while the solvothermally synthesized COF proved ineffective under similar conditions.

Metabolic syndrome - a truly psychosomatic disorder? a global hypothesis - Ghike, Shrikant Madhukar (Medical Hypotheses, 2016)
Exact cause of the metabolic syndrome [MS], a global epidemic, is still unclear. Man has same fundamental needs to live as animals but modern man's life-style compels him to acquire certainty of resources for all his needs in a complex social network. Today money has become the sole life essential need. Contrarily none of the animals needs to earn money. Brain is also an organ of the human body with a unique thought process to define logical actions to achieve a person's goals. This way life is a flow of desires followed by logical actions. The person struggles to attain desired goals via the allostatic load but a perceived insurmountable threat can make his flow of life stalled to freeze him. Published data from varied branches of medical science indicates role of hormones in overall homeostasis. Particularly multifaceted role of serotonin is well documented. Adrenalin being the primary mediator of Cod cycle is also well known. From the integration of observations from published data with reference to common human's modern lifestyle, it is hypothesized that a perceived trapped situation in life creates acute chaos of thoughts in brain, which results in acute excess of stress hormones and concurrent depletion of resting hormones, which in turn triggers MS. In global terms, MS indicates an acute imbalance of a few hormones and implies psychosomatic roots of the disorder. This may pave a better way in deciding a personalized holistic protocol with combination of counter regulatory psychoactive medications. (C) 2016 Elsevier Ltd. All rights reserved.

Metal phosphine-sulfonate acetonitrile complex for insertion copolymerization of functional olefins - Chikkali, Samir H.; Gaikwad, Shahaji R. (2016)

Modulation of charge carrier mobility by side-chain engineering of bi(thienylenevinylene)thiophene containing PPE-PPVs - Jadhav, Rupali R.; Camaioni, Nadia; Oppelt, Kerstin; Tinti, Francesca; Gazzano, Massimo; Fattori, Valeria; Wadgaonkar, Prakash P.; Rathgeber, Silke; Hoppe, Harald; Egbe, Daniel A. M. (RSC Advances, 2016)
Four 2-dimensional conjugated poly(p-phenylene-ethynylene)-alt-poly(p-phenylene-vinylene) polymers containing a lateral bi(thienylenevinylene)thiophene unit (BTE-PVs) were synthesised and characterised. The investigated polymers share the same conjugated structure, but differ in the anchoring positions of solubilising linear octyloxy/branched 2-ethylhexyloxy side-chains. UV-vis spectra of the polymers in dilute chloroform solutions and as thin films were studied. X-Ray diffraction patterns as well as the bulk charge transport of polymer films cast from chlorobenzene solutions were also investigated. A dramatic effect of the solubilising side-chains on the charge carrier mobility of BTE-PV films was observed, with bulk hole mobility values ranging between 1.3 x 10(-5) cm(2) V-1 s(-1) and 2.2 x 10(-2) cm(2) V-1 s(-1), which is not ascribable to evident structural variations of the polymer films. It is shown that the combination of linear octyloxy and branched 2-ethylhexyloxy side-chains is favorable for the charge transport properties of BTE-PVs, compared to the incorporation of only linear or only branched side-chains.

Molecular cloning and characterization of O-methyltransferase from mango fruit (mangifera indica cv. alphonso) - Chidley, Hemangi G.; Oak, Pranjali S.; Deshpande, Ashish B.; Pujari, Keshav H.; Giri, Ashok P.; Gupta, Vidya S. (Molecular Biotechnology, 2016)
Flavour of ripe Alphonso mango is invariably dominated by the de novo appearance of lactones and furanones during ripening. Of these, furanones comprising furaneol (4-hydroxy-2,5-dimethyl-3(2H)-furanone) and mesifuran (2,5-dimethyl-4-methoxy-3(2H)-furanone) are of particular importance due to their sweet, fruity caramel-like flavour characters and low odour detection thresholds. We isolated a 1056 bp complete open reading frame of a cDNA encoding S-adenosyl-l-methionine-dependent O-methyltransferase from Alphonso mango. The recombinantly expressed enzyme, MiOMTS showed substrate specificity towards furaneol and protocatechuic aldehyde synthesizing mesifuran and vanillin, respectively, in an in vitro assay reaction. A semi-quantitative PCR analysis showed fruit-specific expression of MiOMTS transcripts. Quantitative real-time PCR displayed ripening-related expression pattern of MiOMTS in both pulp and skin of Alphonso mango. Also, early and significantly enhanced accumulation of its transcripts was detected in pulp and skin of ethylene-treated fruits. Ripening-related and fruit-specific expression profile of MiOMTS and substrate specificity towards furaneol is a suggestive of its involvement in the synthesis of mesifuran in Alphonso mango. Moreover, a significant trigger in the expression of MiOMTS transcripts in ethylene-treated fruits point towards the transcriptional regulation of mesifuran biosynthesis by ethylene.
Keywords: Ethylene; expression; Flavour; Mango; Mesifuran; Ripening

Molecular cloning and in silico studies of physiologically significant trehalase from drosophila melanogaster - Shukla, Ekta; Thorat, Leena; Bhavnani, Varsha; Bendre, Ameya D.; Pal, J. K.; Nath, B. B.; Gaikwad, Sushama M. (International Journal of Biological Macromolecules, 2016)
Trehalase, a physiologically important glycosidase is known for its crucial role in insect glycometabolism and stress recovery. The present study describes the molecular cloning of a gene fragment, encoding the catalytically active trehalase from Drosophila melanogaster (DmTre) and its heterologous expression in Escherichia coli. The 1275 bp gene was overexpressed in two different vectors viz., pET28a and pCOLD TF and investigated for variable soluble expression, purification and activity of the recombinant enzyme with optimum pH and temperature of enzyme as 6 and 55 degrees C, respectively. The sequence was characterized in silico by subjecting it to homology search, multiple sequence alignment and phylogenetic tree construction revealing its identity to other trehalases which belong to glycoside hydrolase family 37. The deduced amino acid sequence and modeled 3D structure of DmTre possessed all features of trehalase superfamily, including signature motifs and catalytic domain. The active site pocket of recombinant DmTre was compared with the crystal structure of E. coli trehalase identifying Glu424 and Asp226 as the putative catalytic residues. Additionally, enzyme-substrate docking suggests possible involvement of other residues in the catalysis along with Asp226. The present study holds significance in understanding the structural aspects of Drosophila trehalase in spite of unavailabilty of eukaryotic trehalase crystal structure. (C) 2016 Elsevier B.V. All rights reserved.

Molecular interaction of selected phytochemicals under the charged environment of Plasmodium falciparum chloroquine resistance transporter (PfCRT) model - Patel, Saumya K.; Khedkar, Vijay M.; Jha, Prakash C.; Jasrai, Yogesh T.; Pandya, Himanshu A.; George, Linz-Buoy; Highland, Hyacinth N.; Skelton, Adam A. (Journal of Biomolecular Structure & Dynamics, 2016)
Phytochemicals of Catharanthus roseus Linn. and Tylophora indica have been known for their inhibition of malarial parasite, Plasmodium falciparum in cell culture. Resistance to chloroquine (CQ), a widely used antimalarial drug, is due to the CQ resistance transporter (CRT) system. The present study deals with computational modeling of Plasmodium falciparum chloroquine resistance transporter (PfCRT) protein and development of charged environment to mimic a condition of resistance. The model of PfCRT was developed using Protein homology/analogy engine (PHYRE ver 0.2) and was validated based on the results obtained using PSI-PRED. Subsequently, molecular interactions of selected phytochemicals extracted from C. roseus Linn. and T. indica were studied using multiple-iterated genetic algorithm-based docking protocol in order to investigate the translocation of these legends across the PfCRT protein. Further, molecular dynamics studies exhibiting interaction energy estimates of these compounds within the active site of the protein showed that compounds are more selective toward PfCRT. Clusters of conformations with the free energy of binding were estimated which clearly demonstrated the potential channel and by this means the translocation across the PfCRT is anticipated.
Keywords: homology modeling; molecular dynamics; Plasmodium falciparum chloroquine; resistance transporter model

Molecular-Pillar-supported functionalized reduced graphene-oxide for energy efficient lubrication - Gupta, Bhavana; Kumar, Niranjan; Panda, Kalpataru; Melvin, Ambrose A.; Joshi, Shailesh; Dash, Sitaram (Advanced Materials Interfaces, 2016)
Molecular-pillar-supported basal plane of reduced graphene oxide (rGO) is fabricated by polymerizing polyaniline (PANI). In the presence of poly(ethylene glycol) (PEG200), the gamma-radiolysis is used for modifying the functionalization and improving the structural symmetry of PANI and PEG grafted rGO (PANI-PEG-g-rGO). The PANI is covalently and noncovalently grafted onto the surface of the graphene sheets. Carboxyl groups of rGO are linked to the nitrogen atoms in the PANI backbone and an accompanying noncovalent interaction between alkyl chains of grafted PANI and hydrooxylated rGO is formed. Raman and Fourier transform infra-red results confirm existence of stretching vibrations of benzenoid and quinonoid rings in PANI-PEG-g-rGO-functionalized composite, indicating grafting between PANI and rGO through pi-pi interaction. Furthermore, PEG-functionalization through hydrogen bonding with rGO is confirmed when hydroxyl group from the rGO combines with oxygen of PEG. X-ray photoelectron spectroscopy reveals significant increase in carbon, while loading PANI network with rGO followed by gamma-irradiation. Antifriction and antiwear properties of graphene nanocomposite are considerably enhanced to 68.4% and 48%, respectively, as compared to pristine PEG. The unique lubrication properties are explained by PEG functionalized molecular PANI-pillar structure across basal plane of rGO.

Naphthoquinone based chemosensor 2-(2 `-aminoethylpyridine)-3-chloro-1,4-naphthoquinone: detection of metal ions, X-ray -crystal structures and DFT studies - Patil, Amit; Ware, Anuja P.; Bhand, Sujit; Chakravarty, Debamitra K.; Gonnade, Rajesh G.; Pingale, Subhash S.; Salunke-Gawali, Sunita (Journal of Molecular Structure, 2016)
Naphthoquinone based Chemosensor 2; 2-(2'-aminoethylpyridine)-3-chloro-1,4-napthoquinone have been synthesized and characterized. Chemosensor 2 crystallizes in the orthorhombic space group Pbcn and shows extensive intramolecular as well as intermolecular hydrogen bonding interactions. Each molecule of Chemosensor 2 showed interaction with five neighboring molecules via C-H center dot center dot center dot N, N-H center dot center dot center dot N, C-H center dot center dot center dot Cl and C-H center dot center dot center dot O interactions. Slipped pi-pi stacking interaction was observed in adjacent quinonoid and benzenoid rings. Chemosensor abilities of Chemosensor 2 ligand have been evaluated with metal ions viz. Cu2+, Ni2+, Zn2+, Co2+, Fe3+, Mn2+, Cr3+, Hg2+, La3+ and Cd2+ in methanol, methanol-water mixture and in presence of mild base triethylamine. Stoichiometry of Chemosensor 2 with metal ions such as Cu2+, Ni2+, Zn2+ and Co2+ ions was determined by Jobs method in methanol and were found as 1:1 for Cu2+ and 2:1 for Ni2+, Zn2+ Co2+. The variation in the metal ligand ratio is observed in aqueous media for Cu2+. Chemosensor 2 can be used selectively for naked eye detection of Cu2+ ions. The association constant obtained in methanol shows the trend Cu2+>Ni2+>Co2+. Cu2+ and two (Ni-1 and Ni-2) Ni2+ complexes were synthesized. Ni-2 complex showed coordination of Chemosensor 2 ligands was through pyridine nitrogen's only. The Chemosensor 2 and its deprotonated forms in methanol, water and triethylamine were also studied by TD-DFT studies. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Aminonaphthoquinone; Chemosensor; hydrogen bonding; Naphthoquinone; pi-pi stacking; TD-DFT

Next-generation ammonia pretreatment enhances cellulosic biofuel production - Sousa, Leonardo da Costa; Jin, Mingjie; Chundawat, Shishir P. S.; Bokade, Vijay V.; Tang, Xiaoyu; Azarpira, Ali; Lu, Fachuang; Avci, Utku; Humpula, James; Uppugundla, Nirmal; Gunawan, Christa; Pattathil, Sivakumar; et al. (Energy & Environmental Science, 2016)
A new liquid ammonia pretreatment methodology called Extractive Ammonia (EA) was developed to simultaneously convert native crystalline cellulose I-beta (CI) to a highly digestible cellulose IIII (CIII) allomorph and selectively extract up to B45% of the lignin from lignocellulosic biomass with near-quantitative retention of all polysaccharides. EA pretreated corn stover yielded a higher fermentable sugar yield compared to the older Ammonia Fiber Expansion (AFEX) process while using 60% lower enzyme loading. The EA process preserves extracted lignin functionalities, offering the potential to co-produce lignin-derived fuels and chemicals in the biorefinery. The single-stage EA fractionation process achieves high biofuel yields (18.2 kg ethanol per 100 kg untreated corn stover, dry weight basis), comparable to those achieved using ionic liquid pretreatments. The EA process achieves these ethanol yields at industrially-relevant conditions using low enzyme loading (7.5 mg protein per g glucan) and high solids loading (8% glucan, w/v).

