Understanding positive and negative deviations in polarity of ionic liquid mixtures by pseudo-solvent approach - Beniwal, Vijay; Kumar, Anil (Physical Chemistry Chemical Physics, 2016)
Physico-chemical properties of liquid mixtures in general display large deviations from linear behaviour, arising out of complex specific and non-specific intermolecular interactions. The polarity of liquid mixtures displaying large positive and negative deviations can be minimized and linear mixing can be achieved in liquids using a pseudo-solvent methodology. The work described herein is designed to investigate the influence of different physical parameters on the linear pseudo-solvent composition in ionic liquid mixtures. For this purpose, we have determined the deviations from linearity, Delta E-T(N) values (defined as Delta E-T(N) = E-Texp.(N) - E-Tlin mix.(N) with E-Tlin mix.(N) given by Sigma(n)(i=0) E-Ti(N0) x(i)) for binary mixtures of a variety of ionic liquids, including two molecular solvents, DMSO and formamide. Firstly, the investigations were carried out in three 1-butyl-3-methylimidazolium cation based aprotic ionic liquids and the roles of anionic structure and hydrogen bond acceptor basicities (beta values) of the ionic liquids were determined. The influence of the cationic structure, i.e., the hydrogen bond donor acidity (alpha values) and non-associative nature of the ionic liquids, was determined using C2-methylated analogs, 1-butyl-2,3-dimethylimidazolium cation based ionic liquids. The role of the protic nature of ionic liquids was studied in two protic ionic liquids, viz., 1-methylimidazolium formate and 1-methylimidazolium acetate. The effects of the temperature, pseudo-solvent structure and solvatochromic probe structure on the Delta E-T(N) values were also explored.

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.

Understanding the role of Keggin type heteropolyacid catalysts for glycerol acetylation using toluene as an entrainer - Kale, S. S.; Armbruster, U.; Eckelt, R.; Bentrup, U.; Umbarkar, Shubhangi B. (Applied Catalysis A-General, 2016)
The heterogeneously catalyzed esterification (acetylation) of glycerol toward triacetin in batch mode in presence of toluene as entrainer was studied. Silicotungstic acid, tungstophosphoric acid and phosphomolybdic acid as heteropolyacids (HPAs) supported on silica, alumina or silica-alumina were used as catalysts. The course of the reaction was found to be very sensitive to the nature of the HPA as well as the support. Solid characterization by Raman spectroscopy, XRD, and pyridine-FTIR revealed that only combinations of tungsten-based HPAs and silica support were able to preserve the structure of active component throughout the preparation process, which was essential to obtain active and selective catalysts. The interaction between HPA and support was decisive for stability and dispersion of the catalytically active species. With the best performing catalyst H4SiW12O40/SiO2, selectivity to triacetin reached 71% at complete conversion within 24h. The high selectivity to triacetin is attributed the Brensted acidic sites originated from stabilized Keggin structure and continuous removal of water during course of reaction. Toluene is able to form azeotropic mixtures with water and acetic acid and keeps the reaction temperature below the boiling point of acetic acid. Thus, water-free reaction conditions can be established. The catalyst was reusable; however, the activity and selectivity towards triacetin slightly decreased in a repetition run due to loss of active sites. (C) 2016 Elsevier B.V. All rights reserved.

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

Utilization of banana peel for the removal of benzoic and salicylic acid from aqueous solutions and its potential reuse - Pathak, Pranav D.; Mandavgane, Sachin A.; Kulkarni, Bhaskar D. (Desalination and Water Treatment, 2016)
We report on the adsorptive removal of benzoic acid (BA) and salicylic acid (SA) using banana peel (BP), an abundantly available agricultural waste material, for the first time. BP was characterized by proximate analysis, FT-IR, scanning electron microscopy, BET surface area, and XRF. The number of basic sites on BP (4.9mmolg(-1)) is relatively more than acidic sites (0.75mmolg(-1)). The Langmuir uptake capacity values obtained are 6.62mgg(-1) for BA and 9.80mgg(-1) for SA. A mechanism for binding acid molecule to the BP surface is proposed.
Keywords: Adsorption; Banana peel; Benzoic acids; Salicylic acid; Wastewater treatment

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

Valorization of banana peel: a biorefinery approach - Pathak, Pranav D.; Mandavgane, Sachin A.; Kulkarni, Bhaskar D. (Reviews in Chemical Engineering, 2016)
Banana peel (BP) is an agrowaste produced in large volumes annually, especially by food-processing industries; however, its disposal is of significant concern. However, recent research suggests that BP is a valuable source of bioactive compounds, which can be converted into value-added products. This article reviews the conversion process of value-added products from BP and provides an outline on the chemical composition of BP and its possible applications. In addition, we also discuss the - utilization of BP as a substrate to produce animal feed, biofertilizer, dietary fibers, clean energy, industrial enzymes, as well as its use in the synthesis of nanomaterials. Based on the research conducted so far, it is obvious that BP has a wide variety of applications, and thus, developing a biorefinery approach to adequately utilize BP will help realize its economic benefits to the fullest. Based on the valorization of BP, a scheme for BP biorefinery has been proposed. A material balance for BP biorefinery for 1-ton bone-dry BP is presented and our results show that 432 kg of protein or 170 kg of citric acid, 170 kg of pectin, 325 m(3) of ethanol, and 220 m(3) of methane can be produced.

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.

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

Wide band gap and conducting tungsten carbide(WC) thin films prepared by hot wire chemical vapor deposition(HW-CVD) method - Pawbake, Amit; Waykar, Ravindra; Jadhavar, Ashok; Kulkarni, Rupali; Waman, Vaishali; Date, Abhijit; Late, Dattatray J.; Pathan, Habib; Jadkar, Sandesh (Materials Letters, 2016)
In this letter, we report synthesis of tungsten carbide (WC) thin films having wide band gap(3.22-3.3 eV) with high electrical conductivity (80-1260 S/cm) by HW-CVD using heated using heated W filament and Tetra-fluoro-methane (CF4) gas. Formation of WC was confirmed by low angle XRD, Raman spectroscopy and x-ray photoelectron spectroscopy. UV-Visible spectroscopy analysis revealed that the synthesized films have high transmission at wavelength 500 nm. Electrical properties measured using Hall measurement show that these films are semiconductor. The obtained results imply that the growth of WC thin films is mainly from the atomic species(W and C) evaporated from the hot filament. The HW-CVD opens a novel route to synthesize wide band gap and conducting WC at a cost-efficient way for DSSCs and hydrogen evolution reaction (HER). (C) 2016 Elsevier B. V. All rights reserved.

Abundance matters: role of albumin in diabetes, a proteomics perspective - Bhat, Shweta; Jagadeeshaprasad, Mashanipalya G.; Venkatasubramani, Vinashya; Kulkarni, Mahesh J. (Expert Review of Proteomics, 2017)
Introduction: Human serum albumin (HSA) is a multifaceted protein with vital physiological functions. It is the most abundant plasma protein with inherent capability to bind to diverse ligands, and thus susceptible to various post-translational modifications (PTMs) which alter its structure and functions. One such PTM is glycation, a non-enzymatic reaction between reducing sugar and protein leading to formation of heterogeneous advanced glycation end products (AGEs). Glycated albumin (GA) concentration increases significantly in diabetes and is implicated in development of secondary complications. Areas covered: In this review, we discuss in depth formation of GA and its consequences, approaches used for characterization and quantification of GA, milestones in GA proteomics, clinical relevance of GA as a biomarker, significance of maintaining abundant levels of albumin and future perspectives. Expert commentary: Elevated GA levels are associated with development of insulin resistance as well as secondary complications, in healthy and diabetic individuals respectively. Mass spectrometry (MS) based approaches aid in precise characterization and quantification of GA including early and advanced glycated peptides, which can be useful in prediction of the disease status. Thus GA has evolved to be one of the best candidates in the pursuit of diagnostic markers for prediction of prediabetes and diabetic complications.

Access to fused tricyclic gamma-butyrolactones, a natural product -like scaffold - Kalmode, Hanuman P.; Handore, Kishor L.; Reddy, D. Srinivasa (Journal Of Organic Chemistry, 2017)
Serendipitous findings of an acid mediated skeletal rearrangement of bicydo-beta-ketoester having cyclopropyl ring to access fused tricyclic gamma-butyrolactones has been described. This novel transformation has been optimized to 30 mol% p-toluenesulfonic acid (p-TSA) in toluene using Dean Stark apparatus, where the aldol condensation, cyclopropyl ring opening followed by cyclization took place in a single-pot operation. The resulting tricyclic compounds are interesting chemotype with natural product resemblance and may find useful applications in the future.

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

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

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

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.