N-heterocyclic-carbene-catalyzed regioselective oxidative ring-opening of epoxides with aromatic aldehydes: a facile entry to alpha-acyloxyketones - Reddi, Rambabu N.; Gontala, Arjun; Prasad, Pragati K.; Sudalai, Arumugam (Asian Journal of Organic Chemistry, 2016)
A high-yielding synthesis of -acyloxyketones using a N-heterocyclic-carbene (NHC)-catalyzed, oxidative ring-opening of epoxides with aromatic aldehydes is described. This regioselective, oxidative process utilizes a N-bromosuccinimide (NBS)/DMSO combination as the oxidant system and Et3N as the base under mild reaction conditions.
Keywords: aldehydes; epoxides; halogen oxidants; N-heterocyclic carbenes; oxygen

Notch1-MAPK signaling axis regulates CD133+ cancer stem cell-mediated melanoma growth and angiogenesis - Kumar, Dhiraj; Kumar, Santosh; Gorain, Mahadeo; Tomar, Deepti; Patil, Harshal S.; Radharani, Nalukurthi N. V.; Kumar, Totakura V. S.; Patil, Tushar V.; Thulasiram, Hirekodathakallu V.; Kundu, Gopal C. (Journal of Investigative Dermatology, 2016)
Functional characterization and understanding of the intricate signaling mechanisms in stem-like cells is crucial for the development of effective therapies in melanoma. We have studied whether melanoma cells are phenotypically distinct and hierarchically organized according to their tumorigenic nature. We report that melanoma-specific CD133(+) cancer stem cells exhibit increased tumor-initiating potential, tumor-endothelial cell interaction, and lung metastasis. These cells are able to transdifferentiate into an endothelial-like phenotype when cultured under endothelial differentiation-promoting conditions. Mechanistically, Notch1 upregulates mitogen-activated protein kinase activation through CD133, which ultimately controls vascular endothelial growth factor and matrix metalloproteinase expression in CD133(+) stem cells leading to melanoma growth, angiogenesis, and lung metastasis. Blockade or genetic ablation of Notch1 and mitogen-activated protein kinase pathways abolishes melanoma cell migration and angiogenesis. Chromatin immunoprecipitation and reporter assays revealed that Notch1 intracellular domain regulates CD133 expression at the transcriptional level. Andrographolide inhibits Notch1 intracellular domain expression, Notch1 intracellular domaindependent CD133-mediated mitogen-activated protein kinase and activator protein-1 activation, and epithelial to mesenchymal-specific gene expression, ultimately attenuating melanoma growth and lung metastasis. Human malignant melanoma specimen analyses revealed a strong correlation between Notch1 intracellular domain, CD133, and p-p38 mitogen-activated protein kinase expression and malignant melanoma progression. Thus, targeting Notch1 and its regulated signaling network may have potential therapeutic implications for the management of cancer stem cell-mediated melanoma progression.

Omniphilic polymeric sponges by ice templating - Chatterjee, Soumyajyoti; Sen Gupta, Sayam; Kumaraswamy, Guruswamy (Chemistry of Materials, 2016)
Sponges that absorb a large quantity of solvent relative to their weight, independent of the solvent polarity, represent useful universal absorbents for laboratory and industrial spills. We report the preparation of macroporous polymer sponges by ice templating of polyethylenimine aqueous solutions and their cross-linking in the frozen state. The as-prepared monolith is hydrophilic and absorbs over 30 fold its weight in water. Modification of this sponge using valeroyl chloride renders it omniphilic; viz., a modified sponge absorbs over 10-fold its dry weight of either water or hexane. Modification using palmitoyl chloride that has a longer chain length results in the preparation of a hydrophobic sponge with a water contact angle around 130, which retains its oleophilicity underwater. The solvent absorbed in these sponges can be simply squeezed out, and the sponges are stable to several hundred cycles of compression. The large pore sizes of these sponges allow rapid absorption of even high viscosity solvents such as pump oil. Finally, we demonstrate that these sponges are also able to separate apolar oils that are emulsified in water using surfactants. These high porosity sponges with controllable solvophilicity represent inexpensive, high performance universal absorbents for general solvent spills.

Palladium supported on fluorite structured redox CeZrO4-δ for heterogeneous suzuki coupling in water: a green protocol - Burange, Anand S.; Shukla, Rakesh; Tyagi, Avesh Kumar; Gopinath, Chinnakonda S. (Chemistry Select, 2016)
Pd on redox CeZrO4-δ catalysts was prepared, characterized and their activity was evaluated for Suzuki coupling reaction in water under reflux condition. Fresh and reduced form of 5 % Pd (R−Pd5) on CeZrO4-δ catalyst exhibited 100 % conversion in 2.5 and 1 h, respectively. R−Pd5 shows significant activity for wide range of substrate compatibility and for less reactive aryl bromides too. The mechanistic investigations proved the important role of redox CeZrO4-δ support on the catalytic activity. It was observed that the presence of oxygen vacancy along with Ce3+ enhances the activity. 1 wt % Pd photodeposited on pre-reduced CeZrO4-δ support requires a mere 20 min. for 100 % conversion of Suzuki coupling. Effect of metal dispersion and particle size on catalytic activity is also discussed. High Pd dispersion with small particle size (4±1 nm), particle size preservation after reaction, strong metal-support interaction and no leaching fully suggest the heterogeneous mechanism is operative for Suzuki coupling on 1 wt % Pd photodeposited on reduced CeZrO4-δ support. Present work hints the possibility of achieving high conversion for Suzuki reaction with very small amount of Pd through better dispersion by taking advantage of redox support and in water.

Parasitism by Chelonus blackburni (Hymenoptera) affects food consumption and development of Helicoverpa armigera (Lepidoptera) and cellular architecture of the midgut - Sanap, Yogita; Dawkar, Vishal V.; Giri, Ashok P.; Sen, Avalokiteswar; Pandit, Radhakrishna S. (Journal of Asia-Pacific Entomology, 2016)
Biological control agents are vital components of an integrated pest management strategy, and this is frequently referred to as natural control. Natural enemies of insect pests include predators, parasitoids, and pathogens. Among them, a parasitoid, Chelonus blackburni (Cameron), was found to be the best biological control agent for the polyphagous pest, Helicoverpa armigera (Hubner). C. blackburni alters the feeding performance of H. annigera larvae upon parasitism and as a result severely affects growth and development. Moreover, it shortens the feeding period of H. armigera and increases mortality. Furthermore, total hemocyte count (THC) was significantly decreased in parasitized larvae than control. Parasitized H. armigera had 26% less number of blood cells compared to healthy larvae. Histological studies showed that the structure of midgut of H. annigera is drastically affected by C. blackburni leading to reduced food consumption, which ultimately led to larval death. The present study provides an insight to changes involved in H. annigera due to parasitism by C blackburni, a parasite that could be used as an effective biocontrol agent to manage H. armigera. (C) 2015 Korean Society of Applied Entomology, Taiwan Entomological Society and Malaysian Plant Protection Society. Published by Elsevier B.V. All rights reserved.

Pb2+-N bonding chemistry: recycling of polyaniline-pb nanocrystals waste for generating high-performance supercapacitor electrodes - Jha, Plawan Kumar; Singh, Santosh K.; Gatla, Suresh; Mathon, Olivier; Kurungot, Sreekumar; Ballav, Nirmalya (Journal of Physical Chemistry C, 2016)
Understanding of Pb-N bonding chemistry is not only fundamentally important in the view of relativistic inert-pair effect but also is important for therapeutic as well as environmental applications. In the present study, an unusual reactivity of N-containing pi-conjugated polyaniline emeraldine base (EB) toward aqueous Pb2+ ions has been identified. In the course of sequestering Pb2+ ions by EB, cuboid-shaped nanocrystals were isolated. Synchrotron-based X-ray absorption near-edge structure and extended X-ray absorption fine structure techniques were employed to understand Pb-N bonding chemistry in EB-Pb nanocrystals. The adopted methodology of slow exposure of HCl vapor to EB-Pb nanomaterial facilitated the isolation of polyaniline emeraldine-salt (ES) with unique morphological patterns, porosity and electrical conductivity. The electrochemical device based on recycled ES showed high-capacitance value (similar to 606 F/g @1 A/g and similar to 663 F/g @10 mV/s), high-energy density (similar to 14.8 Wh/kg at power density of similar to 663 W/kg) and excellent-cycling stability (only similar to 15% degradation after 1100 continued cycles at current density of 5 A/g). Notably, ES materials prepared directly from EB and upon exposing HNO3 vapor exhibited greatly inferior device performance.

Pd-catalyzed reductive cleavage of N-N bond in dibenzyl-1-alkylhydrazine-1,2-dicarboxylates with PMHS: application to a formal enantioselective synthesis of (R)-sitagliptin - Dey, Soumen; Gadakh, Sunita K.; Ahuja, Brij Bhushan; Kamble, Sanjay P.; Sudalai, Arumugam (Tetrahedron Letters, 2016)
An environmentally benign approach involving Pd-catalyzed reductive N-N bond cleavage in dibenzyl-1-alkylhydrazine-1,2-dicarboxylates leading to the synthesis of N-(tert-butoxy)carbamates under very mild conditions has been described. PMHS serves as an inexpensive source of hydride in MeOH/deionized H2O medium. This protocol has been successfully applied in the formal synthesis of (R)-sitagliptin, an anti-diabetic drug. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: anti-Diabetic; Environmentally benign; Hydrazine; PMHS; Reductive cleavage

Pd(II)-catalyzed intramolecular tandem olefin amidation/C-H activation protocol for the syntheses of the protoberberine class of natural products - Garad, Dnyaneshwar N.; Mhaske, Santosh B. (Organic Letters, 2016)
A Pd(II)-catalyzed intramolecular tandem olefin amidation/C-H activation protocol has been developed for the synthesis of an 8-oxoprotoberberine core. It was successfully applied for the syntheses of (+/-)-8-oxocanadine, (+/-)-8-oxotetrahydropalmitine, and (+/-)-8-oxostylopine, which can be easily converted to the respective protoberberine natural products. The short synthetic route demonstrated would be useful for the synthesis of a large number of natural products and their analogues featuring a protoberberine scaffold.

Peeping into genomic architecture by re-sequencing of Ochrobactrum intermedium M86 strain during laboratory adapted conditions - Gohil, K. N.; Neurgaonkar, P. S.; Paranjpe, A.; Dastager, S. G.; Dharne, M. S. (Genomics Data, 2016)
Advances in de novo sequencing technologies allow us to track deeper insights into microbial genomes for restructuring events during the course of their evolution inside and outside the host. Bacterial species belonging to Ochrobactrum genus are being reported as emerging, and opportunistic pathogens in this technology driven era probably due to insertion and deletion of genes. The Ochrobactrum intermedium M86 was isolated in 2005 from a case of non-ulcer dyspeptic human stomach followed by its first draft genome sequence in 2009. Here we report re-sequencing of O. intermedium M86 laboratory adapted strain in terms of gain and loss of genes. We also attempted for finer scale genome sequence with 10 times more genome coverage than earlier one followed by comparative evaluation on Ion PGM and Illumina MiSeq. Despite their similarities at genomic level, lab-adapted strain mainly lacked genes encoding for transposase protein, insertion elements family, phage tail-proteins that were not detected in original strain on both chromosomes. Interestingly, a 5 kb indel was detected in chromosome 2 that was absent in original strain mapped with phage integrase gene of Rhizobium spp. and may be acquired and integrated through horizontal gene transfer indicating the gene loss and gene gain phenomenon in this genus. Majority of indel fragments did not match with known genes indicating more bioinformatic dissection of this fragment. Additionally we report genes related to antibiotic resistance, heavy metal tolerance in earlier and re-sequenced strain. Though SNPs detected, there did not span urease and flagellar genes. We also conclude that third generation sequencing technologies might be useful for understanding genomic architecture and re-arrangement of genes in the genome due to their ability of larger coverage that can be used to trace evolutionary aspects in microbial system.

Photocatalytic degradation of methylene blue on Sn-doped titania nanoparticles synthesized by solution combustion route - Bhange, P. D.; Awate, S. V.; Gholap, Ramkrishna S.; Gokavi, G. S.; Bhange, Deu S. (Materials Research Bulletin, 2016)
Series of tin-doped titania nanoparticles with varying tin content in the range 0-20 mol% have been prepared by solution combustion synthesis route using urea as a fuel. The structure, surface morphology and optical activity of Sn-doped TiO2 nanoparticles were investigated by various analytical techniques such as powder XRD, SEM, TEM, UV-vis and N-2 adsorption study. The crystalline structures of the various phases were studied by rietveld refinement of the XRD data. The photocatalytic performance of Sn-doped titania nanoparticles were tested for degradation of MB under UV and visible light irradiation. The results reveal that the photocatalytic activity increases with increase in tin content which may be due to decrease in crystallite size with increase in surface area. The doping of Sn into TiO2 lattice hinders the recombination of electrons and holes thus enhance the quantum efficiency of photocatalytic reaction. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Catalytic properties; composites; Nanostructures; X-ray diffraction

Photocatalytic H-2 evolution from water-methanol mixtures on InGaO3(ZnO)(m) with an anisotropic layered structure modified with CuO and NiO cocatalysts - Narendranath, Soumya B.; Thekkeparambil, Saranya V.; George, Leena; Thundiyil, Shibin; Devi, R. Nandini (Journal of Molecular Catalysis A-Chemical, 2016)
InGaO3(ZnO)(m) series of oxides is found to be active for photocatalytic H-2 evolution from water-methanol mixtures. The structure of this series is highly anisotropic with InO6 octahedral layers sandwiching Ga/ZnOn polyhedra. The structural anisotropy in which the conducting layer is spatially separated from the charge generation sites may help in suppressing charge recombination and consequently enhance catalytic activity. The band gaps of the series obtained from absorption spectra are above 3.6 eV and hence they are not active under visible light irradiation. H-2 evolution is considerably enhanced under UV light on employing NiO as cocatalyst due to facile electron transfer from InGaO3(ZnO)(m). to NiO. However, when CuO is used as cocatalyst, visible light activity could be brought out. Due to the very low band gap of CuO, it can act as a sensitizer absorbing in visible light. The band positions become conducive for H-2 evolution due to band alignments consequent to electron accumulation in CuO conduction band. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: InGaO3(ZnO)(m); photocatalytic water splitting; visible light; XPS; XRD

Photochromic metal-organic frameworks for inkless and erasable printing - Garai, Bikash; Mallick, Arijit; Banerjee, Rahul (Chemical Science, 2016)
Inkless and erasable printing is the key solution towards a more sustainable paper industry, in terms of reducing paper wastages and the associated environmental hazards from waste paper processing. However, only a few cases have been reported in the literature where inkless printing has been tested in some practical systems. In an attempt to address this solution, we used photochromic metal-organic frameworks (MOFs) and tested their capability as inkless and erasable printing media. The printing was performed using sunlight as the light source on MOF-coated papers. The resulting printing had good resolution and stability, and was capable of being read both by the human eye and smart electronic devices; furthermore, the paper could be reused for several cycles without any significant loss in intensity. Interestingly, different coloured printing with a similar efficiency was achieved by varying the structure of the MOF.

PolyHIPE derived freestanding 3D carbon foam for cobalt hydroxide nanorods based highperformance supercapacitor - Patil, Umakant M.; Ghorpade, Ravindra V.; Nam, Min Sik; Nalawade, Archana C.; Lee, Sangrae; Han, Haksoo; Jun, Seong Chan (Scientific Reports, 2016)
The current paper describes enhanced electrochemical capacitive performance of chemically grown Cobalt hydroxide (Co(OH)(2)) nanorods (NRs) decorated porous three dimensional graphitic carbon foam (Co(OH)(2)/3D GCF) as a supercapacitor electrode. Freestanding 3D porous GCF is prepared by carbonizing, high internal phase emulsion (HIPE) polymerized styrene and divinylbenzene. The PolyHIPE was sulfonated and carbonized at temperature up to 850 degrees C to obtain graphitic 3D carbon foam with high surface area (389 m(2) g(-1)) having open voids (14 mu m) interconnected by windows (4 mu m) in monolithic form. Moreover, entangled Co(OH)(2) NRs are anchored on 3D GCF electrodes by using a facile chemical bath deposition (CBD) method. The wide porous structure with high specific surface area (520 m(2) g(-1)) access offered by the interconnected 3D GCF along with Co(OH)(2) NRs morphology, displays ultrahigh specific capacitance, specific energy and power. The Co(OH)(2)/3D GCF electrode exhibits maximum specific capacitance about similar to 1235 F g(-1) at similar to 1 Ag-1 charge-discharge current density, in 1 M aqueous KOH solution. These results endorse potential applicability of Co(OH)(2)/3D GCF electrode in supercapacitors and signifies that, the porous GCF is a proficient 3D freestanding framework for loading pseudocapacitive nanostructured materials.

Porous thin films towards bridging the material gap in heterogeneous catalysis - Dubey, Anjani; Kolekar, Sadhu K.; Gnanakumar, Edwin S.; Roy, Kanak; Vinod, C. P.; Gopinath, Chinnakonda S. (Catalysis, Structure & Reactivity, 2016)
An attempt has been made to bridge the material gap, existing between ideal single crystals and real-world powder nanocatalyst employed in surface science and heterogeneous catalysis, respectively. Simple wet chemical method (sol–gel and spin-coating deposition) has been applied to make continuous Ce1 − xZrxO2 (x = 0–1) (CZ) thin films with uniform thickness (~40 nm) and smooth surface characteristics. Uniform thickness and surface smoothness of the films over a large area was supported by a variety of measurements. Molecular beam (MB) studies of O2 adsorption on CZ surfaces reveals the oxygen storage capacity (OSC), and sticking coefficient increases from 400 to 800 K. Porous nature of Ce-rich CZ compositions enhances O2 adsorption and OSC, predominantly due to O-diffusion and redox nature, even at 400 K. A good correlation exists between MB measurements made on CZ films for oxygen adsorption, and OSC, and ambient pressure CO oxidation on powder form of CZ; this demonstrates the large potential to bridge the material gap. CZ was particularly chosen as a model system for the present studies, since it has been well-studied and a correlation between surface science properties made on thin films and catalysis on powder CZ materials could be a litmus test. Ambient catalysis on ceria-zirconia nanocatalyst correlates well with surface properties measured through molecular beam on thinfilm and close the material gap.

Potential dual role of eugenol in inhibiting advanced glycation end products in diabetes: proteomic and mechanistic insights - Singh, Priyanka; Jayaramaiah, Ramesha H.; Agawane, Sachin B.; Vannuruswamy, Garikapati; Korwar, Arvind M.; Anand, Atul; Dhaygude, Vitthal S.; Shaikh, Mahemud L.; Joshi, Rakesh S.; Boppana, Ramanamurthy; Kulkarni, Mahesh J.; Thulasiram, Hirekodathakallu V.; et al. (Scientific Reports, 2016)
Medicinally important genus Ocimum harbors a vast pool of chemically diverse metabolites. Current study aims at identifying anti-diabetic candidate compounds from Ocimum species. Major metabolites in O. kilimandscharicum, O. tenuiflorum, O. gratissimum were purified, characterized and evaluated for anti-glycation activity. In vitro inhibition of advanced glycation end products (AGEs) by eugenol was found to be highest. Preliminary biophysical analysis and blind docking studies to understand eugenol-albumin interaction indicated eugenol to possess strong binding affinity for surface exposed lysines. However, binding of eugenol to bovine serum albumin (BSA) did not result in significant change in secondary structure of protein. In vivo diabetic mice model studies with eugenol showed reduction in blood glucose levels by 38% likely due to inhibition of alpha-glucosidase while insulin and glycated hemoglobin levels remain unchanged. Western blotting using anti-AGE antibody and mass spectrometry detected notably fewer AGE modified peptides upon eugenol treatment both in vivo and in vitro. Histopathological examination revealed comparatively lesser lesions in eugenol-treated mice. Thus, we propose eugenol has dual mode of action in combating diabetes; it lowers blood glucose by inhibiting a-glucosidase and prevents AGE formation by binding to epsilon-amine group on lysine, protecting it from glycation, offering potential use in diabetic management.

Prediction of reactivity ratios in free radical copolymerization from monomer resonance-polarity (Q-e) parameters: genetic programming-based models - Shrinivas, K.; Kulkarni, Rahul P.; Shaikh, Saif; Ghorpade, Ravindra V.; Vyas, Renu; Tambe, Sanjeev S.; Ponrathnam, S.; Kulkarni, Bhaskar D. (International Journal of Chemical Reactor Engineering, 2016)
The principal deficiency of the widely utilized Alfrey-Price (AP) scheme for computing reactivity ratios in the widely used free radical copolymerization is that it ignores important factors, such as the steric effects. This often leads to inaccurate reactivity ratio predictions by AP model. Accordingly, in this study, exclusively data-driven, Q-e parameter-based new models have been developed for the reactivity ratio prediction in free radical copolymerization. In the model development, a novel artificial intelligence formalism known as ``genetic programming (GP)'' that performs symbolic regression has been employed. The GP-based models possess a different functional form than AP model. Further, parameters of GP-based models were fine-tuned using Levenberg-Marquardt (LM) nonlinear regression method. A comparison of AP, GP and GP-LM as well as artificial neural network (ANN)-based models indicates that GP and GP-LM models exhibit superior reactivity ratio prediction accuracy and generalization performance (with correlation coefficient magnitudes close to or greater than 0.9) when compared with AP and ANN models. The GPbased reactivity ratio prediction models developed here due to their higher accuracy and generalization capability have the potential of replacing the widely used AP models.
Keywords: Alfrey-Price scheme; free radical copolymerization; genetic programming; reactivity ratio; symbolic regression

Production of bikaverin by a Fusarium fujikuroi mutant in submerged cultures - Lale, Geetanjali; Gadre, R. V. (AMB Express, 2016)
A variety of mutants having different colony characteristics, morphology and soluble pigmentation were generated from Fusarium fujikuroi by exposure to UV radiation. Mutants were selected that formed dry, compact, small colonies with reddish-violet pigment on regeneration agar plates. The production of bikaverin by Mut-4 was examined in shake flasks in media with different nitrogen and carbon sources. The optimal C: N ratio for the maximal bikaverin production by Mut-4 was 150: 1. It produced still higher bikaverin (6.3 g l(-1)) in a medium containing defatted cottonseed meal as nitrogen source, in combination with glucose. Bikaverin produced was extracted, purified and characterized by UV-visible and NMR spectroscopy. Bikaverin production in the present investigation was substantially higher than that reported by earlier investigators in submerged and solid-state fermentations.
Keywords: Bikaverin; Fusarium fujikuroi; Gibberella fujikuroi; Pigment production; Submerged cultures

Proteomic insight reveals elevated levels of albumin in circulating immunecomplexes in diabetic plasma - Bhat, Shweta; Jagadeeshaprasad, Mashanipalya G.; Patil, Yugendra R.; Shaikh, Mahemud L.; Regin, Bhaskaran S.; Mohan, Viswanathan; Giri, Ashok P.; Balasubramanyam, Muthuswamy; Boppana, Ramanamurthy; Kulkarni, Mahesh J. (Molecular & Cellular Proteomics, 2016)
A Hyperglycemic condition in diabetes promotes formation of advanced glycation end products, which are known to elicit immune response and form complexes with immunoglobulins called circulating immune complexes. To investigate the involvement of advanced glycation end product (AGE)-modified proteins in the elicitation of an immune response, circulating immune complexes were isolated and proteins associated were identified and characterized. Label-free-based mass spectrometric analysis of circulating immune complexes in clinical plasma of prediabetic, newly diagnosed diabetes, and diabetic microalbuminurea revealed elevated levels of serum albumin in the circulating immune complexes, which were also observed to be AGE modified. Further, to examine the role of glycation, circulating immune complexeswere analyzed in the streptozotocin-induced diabetic mice treated with or without aminoguanidine, a prototype glycation inhibitor. Mass spectrometric analysis of circulating immune complexes showed elevated levels of serum albumin in plasma from diabetic mice over that of control animals. Aminoguanidine-treated diabetic mice displayed decreased AGE modification of plasma albumin, accompanied by a reduced level of albumin in the circulating immune complexes. In addition, elevated levels of proinflammatory cytokines such as IL-1b, IL-2, and TNF-alpha were observed in diabetes, which were reduced with aminoguanidine treatment, suggesting the involvement of glycation in the immune response.