Agro-industrial wastes for production of biosurfactant by bacillus subtilis ANR 88 and its application in synthesis of silver and gold nanoparticles - Rane, Ashwini N.; Baikar, Vishakha V.; Kumar, D. V. Ravi; Deopurkar, Rajendra L. (Frontiers in Microbiology, 2017)
Biosurfactants, surface-active amphiphilic compounds, despite having a wide range of applications, have a high cost of production, which severely restricts their use. For cheaper production of biosurfactant, we investigated the potential of the indigenously isolated biosurfactant producing organism, Bacillus subtilis ANR 88, to grow on different cheap carbon sources (molasses, whey, and extracts of potato peels, orange peels, banana peels, and bagasse). We found that, B. subtilis ANR 88 used significant amounts of total sugar to produce cell biomass and biosurfactant. The biosurfactant production in minimal medium containing glucose as sole source of carbon was 0.207 g/l and the same with molasses as carbon source was 0.241 g/l. With whey as carbon source, isolate failed to produce biosurfactant. Amongst the extracts of the agro-wastes, the extracts of bagasse and orange peels gave 0.127 and 0.089 g/l of biosurfactant respectively. One-variable-at-a-time (OVAT) studies carried out to optimize the production of biosurfactant by B. subtilis ANR 88 resulted into maximum biosurfactant yield of 0.513 g/l in medium: molasses 4%, ammonium ferric citrate 0.25%, pH 7. Plackett-Burman design based statistical method for optimization increased the production of biosurfactant to 0.746 g/l, which is 3.6-fold of that produced on glucose. The biosurfactant produced by B. subtilis ANR 88 was analyzed by Fourier Transform Infrared Spectroscopy (FT-IR); it showed that the biosurfactant contained alkyl as well as peptide groups. The biosurfactant of B. subtilis ANR 88 was found effective in the synthesis of silver as well as gold nanoparticles in the total absence of conventional chemical reducing agents. Interestingly, nanoparticles produced were almost uniform in their size and shapes i.e., spherical silver (4-18 nm) and hexagonal gold nanoparticles (40-60 nm), as evident in TEM images.

All-solid-state-supercapacitor possessing a non-aqueous gel polymer electrolyte prepared using a UV-assisted in situ polymerization strategy - Vijayakumar, V.; Anothumakkool, B.; Torris, A. T. A.; Nair, S. B.; Badiger, M. V.; Kurungot, S. (Journal of Materials Chemistry A, 2017)
In this work, we report the synthesis of a high ionic conducting and mechanically stable non-aqueous gel polymer electrolyte (GPE) in which a liquid electrolyte (LiClO4/propylene carbonate) is entrapped in a poly(2-hydroxy-3-phenoxy propyl acrylate) matrix by a UV assisted in situ polymerisation strategy. Unlike conventional dry and quasi-solid non-aqueous GPEs, our system (H-P-L-3M-80%) shows an excellent ionic conductivity of 4.7 x 10(-3) S cm(-1), a value which is comparable to those of non-aqueous liquid electrolytes. The high mechanical stability of GPE arises due to the covalent cross-links present in the polymer matrix as well as the reversible non-covalent cross-links between the solvent and the polymer matrix through the Li+ cations. Subsequently, the GPE has been prepared in situ on the inner and the outer surface of the electrode material to fabricate a 2.0 V supercapacitor device with a high mass loading (3.8 mg cm(-2)) of the active material (YP-80F, a high surface area porous carbon). The device shows an equivalent series resistance (ESR) as low as 2.2 Omega, which is close to that of the device fabricated from the corresponding liquid electrolyte and is far better than those of the devices evolved from conventional GPEs and dry polymer electrolytes. The mass specific capacitance of 113 F g(-1) obtained at a current density of 2 mA cm(-2) shows 81% retention even at a high current density of 20 mA cm(-2). The scalability of the strategy is demonstrated by fabricating a large area (area = 16 cm(2), loading = 4.0 mg cm(-2)) all-solid-state flexible-supercapacitor (H-P-L-3M-S-4.0) device which can be operated at a potential window of 2.5 V. The device was found to show a mass specific capacitance of 111 F g(-1) at a current density of 1 mA cm(-2) (0.25 A g(-1)), all the while, retaining a very low ESR of 2.2 Omega. The potential of the strategy to mimic the liquid-like electrode-electrolyte interface, augmented with the ability to tune further, opens up new horizons for energy storage devices.

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

Anti-microbial activity of chrysomycin a produced by streptomyces sp. against mycobacterium tuberculosis - Balaji, Muralikrishnan; Dan, Vipin Mohan; Joseph, Vinodh; Jamsheena, Vellekkatt; Ramachandran, Ranjit; Thomas, Sabu; Dastager, Syed Gulam; Kumar, K. Santhosh; Lankalapalli, Ravi Shankar; Kumar, R. Ajay (RSC Advances, 2017)
Limited efficacy of the BCG (Bacillus Calmette–Guérin) vaccine against adult tuberculosis and the emergence of resistance to existing anti-tuberculosis drugs compel discovery of novel antibiotics against Mycobacterium tuberculosis. Actinomycetes are still an attractive platform for the discovery of new antimicrobials, especially from untapped natural hotspots, despite the belief that they are an exhausted resource after repeated re-discoveries. Herein we report the isolation and identification of chrysomycin A from an actinomycete isolated from a coastal area in Kerala. We show for the first time that it has antimycobacterial activity. It was found to be bactericidal to planktonic and intracellular M. tuberculosis with an MIC of 3.125 μg mL⁻¹; it is non-hemolytic and has negligible cytotoxicity. The actinomycete that produces chrysomycin A was found to be a Streptomyces sp. through 16S rRNA gene sequencing.

Application of unusual grignard reaction for the stereoselective synthesis of antidepressant drug (R)-(-)-venlafaxine - Chavan, Subhash P.; Khatod, Harshali S. (Synthesis-Stuttgart, 2017)
An enantioselective synthesis of antidepressant drug (R)-(-)-venlafaxine is accomplished as an application of recently explored unusual Grignard reaction. An innovative method for the generation of chirality at extremely reactive benzylic center along with determination of absolute stereochemistry has been discussed. The key steps involved in the synthesis include Sharpless asymmetric dihydroxylation for the induction of chirality and an unusual Grignard reaction.

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

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

Biomedical literature mining for protein-protein interactions analysis using electronic mailing system - Karthikeyan, Muthukumarasamy; Vyas, Renu (253rd National Meeting of the American-Chemical-Society (ACS) on Advanced Materials, Technologies, Systems, and Processes, 2017)

Biomimetic synthesis of CdSe nanoparticles with potential bioimaging applications - Ansary, Abu Ayoobul; Uddin, Imran; Khan, Muhammed I. (International Journal of Pharmaceutical Sciences and Research, 2017)
This study presents in vitro biomimetic synthesis of CdSe nanoparticles using the enzyme, NADPH dependent-Nitrate reductase purified from fungus, Fusarium oxysporum. The synthesis of CdSe nanoparticles was accomplished in the presence of a synthetic peptide having amino acid sequence (γ-Glu-Cys-Glu-Cys)-Gly, which acted as binding molecule. The nanoparticles were synthesized in the size range of 3.9–9.0 nm was analysed using TEM. Further characterization of nanoparticles was done using techniques such as UV, PL, XPS, and FTIR. The as-synthesized CdSe nanoparticles were water dispersible containing free reactive amino groups. These CdSe nanoparticles were conjugated with bi-antennary and tri-antennary glycopeptides opening up the possibilities for their applications in bioimaging. These significant observations will help better understand the mechanism of biosynthesis of fluorescent nanoparticles using fungi. These findings promise an alternative strategy for an eco-friendly, economical, and large-scale synthesis of water dispersible CdSe nanoparticles. These CdSe nanoparticles have promising biomedical-imaging applications without a need for further functionalization.

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.

Biosurfactant surfactin as a kinetic promoter for methane hydrate formation - Bhattacharjee, Gaurav; Barmecha, Vivek; Pradhan, Darshan; Naik, Rajesh; Zare, Kirti; Mawlankar, Rahul R.; Dastager, Syed Gulam; Kushwaha, Omkar Singh; Kumar, Rajnish (Energy Procedia, 2017)
In the present study, the effect of the biosurfactant Surfactin on methane hydrate formation kinetics was studied. Initially, several marine derived species were screened for the presence of Surfactin. The polymerase chain reaction technique was used as the preliminary screening step for Surfactin which was then followed up by a couple of different assays to provide conclusive evidence of the same. Based on these tests, the D-9 bacterial strain was identified as a producer of Surfactin. Once the presence of Surfactin had been proven, its effect on methane hydrate formation kinetics was investigated upon by carrying out hydrate formation experiments in a stirred tank reactor. The cell free supernatant containing Surfactin was itself used as the hydrate forming solution without any further processing. It was found that the presence of Surfactin in the system greatly enhances hydrate formation kinetics as compared to pure water. In fact the kinetics in presence of Surfactin also surpassed that obtained with 1 wt% SDS, the most commonly used synthetic kinetic hydrate promoter. This basic study can pave the way for more sophisticated research on the use of biosurfactants as kinetic promoters with a view on rapid methane hydrate formation kinetics for applications such as methane separation, storage and transport.