Proton-coupled electron transfer in a hydrogen-bonded charge transfer complex - Verma, Sandeep; Aute, Sunil; Das, Amitava; Ghosh, Hirendra N. (Journal of Physical Chemistry B, 2016)
A proton-coupled electron transfer (PCET) reaction in a hydrogen bonded charge-transfer (CT) complex of 4-([2,2'-bipyridin]-4-yl)phenol (bpy-phenol) with a F- ion has been investigated by ultrafast time-resolved transient absorption spectroscopy. The phenolic receptor molecule, bpy-phenol, binds to the F- ion through a hydrogen bond and senses the F- ion-via the Stokes-shifted CT band. Upon photoexcitation, CT from the phenol residue to the bpy residue promotes proton transfer from the phenol radical cation (ArOH center dot+) to the fluoride ion at ultrafast time scales of <150 fs (instrument response function limited) and 3 ps, separately. The fast and slow proton-transfer times are linked to two different types of hydrogen-bonding networks between the phenol residue and fluoride ion. Crystalline water in the fluoride salt hydrates mediates the proton-transfer reaction. This work demonstrates the participation of a hydrogen-bonded water bridge within a PCET reaction in a water restricted environment.

Pt- and TCO-free flexible cathode for DSSC from highly conducting and flexible PEDOT paper prepared via in situ interfacial polymerization - Anothumakkool, Bihag; Agrawal, Ishita; Bhange, Siddheshwar N.; Soni, Roby; Game, Onkar S.; Ogale, Satishchandra B.; Kurungot, Sreekumar (ACS Applied Materials & Interfaces, 2016)
Here, we report the preparation of a flexible, free-standing, Pt- and TCO-free counter electrode in dye-sensitized solar cell (DSSC)-derived from polyethylenedioxythiophene (PEDOT)-impregnated cellulose paper. The synthetic strategy of making the thin flexible PEDOT paper is simple and scalable, which can be achieved via in situ polymerization all through a roll coating technique. The very low sheet resistance (4 Omega/square) obtained from a film of 40 mu m thick PEDOT paper (PEDOT-p-5) is found to be superior to the conventional fluorine-doped tin oxide (FTO) substrate. The high conductivity (357 S/cm) displayed by PEDOT-p-5 is observed to be stable under ambient conditions as well as flexible and bending conditions. With all of these features in place, we could develop an efficient Pt- and TCO-free flexible counter electrode from PEDOT-p-5 for DSSC applications. The catalytic activity toward the tri-iodide reduction of the flexible electrode is analyzed by adopting various electrochemical methodologies. PEDOT-p-5 is found to display higher exchange current density (7.12 mA/cm(2)) and low charge transfer resistance (4.6 Omega) compared to the benchmark Pt-coated FTO glass (2.40 mA/cm(2) and 9.4 Omega, respectively). Further, a DSSC fabricated using PEDOT-p-5 as the counter electrode displays a comparable efficiency of 6.1% relative to 6.9% delivered by a system based on Pt/FTO as the counter electrode.
Keywords: counter electrode; dye-sensitized solar cell; flexible and thin devices; impedance analysis; interfacial polymerization; polyethylenedioxythiophene

Purification and characterization of an extracellular beta-xylosidase from Pseudozyma hubeiensis NCIM 3574 (PhXyl), an unexplored yeast - Mhetras, Nutan; Liddell, Susan; Gokhale, Digambar (AMB Express, 2016)
This paper reports on the production of beta-xylosidase from an unexplored yeast, Pseudozyma hubeinsis. The expression of this enzyme could be induced by beech wood xylan when the yeast was grown at 27 degrees C. The enzyme was purified to homogeneity as a glycoprotein with 23 % glycosylation. The purification protocol involved ammonium sulphate precipitation, QAE-Sephadex A50 ion exchange chromatography and sephacryl-200 column chromatography which resulted in 8.3-fold purification with 53.12 % final recovery. The purified enzyme showed prominent single band on SDS-PAGE. It is a monomeric protein of 110 kDa molecular weight confirmed by SDS-PAGE followed by MALDI-TOF mass spectrometry (112.3 kDa). The enzyme was optimally active at 60 degrees C and pH 4.5 and stable at pH range (4-9) and at 50 degrees C for 4 h. Chemical modification studies revealed that active site of the purified enzyme comprised of carboxyl, tyrosine and tryptophan residues. The carboxyl residue is involved in catalysis and tryptophan residue is solely involved in substrate binding. The best match from the search of the NCBInr database was with gi vertical bar 808364558 glycoside hydrolase of Pseudozyma hubeiensis SY62 with 26 % sequence coverage confirming that it is a glycoside hydrolase/beta-glucosidase. From the search of customized SWISSPROT database, it was revealed that SWISSPROT does not contain any entries that are similar to the purified enzyme.

Quenching effect of uranyl species in the photoluminescence emission and visible-light-driven water dissociation activity of CdS and TiO2 photocatalysts - Gupta, Narendra M.; Kelkar, Sarika A.; Korake, Prakash V. (Photochemical & Photobiological Sciences, 2016)
Anchoring of uranyl species (2-4 mol%) led to the complete quenching of photoluminescence emission and the visible-light-driven water photodissociation activity of TiO2 (Degussa-P25) and a hydrothermally synthesized CdS photocatalyst. Photophysical measurements revealed a fast relaxation and the transfer of photogenerated electrons/energy from the TiO2 or CdS substrate to the acceptor uranyl moieties. Besides the position of flat band levels, significant overlap of the absorption/emission spectra of the host matrix and the surface-bound UO22+ species is responsible for this reverse energy transfer from a wide bandgap semiconductor to a material with a smaller band-to-band energy gap.

Radio-frequency triggered heating and drug release using doxorubicin-loaded LSMO nanoparticles for bimodal treatment of breast cancer - Kulkarni, Vaishnavi M.; Bodas, Dhananjay; Dhoble, Deepa; Ghormade, Vandana; Paknikar, Kishore (Colloids and Surfaces B-Biointerfaces, 2016)
Radio-frequency responsive nanomaterials combined with drugs for simultaneous hyperthermia and drug delivery are potential anti-cancer agents. In this study, chitosan coated La0.7Sr0.3MnO3 nanoparticles (C-LSMO NPs) were synthesized and characterized by X-ray diffraction, dynamic light scattering, Fourier transform infra red spectroscopy, vibrating sample magnetometer, scanning electron and atomic force microscopy, Under low radio-frequency (365 kHz, RF), C-LSMO NPs (90 nm) showed good colloidal stability (+22 mV), superparamagnetic nature (15.4 emu/g) and heating capacity (57.4W/g SAR value). Chitosan facilitated doxorubicin entrapment (76%) resulted in DC-LSMO NPs that showed drug release upon a 5 min RF exposure. MCF-7 and MDA-MB-231 cancer cells responded to a 5 min RF exposure in the presence of bimodal DC-LSMO NPs with a significant decrease in viability to 73% and 88% (Pearson correlation, r = 1, P<0.01) respectively, as compared to hyperthermia alone. Internalization of DC-LSMO NPs via the endosomal pathway led to an efficient localization of doxorubicin within the cell nucleus. The ensuing DNA damage, heat shock protein induction, and caspase production triggered apoptotic cell death. Moreover, DC-LSMO NPs successfully restricted the migration of metastatic MDA-MB-231 cancer cells. These data suggest that DC-LSMO NPs are potential bimodal therapeutic agents for cancer treatment and hold promise against disease recurrence and drug resistance. (C) 2016 Elsevier B.V. All rights reserved.

Reductive nitrosylation of nickel(II) complex by nitric oxide followed by nitrous oxide release - Ghosh, Somnath; Deka, Hemanta; Dangat, Yuvraj B.; Saha, Soumen; Gogoi, Kuldeep; Vanka, Kumar; Mondal, Biplab (Dalton Transactions, 2016)
Ni(II) complex of ligand L (L = bis(2-ethyl-4-methylimidazol-5-yl)methane) in methanol solution reacts with an equivalent amount of NO resulting in a corresponding Ni(I) complex. Adding further NO equivalent affords a Ni(I)-nitrosyl intermediate with the NiNO(10) configuration. This nitrosyl intermediate upon subsequent reaction with additional NO results in the release of N2O and formation of a Ni(II)-nitrito complex. Crystallographic characterization of the nitrito complex revealed a symmetric eta(2)-O,O-nitrito bonding to the metal ion. This study demonstrates the reductive nitrosylation of a Ni(II) center followed by N2O release in the presence of excess NO.

Remediation of domestic and industrial effluents using algae - Nene, S. N.; Gera, G.; Yewalkar, S. N. (Algal Biorefinery: An Integrated Approach, 2016)
In the environment, microbial activity is considered as one of the most important mechanisms for the abatement of water-borne pollutants. In the natural and anthropogenic environment the wide range of contaminates are not eliminated by single specie but by the complex interaction of a mixed microbial population performing complementary reactions. This principle is very much applicable for the treatment of the industrial and domestic wastewater, which has excess of nitrogenous compounds (N) and phosphates (P). N and P along with various organic pollutants, if not properly treated, would create a devastating impact on natural aquatic ecosystems. Among the many other disturbing impacts, most prevalent is the phenomenon of eutrophication, which is the accumulation of high levels of organic matter and the decomposing organisms, which deplete the oxygen in water, and causing the death of other organisms, such as fish. The excess nutrients in the aquatic ecosystem support the growth of various phytoplanktons. It not only spoils the water quality but also adversely affects the whole aquatic ecosystem. This chapter will address the possibility of effectively utilizing a natural microbial flora/consortium, enriched with the rapidly growing algae for the remediation of polluted water bodies.

Reporter nanoparticle that monitors its anticancer efficacy in real time - Kulkarni, Ashish; Rao, Poornima; Natarajan, Siva; Goldman, Aaron; Sabbisetti, Venkata S.; Khater, Yashika; Korimerla, Navya; Chandrasekar, Vineethkrishna; Mashelkar, Raghunath Anant; Sengupta, Shiladitya (Proceedings of the National Academy of Sciences of the United States of America, 2016)
The ability to monitor the efficacy of an anticancer treatment in real time can have a critical effect on the outcome. Currently, clinical readouts of efficacy rely on indirect or anatomic measurements, which occur over prolonged time scales postchemotherapy or postimmunotherapy and may not be concordant with the actual effect. Here we describe the biology-inspired engineering of a simple 2-in-1 reporter nanoparticle that not only delivers a cytotoxic or an immunotherapy payload to the tumor but also reports back on the efficacy in real time. The reporter nanoparticles are engineered from a novel two-staged stimuli-responsive polymeric material with an optimal ratio of an enzyme-cleavable drug or immunotherapy (effector elements) and a drug function-activatable reporter element. The spatiotemporally constrained delivery of the effector and the reporter elements in a single nanoparticle produces maximum signal enhancement due to the availability of the reporter element in the same cell as the drug, thereby effectively capturing the temporal apoptosis process. Using chemotherapy-sensitive and chemotherapy-resistant tumors in vivo, we show that the reporter nanoparticles can provide a real-time noninvasive readout of tumor response to chemotherapy. The reporter nanoparticle can also monitor the efficacy of immune checkpoint inhibition in melanoma. The self-reporting capability, for the first time to our knowledge, captures an anticancer nanoparticle in action in vivo.
Keywords: chemotherapy; immunotherapy; monitoring; nanoparticle; reporter

Repurposing of a drug scaffold: identification of novel sila analogues of rimonabant as potent antitubercular agents - Ramesh, Remya; Shingare, Rahul D.; Kumar, Vinod; Anand, Amitesh; Swetha, B.; Veeraraghavan, Sridhar; Viswanadha, Srikant; Ummanni, Ramesh; Gokhale, Rajesh S.; Reddy, D. Srinivasa (European Journal of Medicinal Chemistry, 2016)
The structural similarity between an MmpL3 inhibitor BM212, and a cannabinoid receptor modulator rimonabant, prompted us to investigate the anti-tubercular activity of rimonabant and its analogues. Further optimization, particularly through incorporation of silicon into the scaffold, resulted in new compounds with significant improvement in anti-tubercular activity against Mycobacterium tuberculosis (H37Rv). The sila analogue 18a was found to be the most potent antimycobacterial compound (MIC, 31 ng/mL) from this series with an excellent selectivity index. (C) 2016 Elsevier Masson SAS. All rights reserved.

Repurposing of old drugs: identification of novel sila analogues of rimonabant as potent antitubercular agents - Ramesh, R.; Shingare, R.; Anand, Amitesh; Veeraraghavan, S.; Viswanadha, S.; Ummanni, R.; Gokhale, R.; Reddy, D. S. (International Journal of Infectious Diseases, 2016)

Residue dependent hydrogen-bonding preferences in orthanilic acid-based short peptide beta-turn motifs - Jedhe, Ganesh S.; Vijayadas, Kuruppanthara N.; Kotmale, Amol S.; Sangtani, Ekta; Shinde, Dinesh R.; Gonnade, Rajesh G.; Rajamohanan, Pattuparambil R.; Sanjayan, Gangadhar J. (RSC Advances, 2016)
This communication describes the competition between native beta-turn (C10) and 2-aminobenzenesulfonic acid (SAnt)( orthanilic acid)-based pseudo beta-turn (C11) in their hybrid peptides. Solid-state crystal structure and solution-state NMR studies revealed that C10 and C11 can be simultaneously observed under appropriate conditions. The variable temperature NMR coefficient data suggest that the isolated C11/C14 hydrogen bond is weaker in comparison with the consecutive C10 and C11 turns.

Rhodium-catalyzed ortho C-H bond activation of arylamines for the synthesis of quinoline carboxylates - Gadakh, Sunita K.; Dey, Soumen; Sudalai, A. (Organic & Biomolecular Chemistry, 2016)
The rhodium catalyzed annulation of anilines with alkynic esters allowing for the high-yield synthesis of quinoline carboxylates with excellent regioselectivity is described. This unprecedented reaction employs either formic acid as the C1 source and reductant or copper(II) as the oxidant and is proposed to proceed via rhodacycle of in situ generated amide and enamine ester followed by ortho C-H activation of arylamines with rhodium as the catalyst.

RNAi of selected candidate genes interrupts growth and development of Helicoverpa armigera - Chikate, Yojana R.; Dawkar, Vishal V.; Barbole, Ranjit S.; Tilak, Priyadarshini V.; Gupta, Vidya S.; Giri, Ashok P. (Pesticide Biochemistry and Physiology, 2016)
Helicoverpa armigera is one of the major crop pests and is less amenable to current pest control approaches. RNA interference (RNAi) is emerging as a potent arsenal for the insect pest control over current methods. Here, we examined the effect on growth and development in H. armigera by targeting various enzymes/proteins such as proteases like trypsins (HaTry2, 3, 4 and 6), chymotrypsin (HaChy4) and cysteine protease like cathepsin (HaCATHL); glutathione S-transferases (HaGST1a, 6 and 8); esterases (HaAce4, HaJHE); catalase (HaCAT); super-oxide-dismutase (HaCu/ZnSOD); fatty acid binding protein (HaFabp) and chitin deacetylase (HaCda5b) through dsRNA approach. Significant downregulation of cognate mRNA expression and reduced activity of trypsin and GST-like enzyme were evident upon feeding candidate dsRNAs to the larvae. Among these, the highest mortality was observed in HaAce4 dsRNA fed larvae followed by HaJHE; HaCAT; HaCuZnSOD; HaFabp and HaTry3 whereas remaining ones showed relatively lower mortality. Furthermore, the dsRNA fed larvae showed significant reduction in the larval mass and abnormalities at the different stages of H. armigera development compared to their control diets. For example, malformed larvae, pupae and moth at a dose of 60 pg/day were evident in high number of individual insects fed on dsRNA containing diets. Moreover, the growth and development of insects and moths were retarded in dsRNA fed larvae. These findings might provide potential new candidates for designing effective dsRNA as pesticide in crop protection. (C) 2016 Elsevier Inc. All rights reserved.

Robust highly flexible all-solid-state micro pseudocapacitor based on ternary oxide CuCo2O4 having ultrathin porous nanowall type morphology blended with CNT - Basu, Aniruddha; Bhardwaj, Monika; Gawli, Yogesh; Rode, Chandrasekhar V.; Ogale, Satishchandra B. (Chemistryselect, 2016)
In this work we demonstrate a facile approach to the fabrication of all solid state flexible interdigitated micro pseudocapacitor device using pre-synthesized CuCo2O4 (CCO) ternary metal oxide as the electrode material. The hydrothermally synthesized CCO exhibits a peculiar 3D interconnected aligned porous nanowall type morphology which is highly desirable for storage as well as charge transfer. The device is fabricated using CO2 laser scribing technique and the PVA-H3PO4 gel electrolyte is used as the electrolyte. The as-synthesized CCO as well as its blend with 10 wt.% CNT are examined for the electrochemical performance. CNT blending is shown to reduce the charge transfer resistance dramatically, thereby enhancing the pseudo capacitance. The areal capacitance of 2.29 mF cm(-2) is obtained from the solid state device. Moreover, the CCO-CNT electrode also shows a high stability upto 9000 cycles without a sign of further decay. Importantly, the devices also retain over 65% of their initial capacitance after 1000 large angle (608) bending cycles and 93% of the initial capacitance under 1208 bending condition, thanks to the mechanical flexibility afforded by CNTs without disrupting conducting paths.

Salvia miltiorrhiza: A medicinal herb from metabolites to pathway engineering - Gupta, S. K.; Sharma, P.; Agrawal, D. C.; Tsay, H.-S. (Medicinal plants - recent advances in research and development, 2016)
The dried, red-colored roots of Salvia miltiorrhiza (Lamiaceae) also called “danshen” in colloquial language in China have been used in traditional Chinese medicine for thousands of years to treat hypertension and other cardiovascular ailments. The main constituents of danshen are hydrophilic phenolic acids and lipophilic tanshinones. The various uses of danshen in traditional as well as modern medicines have motivated an intensive research on compounds in S. miltiorrhiza. In recent years, more than 110 compounds have been isolated from S. miltiorrhiza and their structure was identified. Tanshinones and their derivatives have been demonstrated to possess properties of slowing down or curing various ailments related to cardiovascular, cerebrovascular, respiratory, liver, nervous system, cancer, Alzheimer’s, and Parkinson’s diseases. With the increasing demand of this herb, an unrestricted collection to supply raw materials and the extraction of its constituents have severely threatened the natural habitats of S miltiorrhiza. This has prompted the researchers to develop alternative strategies for metabolite production. Several in vitro methodologies have been established to generate callus, cell suspension culture, hairy roots, and plant regeneration. Different regulators and elicitors for plant growth have been employed to enhance levels of different constituents. The advent of sequencing technologies, whole genome, and expression data has helped to provide insights and identification of pathway genes involved in the biosynthesis. This book chapter gives a brief description of in vitro methodologies, use of different elicitors, gene functions, genetic modifications, expression profiling for a better understanding, and enhancement of the constituents in S. miltiorrhiza.

Seeding of Au on CdSe/CdS nanoplates using Langmuir-Blodgett technique - Das, Subhasis; Satpati, Biswarup; Chauhan, Himani; Deka, Sasanka; Ghosalya, Manoj Kumar; Gopinath, Chinnakonda S.; Bala, Tanushree (RSC Advances, 2016)
Oleyl amine capped CdSe/CdS nanoplates were synthesized by hot injection technique which formed a stable monolayer over both a water subphase and an aqueous HAuCl4 subphase using a Langmuir-Blodgett trough. Au islands were generated at the edge as well as on one specific surface of the flat nanoplates by exploiting the reducing capacity of oleyl amine to form Au nanoseeds from AuCl4- ions. The initial Au nanoseeds changed to a shell surrounding these nanoplates on prolonged exposure to the subphase containing the Au precursor. Monolayer of the hybrid structures was deposited onto suitable substrates for characterization by a number of different techniques and to study the photocatalytic activity. The same substrate with the monolayers could be re-used in several cycles of photocatalysis.

Selective detection of Fe3+, Cr3+ and Cu2+ in water using highly luminescent Gd2O3:Eu3+ nanoparticles - Ghosh, Debasish; Luwang, Meitram Niraj (Journal of Luminescence, 2016)
Rod shaped Eu3+ doped Gd2O3 nanoparticles were synthesised by a simple wet-chemical method followed by high temperature heating at 700 degrees C. The nanoparticles were characterised by X-ray diffraction (XRD), infra-red (IR), transmission electron microscopy (TEM), x-ray photonelectron spectroscopy (XPS), photoluminescence (PL) studies and lifetime measurement. The particles show strong host sensitised luminescence in water. Luminescence in water is selectively quenched by Fe3+, Cr3+ and Cu2+ ions. This luminescence quenching phenomenon has been utilised to detect metal ions in synthetic water and environmental water samples. Results obtained by luminescence quenching for environmental water samples are in good agreement with the results obtained from inductively coupled plasma atomic emission spectroscopy (ICP-AES) study. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Detection; Luminescence; Nanoparticles; Quenching; Sensitization

Selective synthesis of N-unsubstituted and N-arylindoles by the reaction of arynes with azirines - Thangaraj, Manikandan; Bhojgude, Sachin Suresh; "Jain, Shailja"; Gonnade, Rajesh G.; Biju, Akkattu T. (Journal of Organic Chemistry, 2016)
The transition-metal-free and temperature-dependent highly selective reaction of arynes with 2H-azirines allowing the synthesis of either N-unsubstituted or N-arylindoles has been developed. At 60 degrees C, arynes generated from 2-(trimethylsilyl)aryl triflates smoothly insert into 2H-azirines to form 2,3-diarylindoles with high selectivity. Interestingly, when the reaction was performed at -10 degrees C, the selectivity was switched to the formation of 1,2,3-triarylindoles in good yields.

Self-exfoliated metal-organic nanosheets through hydrolytic unfolding of metal-organic polyhedra - Garai, Bikash; Mallick, Arijit; Das, Anuja; Mukherjee, Rabibrata; Banerjee, Rahul (Chemistry-A European Journal, 2016)
Few-layers thick metal-organic nanosheets have been synthesized using water-assisted solid-state transformation through a combined top-down and bottom-up approach. The metal-organic polyhedra (MOPs) convert into metal-organic frameworks (MOFs) which subsequently selfexfoliate into few-layered metal-organic nanosheets. These MOP crystals experience a hydrophobicity gradient with the inner surface during contact with water because of the existence of hydrophobic spikes on their outer surface. When the amount of water available for interaction is higher, the resultant layers are not stacked to form bulk materials; instead few-layered nanosheets with high uniformity were obtained in high yield. The phenomenon has resulted high yield production of uniformly distributed layered metal-organic nanosheets from three different MOPs, showing its general adaptability.

Sequence characterization and in silico structure prediction of fatty acid desaturases in linseed varieties with differential fatty acid composition - Rajwade, Ashwini V.; Joshi, Rakesh S.; Kadoo, Narendra Y.; Gupta, Vidya S. (Journal of the Science of Food and Agriculture, 2016)
BACKGROUND: Linseed is the richest agricultural source of alpha-linolenic acid (ALA), an omega-3 fatty acid (FA) that offers several nutritional benefits. In the present study, sequence characterization of six desaturase genes (SAD1, SAD2, FAD2, FAD2-2, FAD3A and FAD3B) and 3D structure prediction of their proteins from ten Indian linseed varieties differing in ALA content were performed to determine whether the nucleotide and amino acid (AA) sequence variants have any functional implications in differential accumulation of ALA or other FAs in linseed. RESULTS: The SAD and FAD2 genes exhibited few sequence variations among the ten varieties, forming only one or two protein isoforms. In contrast, the FAD3A and FAD3B genes showed more sequence variations and three or four protein isoforms. Interestingly, the two high-ALA varieties NL260 and Padmini had the same FAD3B nucleotide and protein isoforms, which differed from all other varieties. Surprisingly, no AA changes altered the 3D structures of the desaturase proteins. CONCLUSION: Several nucleotide and AA sequence variations in desaturase genes were observed; however, they did not alter the 3D structure of any desaturase protein and were not correlated with FA levels among the ten linseed varieties, which had different ALA contents. This suggests a complex regulatory process of biosynthesis of FAs in linseed. (C) 2016 Society of Chemical Industry

Shear stress increases cytotoxicity and reduces transfection efficiency of liposomal gene delivery to CHO-S cells - Rawat, Jyoti; Gadgil, Mugdha (Cytotechnology, 2016)
Animal cells in suspension experience shear stress in different situations such as in vivo due to hemodynamics, or in vitro due to agitation in large-scale bioreactors. Shear stress is known to affect cell physiology, including binding and uptake of extracellular cargo. In adherent cells the effects of exposure to shear stress on particle binding kinetics and uptake have been studied. There are however no reports on the effect of shear stress on extracellular cargo delivery to suspension cells. In this study, we have evaluated the effect of shear stress on transfection of CHO-S cells using Lipofectamine 2000 in a simple flow apparatus. Our results show decreased cell growth and transfection efficiency upon lipoplex assisted transfection of CHO-S while being subjected to shear stress. This effect is not seen to the same extent when cells are exposed to shear stress in absence of the lipoplex complex and subsequently transfected, or if the lipoplex is subjected to shear stress and subsequently used to transfect the cells. It is also not seen to the same extent when cells are exposed to shear stress in presence of liposome alone, suggesting that the observed effect is dependent on interaction of the lipoplex with cells in the presence of shear stress. These results suggest that studies involving liposomal DNA delivery in presence of shear stress such as large scale transient protein expression should account for the effect of shear during lipoplex assisted DNA delivery.