Biotechnological interventions to modulate terpenoid indole alkaloid pathway in catharanthus roseus using in vitro tools and approaches - Verma, P.; Khan, S. A.; Parasharami, V.; Mathur, A. K. (Catharanthus Roseus: Current Research and Future Prospects, 2017)
Catharanthus roseus plant is valued for harboring more than 130 bioactive terpenoid indole alkaloids (TIAs) including the two of its leaf derived bisindole alkaloids-vinblastine and vincristine which are indispensible constituents of antineoplastic drugs used in metastatic malignancy associated with acute lymphoblastic leukaemia's and Hodgkin's/Non-Hodgkin's lymphomas. The extremely low in planta occurrence of TIAs in C. roseus plants resulting in high commercial demand and exorbitant price have brought this herb in focus of an intense scientific scrutiny in last 30 years. Research efforts have so far advanced in two major directions: towards understanding the enzymology and genetic regulation of the concerned metabolic pathway(s) leading to TIAs biosynthesis in plant and, secondly, exploring the possibility of developing cell/tissue culture based platforms for in vitro TIAs production to meet the industry's demand. Designing plants, free from such metabolic constraints, can be a possible approach to enhance the production of plant based medicines. This subject of plant metabolic engineering is gaining lot of attention these days. Pathway manipulation using the modern tools of genetic engineering to over-express a limiting enzyme or to suppress the expression of an enzyme using a shared substrate of a branched pathway are attractive options of metabolic engineering for diverting the metabolic flux towards the synthesis of a desired end product. Knowledge, thus gained, indicates that TIAs biogenetic route is characterized by extensive metabolic cross-talk and shuttling of at least 35 intermediates synthesized via 30 enzymatic reactions occurring in four different types of tissues (epidermis, internal phloem parenchyma, idioblasts and leticifers) and five different sub-cellular compartments (cytosol, vacuole, thyllakoid membrane, nucleus and endoplasmic reticulum). The complexity is further compounded by extremely high level of recalcitrancy of C. roseus plant for regeneration and Agrobacterium- mediated genetic transformation for pathway engineering. As a consequence, all genetic modulation efforts so far made in C. roseus are confined to cell suspension and transformed hairy root cultures that lack the required level of cyto- and tissue- differentiation essential for the expression of entire TIAs pathway genes and enzymes. A perusal of published work in C. roseus clearly suggests that inspite of several pathway manipulation/engineering attempts, the level of TIAs production in cell/tissue/hairy root cultures of this herb could never be enhanced to the level of expectations. The enzymatic, developmental and environmental rigidity/complexi- ties associated with the biosynthetic pathway of these alkaloids have often been cited as possible reasons for these disappointing outcomes Therefore, three major areas of investigation are in focused attention of Catharanthus researchers' the world over are: (1) how to select or design the starting cells or tissue(s) to realize the full potential of applying metabolic engineering tools for up-regulating the TIAs pathway in them; (2) how to overcome the strong recalcitrancy of Catharanthus plant tissues for de novo organogenesis and in vitro plant regeneration for whole plant-level expression of a transgene coding either for a limiting pathway enzyme or a transcription factor that can control the global expression of several pathway genes and, (3) how to overcome the inability of non-differentiated cell cultures to execute those pathway steps that are expressed only in specialized tissues/cells of C. roseus plants. Various biotechnological approaches and generation of novel tissue types have been discussed in the present chapter for the modulation and increased TIAs flux in C. Roseus.

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

Capillary uptake in macroporous compressible sponges - Chatterjee, Soumyajyoti; Doshi, Pankaj; Kumaraswamy, Guruswamy (Soft Matter, 2017)
The capillarity-driven uptake of liquid in swellable, highly porous sponges is of significant industrial importance. Sponges prepared using polymers and their composites with carbon nanotubes and graphene have been reported, with extraordinary solvent uptake capacities and with the ability to separate oil from water. However, the effect of systematic variation of sponge characteristics on solvent uptake has not been investigated. Here, we report experiments that study capillary uptake in a variety of flexible, centimetre-sized macroporous cylindrical sponges. We used ice-templating to prepare a series of model macroporous sponges in which the porosity, modulus and composition were systematically varied. We investigated two kinds of sponge: (a) those composed purely of cross-linked polymers and (b) those prepared as composites of inorganic particles and polymers. Both kinds of sponge are flexible and exhibit elastic recovery after large compressive deformation. All sponges were characterized thoroughly with respect to their pore microstructure and elastic modulus. When one end of a sponge is plunged into a large reservoir, water rises through capillary action against gravity. We observed a transition from an inertial capillary regime, where the liquid column height rose linearly with time, t, to a viscous capillary regime, where the liquid height rose with time t(0.5). We showed that these results can be rationalized using analyses developed for rigid sponges. We combined differential momentum balance equations for uptake in rigid capillaries with the phenomenological Ergun-Forchheimer relations to account for the effect of the sponge microstructure. This approach works remarkably well in the viscous capillary regime and shows that capillary uptake is governed primarily by the total porosity and pore dimensions of soft sponges.
Keywords: aerogels; Building blocks; Catalyst Supports; Contact-angels; Dynamics; flow; Organic Liquids; Porous-Media; Rise

Carbonylation of glycerol with urea to glycerol carbonate over supported Zn catalysts - Kondawar, S. E.; Mane, R. B.; Vasishta, A.; More, S. B.; Dhengale, S. D.; Rode, C. V. (Applied Petrochemical Research, 2017)
Glycerol carbonylation with urea is a very feasible option to produce glycerol carbonate with a net result of CO2 fixation through urea synthesis. The prerequisite of an efficient catalyst for this reaction is to possess both acid and basic sites together. Several acidic supports were screened for ZnO catalyst in this work and Zn/MCM-41 was found to exhibit the best activity and almost complete selectivity to glycerol carbonate (GC). Although, non-catalytic glycerol carbonylation resulted in GC formation but glycerol conversion achieved was twice with Zn/MCM-41 as a catalyst. Further to that increase in Zn loading from 2 to 5% resulted in increase in glycerol conversion from 63 to 82%. The prepared catalysts were characterized by XRD, NH3 and CO2-TPD and effects of reaction parameters such as catalyst loading, glycerol to urea mole ratio and temperature on glycerol conversion and GC selectivity in batch mode of operation were also studied. Time on stream activity of 5% Zn/MCM-41 catalyst for continuous carbonylation of glycerol was also studied for ~100 h with an average conversion of ~55% and complete selectivity to GC. This indicated five times lower productivity of GC per h due to lower residence time than that in a batch operation as compared to that of a continuous operation. Activation energy estimated from the Arrhenius plot was found to be 39.82 kJ mol−1 suggesting that the reaction is kinetically controlled. A reaction pathway mediated by acid and basic sites of the Zn/MCM-41 catalyst is also proposed.
Keywords: Acid–base ratio; Continuous process; Glycerol carbonate; Glycerol-urea carbonylation; reaction pathway; Supported Zn; Zn loading

Catalyst-free oxidation of sulfides to sulfoxides and diethylamine catalyzed oxidation of sulfides to sulfones using oxone as an oxidant - Kupwade, R. V.; Khot, S. S.; Lad, U. P.; Desai, U. V.; Wadgaonkar, P. P. (Research on Chemical Intermediates, 2017)
We describe here our journey from the failure of our attempts in controlled oxidation of sulfides to sulfoxides using an Oxone(A (R))-KBr combination to our success in the development of a catalyst-free protocol for the oxidation of sulfides to sulfoxides using Oxone as an oxidant. We also describe the failure of our attempts at the oxidation of sulfides to sulfones using an excess of Oxone-KBr as well as Oxone, and our success towards the development of a rapid, scalable and chromatography-free protocol for the oxidation of sulfides to sulfones using diethylamine-Oxone as an unprecedented catalyst-oxidant combination. [GRAPHICS] .
Keywords: diethylamine; organocatalysis; Oxidation; Oxone; Sulfones; Sulfoxides

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.

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

Chemistry that impacts us (and the scientists behind them) - Kumaraswamy, G. (Resonance, 2017)

Chickpea-fusarium oxysporum interaction transcriptome reveals differential modulation of plant defense strategies - Upasani, Medha L.; Limaye, Bhakti M.; Gurjar, Gayatri S.; Kasibhatla, Sunitha M.; Joshi, Rajendra R.; Kadoo, Narendra Y.; Gupta, Vidya S. (Scientific Reports, 2017)
Fusarium wilt is one of the major biotic stresses reducing chickpea productivity. The use of wilt-resistant cultivars is the most appropriate means to combat the disease and secure productivity. As a step towards understanding the molecular basis of wilt resistance in chickpea, we investigated the transcriptomes of wilt-susceptible and wilt-resistant cultivars under both Fusarium oxysporum f.sp. ciceri (Foc) challenged and unchallenged conditions. Transcriptome profiling using LongSAGE provided a valuable insight into the molecular interactions between chickpea and Foc, which revealed several known as well as novel genes with differential or unique expression patterns in chickpea contributing to lignification, hormonal homeostasis, plant defense signaling, ROS homeostasis, R-gene mediated defense, etc. Similarly, several Foc genes characteristically required for survival and growth of the pathogen were expressed only in the susceptible cultivar with null expression of most of these genes in the resistant cultivar. This study provides a rich resource for functional characterization of the genes involved in resistance mechanism and their use in breeding for sustainable wilt-resistance. Additionally, it provides pathogen targets facilitating the development of novel control strategies.