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.

Solution-phase synthesis of the macrocyclic core of teixobactin - Dhara, Santu; Gunjal, Vidya B.; Handore, Kishor L.; Reddy, D. Srinivasa (European Journal of Organic Chemistry, 2016)
Towards the total chemical synthesis of the exceptionally potent antibiotic teixobactin, we synthesized the macrocyclic core of a natural product by using a solution-phase approach. The gramscale synthesis of L-allo-enduracididine and Shiina macrolactonization are highlights of the present disclosure.

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

Study of magnetic and thermal properties of SmCrO3 polycrystallites - Gupta, Preeti; Poddar, Pankaj (RSC Advances, 2016)
In the present work, we have studied the magnetic and thermal properties of sol gel derived samarium chromite (SCO) polycrystallites. The magnetic measurements of SCO polycrystallites show a characteristic antiferromagnetic transition T-N similar to 190 K and spin reorientation temperature T-SR similar to 33 K, which is in the region of interest to study a possible magnetocaloric effect (MCE). The isothermal magnetic entropy change (Delta S-M) is estimated by an indirect method from the isothermal magnetization curves measured in this temperature range. The SCO polycrystallites possesses both inverse (positive) and normal (negative) MCE at and above around the spin reorientation transition (TSR) with Delta S-M(max) M values of similar to -24 x 10(-2) & 13 x 10(-2) J kg(-1) K-1, respectively. The SCO also shows another normal (negative) MCE peak around its Neel transition (T-N) with -Delta S-M(max) M similar to 11 x 10(-2) J kg(-1) K-1. The presence of two successive MCE peaks in SCO in the temperature range of 3-50 K, leads to an similar to 47 K operating temperature window with one thermodynamic cycle. In addition, the low temperature heat capacity (C-P) measurements of SCO polycrystallites reveal a lambda-shaped peak at T-N which is associated with a conventional second- order, paramagnetic to antiferromagnetic (AFM), phase transition. The temperature and magnetic field dependence of the specific heat capacity was studied and analyzed to estimate the adiabatic temperature change (Delta T-ad). In addition the C-P vs. T curve in SCO also shows a weak anomaly around the similar to T-SR along with a Schottky anomaly below 10 K.

Substrate-controlled selectivity switch in the three-component coupling involving arynes, aromatic tertiary amines, and CO2 - Bhojgude, Sachin Suresh; Roy, Tony; Gonnade, Rajesh G.; Biju, Akkattu T. (Organic Letters, 2016)
The transition-metal-free multicomponent coupling involving arynes, aromatic tertiary amines, and CO2 is reported. The reaction exhibits switchable selectivity depending on the electronic nature of the aromatic amines used. With amines bearing electron-releasing/neutral groups as the nucleophilic trigger, the reaction afforded 2-arylamino benzoates via a nitrogen to oxygen alkyl group migration. Employing electron-deficient amines in the reaction furnished 2-aminoaryl benzoates proceeding via the aryl to aryl amino group migration resembling a Smiles rearrangement.

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 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 characterization of FeTiO3 ceramics - Gambhire, Anil B.; Lande, Machhindra K.; Rathod, Sandip B.; Arbad, Balasaheb R.; Vidhate, Kaluram N.; Gholap, Ramakrishna S.; Patil, Kashinath R. (Arabian Journal of Chemistry, 2016)
Nanocrystalline FeTiO3 ceramics powders were prepared by the sol-gel process combined with a surfactant-assisted template method. The resulting powders were calcined at different temperatures ranging from 150 degrees C to 600 degrees C for 2 h in an air. The results revealed that a pure hexagonal phase of FeTiO3 could be obtained at low temperature, 600 degrees C. The phase evolution of FeTiO3 was investigated by X-ray diffraction patterns (XRD), Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). Particle size and morphology was studied by transmission electron microscopy (TEM). (C) 2011 Production and hosting by Elsevier B.V. on behalf of King Saud University.
Keywords: Electron microscopy; hexagonal phase; Nanoparticles; sol-gel process; Ti-O bond

Synthesis and characterization of thermally stable polyimides with a pendent phenothiazine unit based on new diamine 10-(3,5-diaminobenzoyl)phenothiazine - Ghorpade, Ravindra V.; Thorave, Asmita K.; Rajan, C. R.; Chavan, Nayaku; Ponrathnam, S. (High Performance Polymers, 2016)
A novel diamine 10-(3,5-diaminobenzoyl)phenothiazine (DBPT) with a side chain containing phenothiazine unit was synthesized. A new family of polyimides (PIs) containing phenothiazine unit in the side chains has been successfully synthesized by direct polycondensation of DBPT with pyromellitic dianhydride, 3,3',4,4'-benzophenone tertacarboxylic dianhydride, and 4,4'-oxydiphthalic anhydride (ODA) via a conventional two-step chemical imidization process. The yield of polymers was good enough, which were soluble in most organic solvents. The molecular orbital energy gaps, thermal stability, and crystallinity of PIs were investigated by molecular modeling, thermogravimetric analysis, and wide-angle X-ray scattering, respectively. Thermal properties of polymers were good enough to permit the use of these PIs in various applications; only 49% weight loss is detected at 900 degrees C in nitrogen atmosphere. X-Ray diffraction clearly reveals the amorphous nature of PIs. A quantum modeling study (density functional theory) has shown the influence of dianhydride structure on the energy difference of highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels.
Keywords: phenothiazine-containing diamine; Polyimide; thermally stable polymer

Synthesis and self-assembly of dumbbell shaped ZnO sub-micron structures using low temperature chemical bath deposition technique - Borade, P.; Joshi, K. U.; Gokarna, A.; Lerondel, G.; Walke, P.; Late, Dattatray J.; Jejurikar, S. M. (Materials Chemistry and Physics, 2016)
We report well dispersed horizontal growth of ZnO sub-micron structures using simplest technique ever known i.e. chemical bath deposition (CBD). A set of samples were prepared under two different cases A) dumbbell shaped ZnO grown in CBD bath and B) tubular ZnO structures evolved from dumbbell shaped structures by dissolution mechanism. Single phase wurtzite ZnO formation is confirmed using X-ray diffraction (XRD) technique in both cases. From the morphological investigations performed using scanning electron microscopy (SEM), sample prepared under case A indicate formation of hex bit tool (HBT) shaped ZnO crystals, which observed to self-organize to form dumbbell structures. Further these microstructures are then converted into tubular structures as a fragment of post CBD process. The possible mechanism responsible for the self-assembly of HBT units to form dumbbell structures is discussed. Observed free excitonic peak located at 370 nm in photoluminescence (PL) spectra recorded at 18 K indicate that the micro/nanostructures synthesized using CBD are of high optical quality. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Electron microscopy (STEM; Microstructure; Nanostructures; Optical properties; Photoluminescence spectroscopy; Raman spectroscopy and scattering; TEM and SEM)

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 of 2-phenoxy-2-phenylethyl acrylate and copolymerization with 2-phenylethyl acrylate: estimation of monomer reactivity ratios, thermal and optical properties - Ghorpade, Ravindra V.; Ponrathnam, Surendra; Chavan, Nayaku (Journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2016)
A new aromatic based monomer 2-phenoxy-2-phenylethyl acrylate (PPEA) was synthesized. Copolymers of PPEA with 2-phenylethyl acrylate (PEA) were prepared by free radical polymerization. The reactivity ratios were estimated using various graphical methods. Structural parameters of the copolymers were obtained by calculating the dyad monomer sequence fractions and the mean sequence length. Optical properties of polymers such as refractive indices and UV-Visible absorption were investigated. The glass transition temperature and thermal degradation behavior of the copolymers were studied. Combined with the RI, transparency and thermal properties, prepared copolymers hold great promise as materials for intraocular lens applications.
Keywords: 2-Phenoxy-2-phenylethyl acrylate; 2-phenylethyl acrylate; copolymerization; Optical properties; reactivity ratios; Thermal properties

Synthesis of 4H-chromenes by an unexpected, K3PO4-mediated intramolecular rauhut–currier type reaction - Bhunia, Anup; Yetra, Santhivardhana Reddy; Gonnade, Rajesh G.; Biju, Akkattu T. (Organic & Biomolecular Chemistry, 2016)
In an attempt to develop the umpolung of Michael acceptors using chalcones having an enoate moiety under N-heterocyclic carbene (NHC) catalysis, a K3PO4-mediated intramolecular Rauhut–Currier type reaction was observed. This C(sp2)–C(sp2) coupling reaction afforded the biologically important 4H-chromenes in moderate to good yields. It is likely that the enol ether functionality acts as the nucleophilic trigger in this reaction.

Synthesis of functionalized amino epoxides by a three-component coupling involving aziridines, arynes and aldehydes - Roy, Tony; Thangaraj, Manikandan; Gonnade, Rajesh G.; Biju, Akkattu T. (Chemical Communications, 2016)
A transition-metal-free three-component coupling involving N-substituted aziridines, arynes and aldehydes resulting in the formation of trisubstituted N-aryl alpha-amino epoxides has been demonstrated. The reaction likely proceeds via the highly strained cyclic nitrogen ylide intermediates generated from aziridines and arynes.

Synthesis of quinoline-based NNN-pincer nickel(II) complexes: a robust and improved catalyst system for C–H bond alkylation of azoles with alkyl halides - Patel, Ulhas N.; Pandey, Dilip K.; Gonnade, Rajesh G.; Punji, Benudhar (Organometallics, 2016)
The quinoline-based pincer nickel(II) complexes κN,κN,κN-{R2N-C6H4-(μ-N)-C9H6N}NiX ((R2NNNQ)NiCl: R = Me, 2a; R = Et, 2b) were synthesized by the reaction of the ligand precursors (R2NNNQ)H (R = Me, 1a; R = Et, 1b) with (DME)NiCl2 in the presence of Et3N. Similarly, the pincer nickel(II) derivatives (R2NNNQ)NiX (R = Me, X = Br, 3a; R = Et, X = Br, 3b; R = Me, X = OAc, 4a) were obtained by treatment of the ligands (R2NNNQ)H with the nickel precursor (THF)2NiBr2 or Ni(OAc)2. All of these complexes were characterized by 1H and 13C NMR spectroscopy as well as by elemental analysis. Further, the molecular structures of 2a and 3a,b were elucidated by X-ray crystallography. Complex 2a is found to be an efficient catalyst for the direct C–H bond alkylation of substituted benzothiazoles and oxazoles with various unactivated alkyl halides containing β-hydrogens under mild reaction conditions. The catalyst 2a is very robust and was recycled and reused five times for the alkylation reaction without a decrease in its catalytic activity. Preliminary studies reveal that the catalyst 2a acts as an active catalyst and the alkylation reaction appears to operate via a radical pathway.

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.