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

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

Comparable ionicity of the solutions of aprotic and protic ionic liquids by anion substitution - Jain, Preeti; Kumar, Anil (Journal of Solution Chemistry, 2017)
Temperature dependent molar conductances and fluidities of bisulfate and ethyl sulfate anion-based ionic liquids were measured. The extent of dissociation of the ionic liquids was estimated from the Walden plot in term of ionicity. The ionicity mainly depends on the magnitude of Coulombic forces, altered by the anion’s Lewis basicity. Aqueous solutions of aprotic ionic liquids, in general, possesses ionicity in the range of ≈70–99%. This article reveals that the substitution of the anion by bisulfate and ethylsulfate reduces the ionicity of aqueous solution of these ionic liquids to the range of 10–37%. This is very close to that exhibited by some of the protic ionic liquids and phosphonium based ionic liquids with sweetner anions. The concentration dependent molar conductance of these ionic liquids has been fitted to Mahiuddin and Ismail’s equation. To our surprise, the molar conductances of bisulfate-based aprotic ionic liquids are remarkably high, even though these ionic liquids possess lower ionicity.

Compositional dependence of electrical conduction in solution grown Zn1-xCrxSe thin films: a correlation - Deshmukh, S. L.; Pingale, P. C.; Chavan, G. T.; Pawar, S. T.; Prakshale, V. M.; Kamble, S. S.; Jadkar, S. R.; Chaure, N. B.; Gopinath, C. S.; Maldar, N. N.; Deshmukh, L. P. (Journal of Materials Science: Materials in Electronics, 2017)
Zinc selenide (ZnSe) has a typical band gap of 2.7 eV suitable for window application and can easily be synthesized using a liquid phase chemical bath deposition. An attempt is made to tune its band gap and other characteristics to cope with a maxima of the solar spectrum by deliberate addition of Cr3+. ZnSe and Zn1-xCrxSe (0 <= x <= 0.35) thin films were obtained under the controlled deposition conditions (temperature = 70 A degrees C, time = 210 min, pH = 10, etc). The compositional analysis showed Zn2+ replacement by Cr3+. The X-ray photoelectron spectroscopy revealed chemical states of the constituents Zn, Cr and Se as 2(+), 3(+) and 2(-) respectively. The electrical conductivity and thermo-power measurements in the 300-550 K temperature range showed semiconducting nature of the material and that the electrical conduction is of the n-type. The electrical conductivity is found to be increased continuously up to x = 0.05 and then decreased for further increase in x. The Hall-probe measurements also confirmed n-type conduction. The average Hall coefficient for pure ZnSe is -1.03 x 10(7) cm(3)/C whereas, it is -4.55 x 10(6) cm(3)/C for a sample with x = 0.35.

Computational survey of ligand properties on iron(III)-iron(II) redox potential: exploring natural attenuation of nitroaromatic compounds - Rizvi, Masood Ahmad; Mane, Manoj; Khuroo, Mohammad Akbar; Peerzada, Ghulam Mustafa (Monatshefte Fur Chemie, 2017)
This study is a computational investigation of the ligand effect on the redox potential of iron redox couple aimed at screening these systems for novel applications. The influence of common and naturally available organic compounds with diverse ligand characteristics (nature of donor site, chelation, pre-organization, degree of back acceptance) on the redox potential of iron(III)-iron(II) redox couple has been theoretically calculated using an appropriate level of density functional theory (DFT). The DFT calculated redox potentials of iron complexes are explored to supplement, corroborate, and predict the experimental behavior of the studied systems towards environmental reduction of nitroaromatic compounds to corresponding anilines. The comparative avidity of iron complexes with cysteine derivatives for the reduction of nitroaromatic compounds has been theoretically explored and based on structure-activity relationship; new iron complexes with a range of reactivity and enhanced ability towards nitroaromatic reduction have been predicted.
Keywords: Catechol derivatives; computational chemistry; Density functional theory; Iron complexes; Ligand effect on redox potential; Natural attenuation; Nitroaromatic compounds

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

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

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

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

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

Corrigendum: Agro-Industrial wastes for production of biosurfactant by bacillus subtilis ANR 88 and its application in synthesis of silver and gold nanoparticles [Front. Microbiol. 8, (492)] DOI: 10.3389/fmicb.2017.00492 - Rane, A.N.; Baikar, V. V.; Ravi Kumar, V.; Deopurkar, R. L. (Frontiers in Microbiology, 2017)

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

Critical role of select peptides in the loop region of G-rich PNA in the preferred G-quadruplex topology and stability - Bose, Tanaya; Kumar, Vaijayanti A. (Tetrahedron, 2017)
An uncharged PNA 15mer sequence formed unimolecular antiparallel G-quadruplex similar to that observed for DNA-TBA. Replacement of `tt' loop regions by peptides which induce helices or turns were found to have unpresidented effect on the quadruplex topology and stability. This study opens up a completely new strategy of utilizing G-quadruplex formation to display the array of functional groups in the three dimensional space thus creating a possibility of getting closer to the dream of designed peptides with three dimensional structures as observed in catalytic protein folds. (C) 2017 Elsevier Ltd. All rights reserved.
Keywords: ESI-MS study; G-quadruplex; Peptide nucleic acid; topology

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

Cucurbit[7]uril induced formation of fret-enabled unilamellar lipid vesicles - Kushwaha, Shilpi; Maity, Arunava; Gangopadhyay, Monalisa; Ravindranathan, Sapna; Rajamohanan, Pattuparambil R.; Das, Amitava (Langmuir, 2017)
A unique fluorescence resonance energy transfer (FRET) process is found to be operational in a unilamellar lipid self-assembly in the aqueous phase. A newly synthesized naphthyl based long chain lipid derivative [N-(naphthalene-1-ylmethyl)tetradecane-1-ammonium chloride, 14NA(+)] forms various self-assembled architectures in the aqueous phase. Controlled changes in lipid concentration lead to a transition of the self-assemblies from micelles to vesicles to rods. In the presence of cucurbit[7]uril (CB7), 14NA(+) forms a host-guest [2]pseudorotaxane complex (CB7(sic)14NA(+)) and secondary interactions lead to the formation of a lipid bilayer with hydrophobic pockets situated in between the layers. The change in the structure of 14NA(+) assemblies, interaction with CB7 and formation of supramolecular assemblies of CB7(sic)14NA(+) were examined using light scattering, spectroscopic, and microscopic techniques. Entrapment of a luminescent dye, anthracene within the hydrophobic bilayer of the supramolecular assembly CB7(sic)14NA(+) favors a modified luminescent response due to an efficient FRET process. Further, the FRET process could be controlled by thermal and chemical stimuli that induce transformation of unilamellar vesicles.

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

Data on the effect of oral feeding of Arachidonic acid or Docosahexanoic acid on haematopoiesis in mice - Limbkar, K. (Data in Brief, 2017)
Stem cells have peculiar property to self-renew and differentiate. It is important to control their fate in safe and effective ways for their therapeutic use. The mediators of essential polyunsaturated fatty acids (PUFAs) namely Arachidonic acid (AA) and Docosahexanoic acid (DHA) are known to play a role in haematopoiesis via various metabolic pathways [1]. However the direct effect of purified AA or DHA on haematopoiesis has not been well investigated yet. We have reported that oral administration of PUFAs enhanced haematopoiesis in mice [2]. Signaling Leukocyte Antigen Molecule (SLAM) (CD48−CD150+) phenotype consists of pure population of haematopoietic stem cells (HSCs). Herein we observed higher percentage of SLAM (CD48−CD150+) phenotype in the bone marrow (BM) cells of mice fed with AA or DHA compared to PBS fed control mice. Data from engraftment study depicts that BM from AA/DHA-fed mice showed higher absolute number of donor cells in recipient mice compared to control. The enhanced hematopoiesis observed in AA/DHA-fed mice was returned to normal when the mice were kept on normal diet for six weeks (after ten days of oral feeding). We confirmed GCMS (Gas Chromatography-Mass Spectroscopy) retention times of AA and DHA by co-injecting fatty acid extract from AA or DHA fed mice with purified AA or DHA standards respectively. Representative flow cytometry profile of Lin−Sca-1+c-kit+(LSK) cells showed higher expression of CXCR4 protein and ligands of Wnt, Notch1 signaling in BM of AA/DHA-fed mice

DBU-mediated diastereoselective aldol-type cyanomethylation of isatins - Rao, V. U. Bhaskara; Kumar, Krishna; Das, Tamal; Vanka, Kumar (Journal of Organic Chemistry, 2017)
An efficient, metal-free approach to 3-substituted 3-hydroxybxindole by DBU-mediated highly diastereoselective addition of aryl acetonitrile to N-protected isatin under mild conditions has been developed. The reaction proceeds smoothly to produce respective cyanomethylated adducts in good yield and excellent diastereoselectivity. Further transformation of the cyanide group allowed the synthesis of an advance intermediate of corresponding (+/-) CPC analogue. The mechanistic insight :toward the aldol-type cyanomethylation, of N-tritylisatin with benzyl cyanide was obtained by DFT calculations.