Theoretical study of the ground and excited state tautomersim in curcumin using DFT based methods - Grewal, Baljinder; Ghosh, Debashree (Abstracts of Papers of the American Chemical Society, 2016)

Is there any real effect of low dimensional morphologies towards light harvesting? a case study of Au-rGO-TiO2 nanocomposites - Melvin, Ambrose A.; Bharad, Pradnya A.; Illath, Kavya; Lawrence, Meenu P.; Gopinath, Chinnakonda S. (Chemistry Select, 2016)
Nanotube and nanosheet morphologies have been celebrated for their electron transport properties. Present work has been explored to exploit the same by combining 1D TiO2 nanotube (1D-TN) with 2D reduced graphene oxide (rGO) along with nano gold for visible light sensitization for photocatalytic H2 generation under one sun condition and visible light (λ≥ 400 nm). Vertical and horizontal electron transport in 1D-TN and rGO, respectively, is combined with the visible light absorption capability of Au nanoparticle. H2 yield (HY) varies between 100 and 655 µmol/g.h with an apparent quantum yield between 0.45 and 3.2 %, respectively, depending on Au/rGO/1D-TN preparation method and reaction conditions. It has been demonstrated that interfacial contact between rGO/1D-TN and Au is crucial for high photocatalytic HY. Preparation method influences charge utilization, and hence HY, to a large extent. Nonetheless, the maximum HY reported in the present work is just comparable to HY reported in literature with the most commonly found spherical morphology, and this leads to a question of, is there any real influence of 1D and/or 2D materials, particularly, towards light harvesting applications?

Three way catalytic converter reactions aspects at near ambient temperatures on modified pd-surfaces - Roy, Kanak; Jain, Ruchi; Ghosalya, Manoj Kumar; Reddy, Kasala Prabhakar; Gopinath, Chinnakonda S. (Comptes Rendus Chimie, 2016)
The dissolution of oxygen in palladium plays an important role in palladium catalysis. The present study shows that the surface modification (SM) due to the dissolution of atomic oxygen into the subsurfaces of palladium can be used as a control to tune its catalytic activity. CO oxidation and NO + H-2 + O-2 reaction was separately carried out on metallic Pd and on surface modified Pd using a molecular beam instrument and the results were compared. The metallic Pd does not show activity below 400 K for both reactions, whereas the SM-Pd shows activity at near-ambient temperatures. The electronic change due to SM was investigated using ambient pressure photoelectron spectroscopy, and the investigation clearly shows the effect of subsurface oxygen in the ambient temperature activity of palladium. (C) 2016 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

TiO2 modification by gold (Au) for photocatalytic hydrogen (H-2) production - Gupta, Bhavana; Melvin, Ambrose A.; Matthews, Tom; Dash, Sitaram; Tyagi, A. K. (Renewable & Sustainable Energy Reviews, 2016)
TiO2 is indeed one of the widely used semiconductors employed for photocatalytic hydrogen production. Most of its photocatalytic activity-is achieved in its crystalline form. However, its photocatalytic activity is limited to ultraviolet region. For making TiO2 visible light active; Au deposition is strongly recommended due to its surface plasmon feature. Au deposition enhances the photocatalytic activity of both crystalline and nanocrystalline TiO2. Efficiency of photocatalytic activity is controlled by shape and size of Au nanoparticle subsequently the synthetic methodology plays an important role. Herein, we furnish a brief description of TiO2-Au nanocomposite synthesis by different methods viz. sol-gel, photodeposition, deposition-precipitation simple reducing method and dispersion method. A discussion on physical properties of the resultant material is also provided. Three different types of mechanism has been described depending on the type of irradiation and form of TiO2 (crystalline and nanocrytalline). A comparative hydrogen production yield is also tabulated to get an idea about the best synthesis methodology and form of TiO2 for efficient photocatalysis. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: Gold nanoparticle; Hydrogen generation; Nanocomposite; Photocatalysis; TiO2

Total synthesis of isocladosporin and 3-epi-isocladosporin - Mohapatra, Debendra K.; Maity, Saurabh; Banoth, Shivalal; Gonnade, Rajesh G.; Yadav, J. S. (Tetrahedron Letters, 2016)
A convergent total synthesis of isocladosporin and 3-epi-isocladosporin is reported starting from commercially available homoallyl alcohol in 10 longest linear steps with 28% overall yield. The key steps involved in the synthesis are cross-metathesis, tandem isomerization followed by C-O and C-C bond formation reactions for the synthesis of trans-2,6-disubstituted dihydropyrans developed by us, acylation reaction and Luche reaction. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Acylation reaction; Cross-metathesis; Iodocyclization; Isocladosporin 3-epi-Isodadosporin; Luche reduction

Total synthesis of the marine natural product solomonamide B necessitates stereochemical revision - Kashinath, K.; Jachak, Gorakhnath R.; Athawale, Paresh R.; Marelli, Udaya Kiran; Gonnade, Rajesh G.; Reddy, D. Srinivasa (Organic Letters, 2016)
The first total synthesis of the proposed structure of solomonamide B has been achieved. However, the H-1 and C-13 NMR spectral data of the synthesized compound was not exactly matching with that of the natural solomonamide B. This prompted us to revise the originally proposed structure, in particular, the stereochemistry of the nonpeptide part, which was confirmed by its total synthesis. During the course of the synthesis, we have developed an interesting hydroxy group directed Wacker oxidation of internal olefins in a macrocyclic setting.

Toughening of epoxy novolac resin using cardanol based flexibilizers - Gour, Rajeshwari S.; Kodgire, Vivek V.; Badiger, Manohar V. (Journal of Applied Polymer Science, 2016)
In this work, two different cardanol based epoxies (Cardolite NC-514 and Cardanol NC-547) were employed as flexibilizers to toughen an epoxy novolac resin namely, poly[(phenylglycidyl ether)-co-formaldehyde] (PPGEF). 4,4-Diamino-3,3-dimethyl dicyclohexyl methane (BMCHA) was used as a curing agent. Differential scanning calorimetry and dynamic mechanical thermal analysis of the composites showed a gradual decrease in glass transition temperatures (T-g) with increase in cardolite content confirming the incorporation of flexible moieties into the brittle resin matrix. Improvement in toughening of PPGEF/Cardolite composites was manifested by increase in the izod impact strength of both the composites. The tensile strength increased marginally for composites with increasing amount of Cardolite NC-514 but decreased for the composites containing Cardolite NC-547. This was attributed to the lack of rotational motion in the chain due to close proximity of rigid phenyl rings in NC-547. SEM of the cryo-fractured surfaces of composites showed good compatibility between PPGEF and cardanol based flexibilizers. (c) 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43318.
Keywords: composites; crosslinking; glass transition

Tracing the architecture of caffeic acid phenethyl ester cocrystals: studies on crystal structure, solubility, and bioavailability implications - Ketkar, Sameer; Pagire, Sudhir K.; Goud, N. Rajesh; Mahadik, Kakasaheb R.; Nangia, Ashwini; Paradkar, Anant (Crystal Growth & Design, 2016)
Caffeic acid phenethyl ester (CAPE) is a polyphenolic active compound present in popular apiproduct, "propolis", obtained from beehives, Though it has broad therapeutic capability, the bioavailability of CAPE is limited due to poor solubility. In this study, we report novel cocrystals of CAPE engineered using coformers such as caffeine (CAP), isonicotinamide (INIC), and nicotinamide (NIC) with enhanced solubility and bioavailability of CAPE. The cocrystals were prepared by microwave-assisted cocrystallization and characterized using PXRD, DSC, and Raman spectroscopy. PXRD and DSC confirm the successful formation and phase purity of CAPE-CAF, CAPE-INIC, and CAPE-NIC cocrystals. Raman spectra of CAPE cocrystals complement these results in confirming the formation of novel crystalline phases. CAPE-NIC cocrystal was further subjected X-ray crystallography to understand its molecular arrangement and hydrogen bonding in the crystal structure. The CAPE-NIC cocrystal structure is found to be stabilized by a rare 1,2-benzenediol-amide heterosynthon. Cocrystallization of CAPE with NIC improved its aqueous solubility and pharmacokinetic profile, thereby demonstrating a 2.76-fold escalation in bioavailability.

Tunable nanocarrier morphologies from glycopolypeptide-based amphiphilic biocompatible star copolymers and their carbohydrate specific intracellular delivery - Pati, Debasis; Das, Soumen; Patil, Naganath G.; Parekh, Nimisha; Anjum, Dalaver H.; Dhaware, Vinita; Ambade, Ashootosh V.; Sen Gupta, Sayam (Biomacromolecules, 2016)
Nanocarriers with carbohydrates on the surface represent a very interesting class of drug-delivery vehicles because carbohydrates are involved in biomolecular recognition events in vivo. We have synthesized biocompatible miktoarm star copolymers comprising glycopolypeptide and poly(e-caprolactone) chains using ring-opening polymerization and ``click chemistry''. The amphiphilic copolymers were self-assembled in water into morphologies such as nanorods, polymersomes, and micelles with carbohydrates displayed on the surface. We demonstrate that the formation of nanostructure could be tuned by chain length of the blocks and was not affected by the type of sugar residue. These nanostructures were characterized in detail using a variety of techniques such as TEM, AFM, cryogenic electron microscopy, spectrally resolved fluorescence imaging, and dye encapsulation techniques. We show that it is possible to sequester both hydrophobic as well as hydrophilic dyes within the nanostructures. Finally, we show that these noncytotoxic mannosylated rods and polymersomes were selectively and efficiently taken up by MDA-MB-231 breast cancer cells, demonstrating their potential as nanocarriers for drug delivery.

Tuning emission responses of a triphenylamine derivative in host-guest complexes and an unusual dynamic inclusion phenomenon - Gangopadhyay, Monalisa; Mandal, Amal K.; Maity, Arunava; Ravindranathan, Sapna; Rajamohanan, Pattuparambil R.; Das, Amitava (Journal of Organic Chemistry, 2016)
A newly synthesized triphenylamine derivative (1Cl(3)) shows significant differences in inclusion complex formation with two different macrocyclic hosts, cucurbit[7]uril (CB[7]) and beta-cyclodextrin (beta-CD). Detailed investigations by NMR spectroscopy reveal that CB[7] forms a 1:3 host-guest complex ([1 center dot 3{CB[7]}]Cl-3) in which three arms of 1Cl(3) are bound to three host molecules. On the other hand, beta-CD forms a dynamic 1:1 inclusion complex ([1 center dotbeta-CD]Cl-3) by binding to only one of the three arms of 1Cl(3) at a given time. The formation of a 1:1 host-guest complex with beta-CD and 1:3 host-guest complex with CB[7] was also confirmed from the results of the isothermal titration calorimetric studies. Interestingly, 1Cl(3) exhibits a rare dual emission property in solution at room temperature with the lower and higher energy bands arising from a locally excited state and an intramolecular charge-transfer transition, respectively. The difference in inclusion complex formation behavior of 1Cl(3) with the two macrocyclic hosts results in the stabilization of different emission states in the two inclusion complexes. The fundamental difference in the electrostatic surface potentials, cavity polarities, and shapes of the two macrocyclic hosts could account for the formation of the different inclusion complexes with distinct luminescence responses.

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.

Understanding the electron transfer process in ZnO-naphthol azobenzoic acid composites from photophysical characterisation - George, Leena; Kunhikannan, Athira K.; Illathvalappil, Rajith; Ottoor, Divya; Kurungot, Sreekumar; Devi, R. Nandini (Physical Chemistry Chemical Physics, 2016)
Semiconductor nanoparticles surface modified with organic molecules capable of visible light absorption and effectively transferring the electrons to the catalytic sites have the potential to be good photocatalysts. ZnO nanoparticles of size similar to 3 nm are grafted with two azonaphthols, one conjugated and the other non-conjugated. The photophysical properties of modified ZnO indicate an effective electron transfer from the conjugated azonaphthol to ZnO but not in the case of the non-conjugated molecule. It is also observed from lifetime studies that the conjugated molecule stabilises the defect sites on ZnO nanoparticles. It is possible that excited electrons from the conjugated molecule are transferred to specific defect sites in ZnO. This apparently does not occur in the non-conjugated molecule, bringing to focus the importance of the photophysical characteristics of organic modifiers in designing visible light active photocatalysts.

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.