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

Degradation of metaldehyde in water by nanoparticle catalysts and powdered activated carbon - Li, Zhuojun; Kim, Jong Kyu; Chaudhari, Vrushali; Mayadevi, Suseeladevi; Campos, Luiza C. (Environmental Science and Pollution Research, 2017)
Metaldehyde, an organic pesticide widely used in the UK, has been detected in drinking water in the UK with a low concentration (< 1 mu g L-1) which is still above the European and UK standard requirements. This paper investigates the efficiency of four materials: powdered activated carbon (PAC) and carbon-doped titanium dioxide nanocatalyst with different concentrations of carbon (C-1.5, C-40, and C-80) for metaldehyde removal from aqueous solutions by adsorption and oxidation via photocatalysis. PAC was found to be the most effective material which showed almost over 90% removal. Adsorption data were well fitted to the Langmuir isotherm model, giving a q (m) (maximum/saturation adsorption capacity) value of 32.258 mg g(-1) and a K-L (Langmuir constant) value of 2.013 L mg(-1). In terms of kinetic study, adsorption of metaldehyde by PAC fitted well with a pseudo-second-order equation, giving the adsorption rate constant k(2) value of 0.023 g mg(-1) min(-1), implying rapid adsorption. The nanocatalysts were much less effective in oxidising metaldehyde than PAC with the same metaldehyde concentration and 0.2 g L-1 loading concentration of materials under UV light; the maximum removal achieved by carbon-doped titanium dioxide (C-1.5) nanocatalyst was around 15% for a 7.5 ppm metaldehyde solution.

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

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

Designing multicomponent nanosystems for rapid detection of circulating tumor cells - Banerjee, Shashwat S.; Khobragade, Vrushali; Khandare, Jayant J. (Methods in Molecular Biology, 2017)
Detection of circulating tumor cells (CTCs) in the blood circulation holds immense promise as it predicts the overall probability of patient survival. Therefore, CTC-based technologies are gaining prominence as a “liquid biopsy” for cancer diagnostics and prognostics. Here, we describe the design and synthesis of two distinct multicomponent magnetic nanosystems for rapid capture and detection of CTCs. The multifunctional Magneto-Dendrimeric Nano System (MDNS) composed of an anchoring dendrimer that is conjugated to multiple agents such as near infrared (NIR) fluorescent cyanine 5 NHS (Cy5), glutathione (GSH), transferrin (Tf), and iron oxide (Fe3O4) magnetic nanoparticle (MNP) for simultaneous tumor cell-specific affinity, multimodal high resolution confocal imaging, and cell isolation. The second nanosystem is a self-propelled microrocket that is composed of carbon nanotube (CNT), chemically conjugated with targeting ligand such as transferrin on the outer surface and Fe3O4 nanoparticles in the inner surface. The multicomponent nanosystems described here are highly efficient in targeting and isolating cancer cells thus benefiting early diagnosis and therapy of cancer.

Diethylamine Dess-Martin periodinane: an efficient catalyst-oxidant combination in a sequential, one-pot synthesis of difficult to access 2-amino-3,5-dicarbonitrile-6-sulfanylpyridines at ambient temperature - Kupwade, Ravindra V.; Khot, Supriya; Kulkarni, M. A.; Desai, Uday V.; Wadgaonkar, Prakash P. (RSC Advances, 2017)
Herein, diethylamine Dess–Martin periodinane has been demonstrated for the first time as an efficient catalyst–oxidant combination in a sequential, one-pot synthesis of medicinally privileged but difficult to access 2-amino-3,5-dicarbonitrile-6-sulfanylpyridines via a pseudo-four component reaction between 2,6-disubstituted benzaldehydes, malononitrile, and thiols. Ambient reaction conditions, excellent yields, and total avoidance of conventional isolation as well as purification are the noteworthy merits of this developed protocol.

Differential accumulation of vimentin fragments in preeclamptic placenta - Mary, Sheon; Kulkarni, Mahesh J.; Mehendale, Savita S.; Joshi, Sadhana R.; Giri, Ashok P. (Cytoskeleton, 2017)
Preeclampsia is a pregnancy complication that is the result of abnormal placentation because of inadequate trophoblast invasion into spiral arteries that prevent normal blood flow to the placenta. We report the alteration in vimentin protein proteolysis in placenta of normotensive and preeclamptic women, which is known to have a role in many physiological functions other than its major function in the structural integrity of the cell. Placental proteome from normotensive (n=25) and preeclamptic pregnancies (n=25) showed eight differentially accumulated protein spots of vimentin (proteolytic fragments) by two-dimensional electrophoresis. Immunoblots of normotensive and preeclamptic placenta revealed a difference in proteolytic processing of vimentin. In particular, lower molecular weight vimentin fragments of 32 and 20 kDa were 3.3 and 2.6-fold (p<0.0001) higher, respectively, in preeclampsia compared with normotensive placenta.

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

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

Dissociative adsorption of molecular hydrogen on BN-doped graphene-supported aluminum clusters - Kumar, Deepak; Krishnamurty, Sailaja; Pal, Sourav (Journal of Physical Chemistry C, 2017)
The present work demonstrates dissociative adsorption of molecular hydrogen on supported and unsupported aluminum Wclusters (Al-n, n = 4-8, 13) using density functional theory based calculations. The studies reveal that the presence of a BN-doped graphene surface support reduces the dissociative adsorption barrier of the bond in molecular hydrogen on even atom clusters. In particular, supported Al-6 demonstrates a barrier-less dissociative adsorption toward the H-2 molecule. These results demonstrate the excellent potential of supported Al nanoparticles for hydrogen storage and also the potential of doped graphene systems are catalyzing supports.

Domibacillus mangrovi sp nov and domibacillus epiphyticus sp nov., isolated from marine habitats of the central west coast of India - Verma, Ashish; Ojha, Anup Kumar; Dastager, Syed G.; Natarajan, Rameshkumar; Mayilraj, Shanmugam; Krishnamurthi, Srinivasan (International Journal of Systematic and Evolutionary Microbiology, 2017)
While studying culturable bacterial diversity in different marine habitats of the central west coast of India, two novel Gramstain-positive, strictly aerobic, motile, endospore-forming and rod-shaped bacterial strains designated as SAOS 44(T) and SAB 38(T) were isolated from mangrove sediment soil and the surface of a macroalga, respectively. The strains were taxonomically characterized by using a polyphasic approach and genomic methods. The phylogenetic analysis based on 16S rRNA gene sequencing placed the strains firmly in the genus Domibacillus and were most closely related to Domibacillus antri KCTC 33636(T). The predominant fatty acids were iso-C-15 : 0 and anteiso-C-15 : 0. The major polar lipids were diphosphatidylglycerol and phosphatidylglycerol in addition to an aminophosphoglycolipid. MK-6 was the only respiratory quinone. The range of values of digital DNA-DNA hybridization (19.2-24.9 %) and the ortho-average nucleotide identity (74.1-81.4 %) among strains SAOS 44(T), SAB 38(T) and other Domibacillus species clearly supports their status as a distinct and novel species for which the names Domibacillus mangrovi sp. nov. SAOS 44(T) (=DSM 100930(T)=KCTC 33820(T)=MTCC 12571(T)) and Domibacillus epiphyticus sp. nov. SAB 38(T) (=DSM 100929(T)= KCTC 33830(T)=MTCC 12575(T)) are proposed, respectively.

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

Effect of shape of protrusions and roughness on the hydrophilicity of a surface - Chowdhury, Sheelan Sengupta; Pandey, Prithvi Raj; Kumar, Rajnish; Roy, Sudip (Chemical Physics Letters, 2017)
We have investigated wetting of model rough surfaces made up of hydrophilic triangular and hexagonal pillars (protrusions). The surface roughnesses are altered by varying the area of the rough surface, the height of the pillars, and the surface interactions to the water. We have established a correlation between structure i.e., the shape of a pillar, which actually depends on the number of edges (due to shape), and the wetting phenomena. We have found that surface with higher number of edges repels water at lower roughness value. We explain the correlation by analyzing the variation of interactions energy components and density profiles of water on the structured surfaces. (C) 2017 Elsevier B.V. All rights reserved.

Effects of micellization on growth kinetics of methane hydrate - Bhattacharjee, Gaurav; Kushwaha, Omkar Singh; Kumar, Asheesh; Khan, Muzammil Yusuf; Patel, Jay Narayan; Kumar, Rajnish (Industrial & Engineering Chemistry Research, 2017)
Surfactants are Specific functional materials, that form various types of self-assemblies and affect local water ordering alongside solution properties. Such surface active agents are used extensively in gas hydrate based applications as kinetic hydrate promoters. To understand the effect of surfactant micelles on hydrate formation kinetics, a novel surfactant system capable of producing micelles at hydrate forming temperature was developed. The presence of surfactant micelles in this new system (a combination of anionic surfactant SDS and zwitterionic surfactant CAPB) was determined through DLS measurements. Pure methane and a coal bed methane mixture were individually used to assess the efficacy of the surfactant mixture for hydrate formation. This study conclusively proves for the first time that the presence of surfactant micelles enhances hydrate formation kinetics. The findings reported here can contribute significantly toward improving the utility of surfactants in gas hydrate based technological applications such as gas separation and methane storage.

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

Efficient exciton to dopant energy transfer in Mn2+-Doped (C4H9NH3)2PbBr4 two-dimensional (2D) layered perovskites - Biswas, A. (Chemistry of Materials, 2017)
Three-dimensional ABX3 perovskite material has attracted immense interest and applications in optoelectronic devices, because of their enabling properties. Recently, Mn2+ doping directly into APbCl3-type three-dimensional (3D) nanocrystals, manifesting host-to-dopant energy transfer, have been reported for LED display applications. Strongly bound excitons in the doped system can enhance the dopant-carrier exchange interactions, leading to efficient energy transfer. Here, we report the simple and scalable synthesis of Mn2+-doped (C4H9NH3)2PbBr4 two-dimensional (2D) layered perovskites. The Mn2+-doped 2D perovskite shows enhanced energy transfer efficiency from the strongly bound excitons of the host material to the d electrons of Mn2+ ions, resulting in intense orange-yellow emission, which is due to spin-forbidden internal transition (4T1 → 6A1) with the highest quantum yield (Mn2+) of 37%. Because of this high quantum yield, stability in ambient atmosphere, and simplicity and scalability of the synthetic procedure, Mn2+-doped 2D perovskites could be beneficial as color-converting phosphor material and as energy down-shift coating for perovskite solar cells. The newly developed Mn2+-doped 2D perovskites can be a suitable material to tune dopant-exciton exchange interactions to further explore their magneto-optoelectronic properties.
Keywords: Doping (additives); Energy Efficiency; Energy Transfer; Exchange interactions; Excitons; Light Emitting Diodes

Efficient oxidation of ethyl benzene using in situ generated molybdenum acetylide oxo-peroxo complex as recyclable catalyst - Khomane, Sonali B.; Doke, Dhananjay S.; Dongare, M. K.; Halligudi, S. B.; Umbarkar, S. B. (Applied Catalysis A-General, 2017)
Selective oxidation of various alkanes/alkyl aromatics to corresponding carbonyl compounds has been carried out with very high conversion (similar to 98%) and selectivity (up to 100%) for carbonyl compounds using cyclopentadienyl molybdenum acetylide complex, CpMo(CO)(3)(C CPh) (1) as catalyst and tert-butyl hydrogen peroxide (TBHP) as an oxidant and turnover number (TON) of 88 was obtained with turnover frequency (TOF) of 2.45 h(-1). Mo acetylide oxo-peroxo species is formed in situ by reaction of 1 with TBHP during the course of reaction as catalytically active species. Interestingly even though the catalytically active species is homogeneous in nature it could be recycled very easily by recovering the catalytically active species as solid after addition of diethyl ether, and separating the products into organic phase. In the case of ethyl benzene oxidation, even after three recycles no appreciable loss in ethyl benzene conversion and acetophenone selectivity was observed. This complex showed high catalytic activity for the oxo functionalization of other alkyl aromatics and alkanes such as substituted ethyl benzenes, toluene as well as cyclohexane. TBHP was found to be more efficient oxidant than hydrogen peroxide for this oxidation. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Alkyl aromatics; Carbonyl compounds; Homogeneous catalysis; Molybdenum acetylide complex; Oxo-peroxo species

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

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

Elastic compressible energy storage devices from ice templated polymer gels treated with polyphenols - Das, Chayanika; Chatterjee, Soumyajyoti; Kumaraswamy, Guruswamy; Krishnarnoorthy, Kothandam (Journal of Physical Chemistry C, 2017)
Design and fabrication of rechargeable energy storage devices that are robust to mechanical deformation is essential for wearable electronics. We report the preparation of compressible supercapacitors that retain their specific capacitance after large compression and that recover elastically after at least a hundred compression expansion cycles. Compressible supercapacitors are prepared using a facile, scalable method that readily yields centimeter-scale macroporous objects. We ice template a solution of polyethylenimine in green tea extract to prepare a macroporous cross-linked polymer gel (PG) whose walls are impregnated with green tea derived polyphenols. As the PG is insulating, we impart conductivity by deposition of gold on it. Gold deposition is done in two steps: first, silver nanoparticles are formed on the PG walls by in situ reduction by polyphenols and then gold films are deposited on these walls. Gold coated PGs (GPGs) were used as electrodes to deposit poly(3,4-ethylenedioxythiophene) as a pseudocapacitive material. The specific capacitance of PEDOT coated GPGs (PGPG) was found to be 253 F/g at 1 A/g. PGPG could be compressed and expanded over a hundred cycles without any suffering mechanical failure or loss of capacitative performance. The capacitance was found to be 243 F/g upon compressing the device to 25% of its original size (viz. compressive strain = 75%). Thus, even large compression does not affect the device performance. This device shows power and energy densities of 2715 W/kg and 22 Wh/kg, respectively, in the uncompressed state. The macroporous nature of PGPG makes it possible to fill the PGPG pores with gel electrolyte. We report that the gel electrolyte filled supercapacitor exhibited a specific capacitance of 200 F/g, which increased by 4% upon 75% compression.

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

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

Engineering cell surface glycans with carbohydrate enantiomers to alter bacterial binding and adhesion - Gade, Madhuri; Chaudhary, Preeti Madhukar; Thulasiram, Hirekodathakallu V.; Kikkeri, Raghavendra (Chemistryselect, 2017)
Chirality of carbohydrate has critical functions in many biological processes. Changes in the configuration of even one sugar molecules may cause abnormal behavior or even inhibit specific processes. Herein, we have shown bioorthogonal conjugation of mannose enantiomers on HeLa cell surfaces induced a different rate of bacterial binding and cell adhesion.
Keywords: Bioorthogonal reaction; Carbohydrate; E. coli; Enantiomer; Surfaces functionalization

Enhanced field emission performance of MoO3 nanorods and MoO3-rGO nanocomposite - Bankar, Prashant K.; Khandare, Lina N.; Late, Dattatray J.; More, Mahendra A. (ChemistrySelect, 2017)
The graphene and semiconducting hybrid based nanostructures have emerged as a new class of multifunctional materials with improved performance in comparison to the pristine semiconductors. Here, as-synthesized MoO3-reduced graphene oxide (rGO) nanocomposite emitter exhibits enhanced field emission (FE) behavior as compared to the pristine 1D MoO3 nanorods. The hydrothermally synthesized 1D MoO3 nanorods (1D) are grafted on the rGO sheet (2D) using a simple room temperature sonochemical method. The morphological and structural analysis confirms the attachment of MoO3 nanorods with rGO and the improved conductivity of the sample indicates a strong electronic interaction between them. Furthermore, the FE studies of as-synthesized MoO3 nanorods and MoO3-rGO nanocomposite emitters, carried out at a base pressure -1 x 10(-8) mbar, reveals the values of turn on field (required to draw an emission current density of 1 mu A/cm(2)) as 1.6 and 1.4 V/mu m, respectively. Interestingly, the maximum emission current density of 2810 mA/cm(2) is achieved at a lower applied field of 2.7 V/mu m from the MoO3-rGO nanocomposite emitter. The enhancement in FE performance of MoO3-rGO nanocomposite is attributed to the improved electrical conductivity, mechanical properties and higher concentration of protruding edges (emission sites). This observation can be extended to other graphene-based 1D inorganic hybrid semiconductor nanocomposites, which can provide a valuable opportunity to explore novel hybrid materials for vacuum nano-electronic devices.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

G - C3N4 (2D)/CdS (1D)/rGO (2D) dual-interface nano-composite for excellent and stable visible light photocatalytic hydrogen generation - Tonda, Surendar (International Journal of Hydrogen Energy, 2017)
A 2D/1D/2D dual-interface nano-composite configuration in the form of CdS nanorods sandwiched between g-C3N4 and rGO sheets with intimate interfacial contact is synthesized by a facile wet-chemical method and is shown to exhibit excellent photocatalytic H2 generation under visible-light irradiation. In particular, the optimal g-C3N4/CdS/rGO dual-interface nano-composite shows H2 production rate of ∼4800 μmol h-1 g-1, which is almost 44, 11 and 2.5 times higher than that shown by pure g-C3N4 nanosheets, and the g-C3N4/rGO and g-C3N4/CdS single interface heterostructures, respectively. It is shown that the synergic effects involving the band structure match and close interfacial contact, which can accelerate the separation and transfer of photoinduced charge carriers, and the enhanced visible-light absorption together contribute to the impressive photocatalytic performance and photostability of the g-C3N4/CdS/rGO ternary nano-composite system. Specific advantages of a dual-interface triple-composite system over a single interface case(s) are also brought out.
Keywords: charge transfer; Dual Interface; G - CN; H Generation; Hetero Structure; Nano - Composite