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

Use genetic programming for selecting predictor variables and modeling in process identification - Verma, Devendra; Goel, Purva; Patil-Shinde, Veena; Tambe, Sanjeev S. (2016 Indian Control Conference (ICC), 2016)
Availability of an accurate and robust dynamic model is essential for implementing the model dependent process control. When first principles based modeling becomes difficult, tedious and/or costly, a dynamic model in the black-box form is obtained (process identification) by using the measured input-output process data. Such a dynamic model frequently contains a number of time delayed inputs and outputs as predictor variables. The determination of the specific predictor variables is usually done via a trial and error approach that requires an extensive computational effort. The computational intelligence (CI) based data-driven modeling technique, namely, genetic programming (GP) can search and optimize both the structure and parameters of a linear/nonlinear dynamic process model. It is also capable of choosing those predictor variables that significantly influence the model output. Thus usage of GP for process identification helps in avoiding the extensive time and efforts involved in the selection of the time delayed input-output variables. This advantageous GP feature has been illustrated in this study by conducting process identification of two chemical engineering systems. The results of the GP-based identification when compared with those obtained using the transfer function based identification clearly indicates the outperformance by the former method.
2nd Indian Control Conference (ICC), Indian Inst Technol, Hyderabad, INDIA, JAN 04-06, 2016
Keywords: dynamic model; genetic programming; predictor variable; process identification; Sensitivity analysis

Valorization of coffee bean waste: a coffee bean waste derived multifunctional catalyst for photocatalytic hydrogen production and electrocatalytic oxygen reduction reactions - Unni, SreeKuttan M.; George, Leena; Bhange, Siddheshwar N.; Devi, R. Nandini; Kurungot, Sreekumar (RSC Advances, 2016)
Here, we report the valorization of coffee bean waste (CBW) by producing nitrogen doped porous carbon (p-Cof) having both photocatalytic and electrocatalytic properties using a silica templating method. Morphological investigation of p-Cof reveals the presence of assemblies of highly porous flat carbon blocks. p-Cof exhibits a high surface area (1213 m(2) g(-1)) and a wide range of micro-and mesopores with good electrical conductivity. Along with this, the surface of p-Cof displays the presence of graphitic and pyridone-type nitrogen coordinations, which help p-Cof to perform as a multifunctional catalyst as revealed from its catalytic activities towards photocatalytic hydrogen production (PHP) and electrocatalytic oxygen reduction reactions. p-Cof produces 334 mu mol h(-1) g(-1) of hydrogen from water under visible light and 575 mmol h(-1) g(-1) of hydrogen under solar light irradiation with excellent stability. Along with this, p-Cof also displays improved oxygen reduction reaction (ORR) activity in alkaline medium. A better onset potential (0.91 V vs. RHE) and half-wave potential (0.75 V vs. RHE) are displayed by p-Cof compared to the catalyst derived from the simple annealing of CBW without employing the silica template. Along with the better electrochemical activity, p-Cof shows excellent ORR kinetics and electrochemical stability compared to the current state-of-the-art Pt/C.

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

[3+2]-Annulation of platinum-bound azomethine ylides with distal C[double bond, length as m-dash]C bonds of N-allenamides - Chakrabarty, Indradweep; Inamdar, Suleman M.; Akram, Manjur O.; Gade, Amol B.; Banerjee, Subhrashis; Bera, Saibal; Patil, Nitin T. (Chemical Communications, 2017)
A Pt-catalyzed, highly regioselective reaction between N-allenamides and imino-alkynes leading to pyrrolo[1,2-a] indoles is described. This represents the first example of [3+2]-annulation of Pt-bound azomethine ylides with the distal CQC bond of N-allenamides. The mechanism of the reaction was established by computational studies.

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.

AgOTf-catalyzed dehydrative [3+2] annulation of aziridines with 2-naphthols - Kaicharla, Trinadh; Jacob, Anu; Gonnade, Rajesh G.; Biju, Akkattu T. (Chemical Communications, 2017)
The reaction of 2-naphthols with aziridines in the presence of AgOTf resulting in a dehydrative, formal [3+2] annulation is reported. The reaction allows the synthesis of functionalized benzoindolines, and tolerates a broad range of functional groups. A preliminary study on themechanism of this reaction indicates an SN1-type ring-opening of aziridines. This method is demonstrated for the one-pot synthesis of benzoindoles.

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.

Ambient CO oxidation on in-situ generated Co3O4 spinel surfaces with random morphology - Dubey, Anjani; Reddy, Kasala Prabhakar; Gopinath, Chinnakonda S. (ChemistrySelect, 2017)
The influence of the Co3O4 morphology on its redox behavior and catalytic performance in the CO oxidation reaction is studied. Three different Co3O4 morphologies were synthesized by precipitation and hydrothermal methods. TEM and SEM observations clearly show the different obtained morphologies: rods, wires and a mixture of plates and cubes. The textural properties depend on the morphology and the redox ones on the particle size. XRD analysis reveals a spinel structure in all solids but a preferential exposition of the [110] plane is presented in the Co3O4 rods. This preferential exposition, along with its higher specific surface area provides the rods with more efficient oxygen storage capacity resulting in an excellent catalytic performance compared to the other two morphologies.

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.

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

Auger decay rates of core hole states using equation of motion coupled cluster method - Ghosh, Aryya; Vaval, Nayana; Pal, Sourav (Chemical Physics, 2017)
The recent development of Linac coherent light source high intense X-ray laser makes it possible to create double core ionization in the molecule. The generation of double core hole state and its decay is identified by Auger spectroscopy. The decay of this double core hole (DCH) states can be used as a powerful spectroscopic tool in chemical analysis. In the present work, we have implemented a promising approach, known as CAP-EOMCC method, which is a combination of complex absorbing potential (CAP) and equation -of-motion coupled cluster (EOMCC) approach to calculate the lifetime of single and double core hole states. We have applied this method to calculate the lifetime of the single core hole (K-LL) and double core hole (KK-KLL) states of CH4, NH3 and HF molecules. The predicted lifetime is found to be extremely short. (C) 2016 Elsevier B.V. All rights reserved.

Base-free and catalyst-free synthesis of functionalized dihydrobenzoxazoles via vinylogous carbonate to carbamate rearrangement - Das, Tamal Kanti; Mondal, Santigopal; Gonnade, Rajesh G.; Biju, Akkattu T. (Organic Letters, 2017)
An unexpected, catalyst-free, and base-free intramolecular cyclization of N-aryloxyacrylate aldimines, under thermal conditions leading to the synthesis of functionalized dihydrobenzoxazoles, is reported. The reaction features a unique rearrangement of vinylogous carbonates to vinylogous carbamates resulting in a new carbon–oxygen and carbon–nitrogen bond construction. The reaction tolerates a broad range of functional groups and the desired products are formed in moderate to good yields.

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.

Biomimetic total synthesis of angiopterlactone B and other potential natural products - Kotammagari, Tharun K.; Gonnade, Rajesh G.; Bhattacharya, Asish K. (Organic Letters, 2017)
A one-pot biomimetic synthesis of (-)-angiopterlactone B and its enantiomer (+)-angiopterlactone B has been accomplished via TBAF-catalyzed tandem ring contraction followed by oxa-Michael/Michael addition sequence. Comparison of specific optical rotations, absolute configurations, and CD spectra of natural, synthesized (-)-angiopterlactone B and (+)-angiopterlactone B unequivocally proves that the isolated angiopterlactone B must be levorotatory. Synthesis of hitherto undiscovered natural products 18 and 20 and analogues of angiopterlactone B demonstrate the versatility of this method.

Biotransformation of penicillin V to 6-aminopenicillanic acid using immobilized whole cells of E. coli expressing a highly active penicillin V acylase - Avinash, Vellore Sunder; Chauhan, Palna Dinesh; Gaikwad, Shraddha; Pundle, Archana (Preparative Biochemistry & Biotechnology, 2017)
The production of 6-aminopenicillanic acid (6-APA) is a key step in the manufacture of semisynthetic antibiotics in the pharmaceutical industry. The penicillin G acylase from Escherichia coli has long been utilized for this purpose. However, the use of penicillin V acylases (PVA) presents some advantages including better stability and higher conversion rates. The industrial application of PVAs has so far been limited due to the nonavailability of suitable bacterial strains and cost issues. In this study, whole-cell immobilization of a recombinant PVA enzyme from Pectobacterium atrosepticum expressed in E. coli was performed. Membrane permeabilization with detergent was used to enhance the cell-bound PVA activity, and the cells were encapsulated in calcium alginate beads and cross-linked with glutaraldehyde. Optimization of parameters for the biotransformation by immobilized cells showed that full conversion of pen V to 6-APA could be achieved within 1 hr at pH 5.0 and 35 degrees C, till 4% (w/v) concentration of the substrate. The beads could be stored for 28 days at 4 degrees C with minimal loss in activity and were reusable up to 10 cycles with 1-hr hardening in CaCl2 between each cycle. The high enzyme productivity of the PVA enzyme system makes a promising case for its application for 6-APA production in the industry.

Can fungi compete with marine sources for chitosan production? - Ghormade, V. (International Journal of Biological Macromolecules, 2017)
Chitosan, a β-1,4-linked glucosamine polymer is formed by deacetylation of chitin. It has a wide range of applications from agriculture to human health care products. Chitosan is commercially produced from shellfish, shrimp waste, crab and lobster processing using strong alkalis at high temperatures for long time periods. The production of chitin and chitosan from fungal sources has gained increased attention in recent years due to potential advantages in terms of homogenous polymer length, high degree of deacetylation and solubility over the current marine source. Zygomycetous fungi such as Absidia coerulea, Benjaminiella poitrasii, Cunninghamella elegans, Gongrenella butleri, Mucor rouxii, Mucor racemosus and Rhizopus oryzae have been studied extensively. Isolation of chitosan are reported from few edible basidiomycetous fungi like Agaricus bisporus, Lentinula edodes and Pleurotus sajor-caju. Other organisms from mycotech industries explored for chitosan production are Aspergillus niger, Penicillium chrysogenum, Saccharomyces cerevisiae and other wine yeasts. Number of aspects such as value addition to the existing applications of fungi, utilization of waste from agriculture sector, and issues and challenges for the production of fungal chitosan to compete with existing sources, metabolic engineering and novel applications have been discussed to adjudge the potential of fungal sources for commercial chitosan production.
Keywords: Cell wall; Chitin/chitosan; Waste Mycelial Biomass; Zygomycetous Fungi

Cascade energy transfer and tunable emission from nanosheet hybrids: locating acceptor molecules through chiral doping - Goudappagouda; Wakchaure, Vivek Chandrakant; Ranjeesh, Kayaramkodath Chandran; Abhai, Chalona Antony Ralph; Babu, Sukumaran Santhosh (Chemical Communications, 2017)
Light harvesting donor-acceptor assemblies are indispensable to efficiently tap photons. In an attempt to improve the light harvesting efficiency of an acceptor doped assembly, we design and synthesize a donor-acceptor-donor triad which exhibits an exceptional intramolecular energy transfer with excellent efficiency. Moreover, a facile cascade energy transfer (energy funnelling) is observed in the presence of a series of second acceptors (63-91% efficiency) with tunable emission colours. Self-assembled nanosheets formed by the triad in the presence of acceptors exhibit cascade energy transfer assisted tunable emission. In addition, use of chiral acceptors induces chirality to the triad and results in the formation of chiral nanosheets alongwith cascade energy transfer. Here chiral induction, nanosheet formation and cascade energy transfer in the presence of chiral acceptors are used as tools to probe the intercalation of acceptor molecules in the donor scaffold.

Catalytic enantioselective aza-piancatelli rearrangement - Gade, Amol B.; Patil, Nitin T. (Synlett, 2017)
The design and development of an enantioselective aza-Piancatelli rearrangement reaction are described. In the presence of a chiral phosphoric acid catalyst, furylcarbinols react with anilines to afford highly functionalized cyclopentenones with excellent diastereo-and enantioselectivities. The process was shown to be scalable, and up to 1 gram of starting material could be employed under mild reaction conditions.

Catalytic macroporous biohydrogels made of ferritin-encapsulated gold nanoparticles - Kumari, Sushma; Haring, Marleen; Sen Gupta, Sayam; Diaz, David Diaz (Chempluschem, 2017)
Reported is a modular approach for the incorporation and stabilization of gold nanoparticles inside a three-dimensional macroporous hydrogel made of ferritin. The strategy, which involves the dynamic templating of surfactant H-1 domains, demineralization, and remineralization helps to overcome aggregation and degradation issues usually associated with bare-metal-based nanocatalysts. The catalytic activity of the so-synthesized bionanocomposite hydrogel was demonstrated in both nitroaldol (Henry) and nitroreduction model reactions in aqueous solution at room temperature. An interesting synergistic effect between basic residues of the protein and the gold nanoparticles was found in the nitroaldol reaction when carried out in water in the presence of a phase-transfer catalyst. Furthermore, the reduction of 4-nitrophenol and 4-nitroaniline catalyzed by the nanocomposite scaffold in the presence of NaBH4 proceeded significantly faster than that using other known Au- and Ag-based catalysts under similar conditions.

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.