Galvanic replacement-based Cu2O self-templating strategy for the synthesis and application of Cu2O–Ag heterostructures and monometallic (Ag) and bimetallic (Au–Ag) hollow mesocages - Bakthavatsalam, Rangarajan; Kundu, Janardan (Crystengcomm, 2017)
Polyhedral Cu2O microparticles as self-templates have been well-demonstrated for the synthesis of Cu2O–M heterostructures (M = Au, Pd, Pt) and Au nano/mesocages utilizing the galvanic replacement reaction (GRR) strategy. However, reports on GRR-based fabrication of Cu2O–Ag heterostructures and the ensuing Ag mesocages are scanty. There is no report that describes the phenomenon of facet selectivity during the GRR-based deposition of Ag on Cu2O template particles. Here, we have identified the underlying rationale behind the observed difficulty in nucleating Ag nanoparticles on an octahedral Cu2O self-template particle. Utilization of an appropriately chosen surfactant/complexant for the silver precursor helps in demonstrating the successful fabrication of Cu2O–Ag heterostructures (octahedral, cubic) with a tunable loading density of Ag NPs on the Cu2O surfaces. This is achieved using Cu2O template particles that undergo GRR with silver nitrate in the presence of nitric acid, and 5-sulfosalicylic acid as the surfactant (key role players). We provide evidence that supports facet selectivity during the deposition of Ag NPs on Cu2O cuboctahedral particles. Hollow octahedral Ag and Au–Ag bimetallic mesocages are fabricated that have rough surfaces, uniform morphology, and excellent shape retention. The fabricated heterostructures and mesocages act as an excellent SERS substrate. This is the first report on the rational synthesis of octahedral Cu2O–Ag heterostructures and octahedral hollow metallic mesocages utilizing the Cu2O self-templating strategy along with the demonstration of facet selectivity of Ag deposition on Cu2O template particles through GRR. The current approach offers a facile and versatile protocol for the synthesis of Cu2O–metal heterostructures and hollow noble metal mesocages.

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

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

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

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

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

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

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

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

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

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

Heteroatom facilitated preparation of electrodes for sodium ion batteries - Bhosale, Manik E.; Banerjee, Abhik; Krishnamoorthy, Kothandam (RSC Advances, 2017)
A conjugated polymer comprising heterocycles was prepared and carbonized to obtain carbon with interlayer spacings between 0.42 and 0.37 nm and exhibited a specific capacity of 250 mA h g(-1).

Heterogeneously catalyzed domino synthesis of 3-indolylquinones involving direct oxidative C-C coupling of hydroquinones and indoles - Kamble, Sumit B.;; Vyas, Praneet P.; Jayaram, Radha V.;; Rode, Chandrashekhar V. (ACS Omega, 2017)
<div id="absImg" style="position: relative; margin: 0px; padding: 5px; border: 1px solid rgb(204, 204, 204); border-radius: 5px; background-image: initial; background-position: initial; background-size: initial; background-repeat: initial; background-attachment: initial; background-origin: initial; background-clip: initial; text-align: center; color: rgb(0, 0, 0); font-family: Helvetica, Arial, sans-serif; font-size: 14px;"><img alt="Abstract Image" src="http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/acsodf/2017/acsodf.2017.2.issue-5/acsomega.7b00201/20170523/images/medium/ao-2017-00201p_0006.gif" style="border: 0px; max-width: 100%;"> <p class="articleBody_abstractText" style="margin: 0px 0px 1.5em; line-height: 1.6em; padding: 0pt; width: 610px; word-wrap: break-word; color: rgb(0, 0, 0); font-family: Helvetica, Arial, sans-serif; font-size: 14px;">A domino synthesis of 3-indolylquinones was achieved successfully via direct oxidative C–C coupling of hydroquinones with indoles over Ag2O and Fe3O4/povidone–phosphotungstic acid (PVP–PWA) catalysts using H2O2 in tetrahydrofuran at room temperature. Ag2O catalyzed the in situ oxidation of hydroquinone and 3-indolylhydroquinone intermediates, whereas ferrite solid acid, Fe3O4/PVP–PWA, with a 1:4:1 ratio of Fe3O4, PVP, and PWA, catalyzed the activation of quinones. The efficiency of this catalytic domino approach was established by a broad scope of substrates involving a variety of hydroquinones and quinones to give high yields (81–97%) of 3-indolylquinones. Fe3O4/PVP–PWA was separated magnetically, whereas simple filtration could separate Ag2O, both of which could be recycled several times without losing their activities.
Keywords: Carbonyl compounds (organic); Electron microscopy; Fourier-transform spectroscopy; Redox reaction

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

Hidden electrostatic basis of dynamic allostery in a PDZ domain - Kumawat, Amit; Chakrabarty, Suman (Proceedings of the National Academy of Sciences of the United States of America, 2017)
Allosteric effect implies ligand binding at one site leading to structural and/or dynamical changes at a distant site. PDZ domains are classic examples of dynamic allostery without conformational changes, where distal side-chain dynamics is modulated on ligand binding and the origin has been attributed to entropic effects. In this work, we unearth the energetic basis of the observed dynamic allostery in a PDZ3 domain protein using molecular dynamics simulations. We demonstrate that electrostatic interaction provides a highly sensitive yardstick to probe the allosteric modulation in contrast to the traditionally used structure-based parameters. There is a significant population shift in the hydrogen-bonded network and salt bridges involving side chains on ligand binding. The ligand creates a local energetic perturbation that propagates in the form of dominolike changes in interresidue interaction pattern. There are significant changes in the nature of specific interactions (nonpolar/polar) between interresidue contacts and accompanied side-chain reorientations that drive the major redistribution of energy. Interestingly, this internal redistribution and rewiring of side-chain interactions led to large cancellations resulting in small change in the overall enthalpy of the protein, thus making it difficult to detect experimentally. In contrast to the prevailing focus on the entropic or dynamic effects, we show that the internal redistribution and population shift in specific electrostatic interactions drive the allosteric modulation in the PDZ3 domain protein.

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

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

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

High-Performance Sensing Behavior Using Electronic Ink of 2D SnSe2 Nanosheets. - Pawar, Mahendra; Kadam, Sunil; Late, Dattatray J. (Chemistry Select, 2017)
Most of the recent research work on layered chalcogenides is understandably focused on single atomic layers. However, it is uncertain if the single layer units are most ideal structures for enhanced gas-solid interactions. To probe this concern, we have synthesized few layer thick SnSe<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2 nanosheets ink using liquid exfoliation method. The morphology, thickness / layering and elemental analysis of the sheets were characterized by using SEM, TEM, AFM, Raman spectroscopy and by XPS. The two dimensional (2D) SnSe<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2 nanosheets sensor device with different thicknesses was assessed for the humidity and gas sensing performances with exposure to humidity in different conditions. The results show that compared to the bulk / thicker counterpart, sensor device of few SnSe<span style="line-height: 0; bottom: -0.25em; margin: 0px; padding: 0px 1px; border: 0px; outline: 0px; font-size: 0.688em; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); position: relative; color: rgb(51, 51, 51); font-family: "Open Sans", Arial, Helvetica, "Lucida Sans Unicode", sans-serif;">2 layers exhibit excellent sensitivity, recovery and ability to be tune the sensing performance with thickness and can be used in lab on chip devices.

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

Identification and functionality prediction of pathogenesis-related protein 1 from legume family - Tellis, Meenakshi; Mathur, Monika; Gurjar, Gayatri; Kadoo, Narendra; Gupta, Vidya (Proteins-Structure Function and Bioinformatics, 2017)
The production and accumulation of pathogenesis-related (PR) proteins in plants is one of the important responses to biotic and abiotic stress. Large number of identified PR proteins has been categorized into 17 functional families based on their structure, phylogenetics, and biological activities. However, they are not widely studied in legume crops. Using 29 PR1 proteins from Arabidopsis thaliana, as query, here we have predicted 92 candidate PR1 proteins through the PSI-BLAST and HMMER programs. These candidate proteins were comprehensively analyzed with, multiple sequence alignment, domain architecture studies, signal peptide, and motif extraction followed by phylogenetic analysis. Further, response of two candidate PR1 proteins from chickpea against Fusarium oxysporum f.sp.ciceri attack was validated using qRT-PCR followed by their 3D structure prediction. To decipher mode of action for PR1s, docking of pathogen extracellular matrix components along with fungal elicitors was performed with two chickpea PR1 proteins. Based on these findings, we propose carbohydrate to be the unique pathogen-recognition feature for PR1 proteins and beta-glucanase activity via beta-glucan binding or modification.

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

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

Impact of rare-earth metal oxide (Eu 2 O 3 ) on the electrochemical properties of a polypyrrole/CuO polymeric composite for supercapacitor applications - Majumder, Mandira; Choudhary, Ram Bilash; Thakur, Anukul. K.; Karbhal, Indrapal (RSC Advances, 2017)
A ternary composite of polypyrrole/copper oxide/europium oxide (PPY/CuO/Eu2O3), synthesized via a facile in situ chemical oxidative polymerization method, exhibits the maximum specific capacitance of 320 F g⁻¹ at the current density of 1 A g⁻¹. Incorporation of the rare-earth metal oxide Eu2O3 in the PPY/CuO matrix can promote charge transportation in the resulting ternary nanocomposite by enhancing the porosity. The interconnected mesoporous networks reduce the internal resistance and the charge transfer resistance (Rct) of the composite electrode material. Moreover, the incorporation of Eu2O3 in the PPY/CuO provides support to the fragile polymer backbone resulting in an excellent cycle stability and a markedly enhanced thermal stability. These together with the exhibition of an excellent coulombic efficiency demonstrates that incorporation of rare earth metal oxide can play a significant role in improving the performance of a polymeric composite opted as an electrode material for high-performance supercapacitor.

Increasing light coupling in a photovoltaic film by tuning nanoparticle shape with substrate surface energy - Kataria, Devika; Krishnamoorthy, Kothandam; Iyer, S. Sundar Kumar (Materials Research Express, 2017)
Tuning metal nanoparticle (MNP) contact angle on the surface it is formed can help maximise the useful optical coupling in photovoltaic films by localized surface plasmon (LSP) resonance-opening up the possibility of building improved photovoltaic cells. In this work experimental demonstration of optical absorption increase in copper phthalocyanine (CuPc) films by tuning silver MNP shape by changing its contact angles with substrate has been reported. Thin films of poly3,4 ethylenedioxythiophene: sodium dodecycl sulphate (PEDOT: SDS) with different surface energies were formed on indium tin oxide (ITO) coated glass by electro-deposition. Silver MNPs thermally evaporated directly on ozonised ITO as well as on the PEDOT: SDS films showed contact angles ranging from 60 degrees to 125 degrees. The CuPc layer was deposited on top of the MNPs. For the samples studied, best optical absorption in the CuPc layer was for a contact angle of 110 degrees.

An innovative approach to enhance methane hydrate formation kinetics with leucine for energy storage application - Veluswamy, H. P.; Kumar, A.; Kumar, R.; Linga, P. (Applied Energy, 2017)
Natural gas storage in dathrate hydrates or solidified natural gas (SNG) offers the safest, cleanest and the most compact mode of storage aided by the relative ease in natural gas (NG) recovery with minimal cost compared to known conventional methods of NG storage. The stochastic nature of hydrate nucleation and the slow kinetics of hydrate growth are major challenges that needs to be addressed on the SNG production side. A deterministic and fast nucleation coupled with rapid crystallization kinetics would empower this beneficial technology for commercial application. We propose a hybrid combinatorial approach of methane hydrate formation utilizing the beneficial aspect of environmentally benign amino acid (leucine) as a kinetic promoter by combining stirred and unstirred reactor operation. This hybrid approach is simple, can easily be implemented and scaled-up to develop an economical SNG technology for efficient storage of natural gas on a large scale. Added benefits include the minimal energy requirement during hydrate growth resulting in overall cost reduction for SNG technology.

Insights in the diffusion controlled interfacial flow synthesis of Au nanostructures in a microfluidic system - Kulkarni, Amol A.; Cabeza, Victor Sebastian (Langmuir, 2017)
Continuous segmented flow interfacial synthesis of Au nanostructures is demonstrated in a microchannel reactor. This study brings new insights into the growth of nanostructures at continuous interfaces. The size as well as the shape of the nanostructures showed significant dependence on the reactant concentrations, reaction time, temperature, and surface tension, which actually controlled the interfacial mass transfer. The microchannel reactor assisted in achieving a high interfacial area, as well as uniformity in mass transfer effects. Hexagonal nanostructures were seen to be formed in synthesis times as short as 10 min. The wettability of the channel showed significant effect on the particle size as well as the actual shape. The hydrophobic channel yielded hexagonal structures of relatively smaller size than the hydrophilic microchannel, which yielded sharp hexagonal bipyramidal particles (diagonal distance of 30 nm). The evolution of particle size and shape for the case of hydrophilic microchannel is also shown as a function of the residence time. The interfacial synthesis approach based on a stable segmented flow promoted an excellent control on the reaction extent, reduction in axial dispersion as well as the particle size distribution.

Interaction of membrane cholesterol with GPCRs: implications in receptor oligomerization - Sengupta, D.; Kumar, G. A.; Chattopadhyay, A. (Receptors, 2017)
G protein-coupled receptors (GPCRs) are the largest family of proteins involved in signal transduction across cell membranes, and represent major drug targets in all clinical areas. Oligomerization of GPCRs and its implications in drug discovery constitute an exciting area in contemporary biology. In this review, we have highlighted the role of membrane cholesterol and the actin cytoskeleton in GPCR oligomerization, using a combined approach of homo-FRET and coarse-grain molecular dynamics simulations. In the process, we have highlighted experimental and computational methods that have been successful in analyzing different facets of GPCR association. Analysis of photobleaching homo-FRET data provided novel information about the presence of receptor oligomers under varying conditions. Molecular dynamics simulations have helped to pinpoint transmembrane helices that are involved in forming the receptor dimer interface, and this appears to be dependent on membrane cholesterol content. This gives rise to the exciting and challenging possibility of age and tissue dependence of drug efficacy. We envision that GPCR oligomerization could be a game changer in future drug discovery.

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

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

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

Introducing the bipolar solvent media using the aqueous mixtures of amino acid anion-based ionic liquids - Beniwal, Vijay; Kumar, Anil (Journal of Physical Chemistry B, 2017)
To carry out a chemical reaction between the reactants with largely different polarities, it becomes important to have a reaction medium that possesses both the polar and nonpolar solvation environments. In an attempt to explore the reaction media with such unique polarity properties, the present study provides a thorough understanding of the bipolar solvent media using the aqueous mixtures of amino acid anion-based ionic liquids. The highly polar behavior of the binary mixtures used in the study has been ascribed to the pure ionic liquid state. However, the less polar solvation shells have been attributed to the presence of a neutral form of the anions. Addition of water in the amino acid anion-based ionic liquids causes the protonation of a certain fraction of the anions of the ionic liquids, resulting into the formation of a less polar nonionic protonated form along with the highly polar natural anionic form. This results into the formation of two solvation spheres with different polarities, which can be seen very clearly from the presence of two absorption bands (lower wavelength absorption band and higher wavelength absorption band) in the UV-vis absorption spectrum of Reichardt's E-T(30) dye and two emission bands (lower wavelength emission band and higher wavelength emission band) in the fluorescence emission spectrum of C481 dye. The values of the E-T(N) polarity parameter corresponding to the two solvation shells having different polarities have been calculated from the deconvoluted absorption spectra of the Reichardt's E-T(30) and were analyzed in three amino acid anion-based ionic liquids. Generation of the neutral form of anions in the aqueous mixtures formed via a protonation transfer reaction has been confirmed by the H-1 NMR spectroscopy and UV-vis absorption spectrum of 18DHAQ dye. The study also establishes that the Reichardt's E-T(30) dye can be used as a valid polarity probe to study the solvatochromic behavior of the binary mixtures of amino acid-based ionic liquids.

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

Kinetic profile and catalytic activity of transition metal-based ionic liquids for reduction of nitroarenes via in situ formation of nanoparticles - Thawarkar, Sachin R.; Khupse, Nageshwar D.; Kumar, Anil (Chemistryselect, 2017)
The experimentally determined apparent rate constant (k(app)) shows that the [BmIm](2)[PdCl4] and [BmIm](2)[NiCl4] act as effective catalysts for the reduction of nitroarenes to aminoarenes in the presence of NaBH4. The TEM, XPS, XRD and dynamic light scattering studies show that there is in situ formation of Pd and Ni metal Nanoparticles (NPs) from the reduction of [BmIm](2)[PdCl4] and [BmIm](2)[NiCl4], respectively which are responsible for the enhancement in the catalytic activity. Thus, in the presence of the ionic liquid stabilized metal NPs show higher catalytic activity in comparison to the NPs stabilized with other capping agents as reported. The order of k(app) as 1) PNP > 2-BrPNP > 2-APNP and 2) PNP > ONP > 2-NR for reduction of nitroarenes using [BmIm](2)[PdCl4] and [BmIm](2)[NiCl4] and its correlation explained on the basis of electronic structure and hydrogen bonding ability of nitroarenes. The thermodynamic parameters such as E-a, Delta H-#, Delta S-# and Delta G(#) are in agreement with the surface catalyzed reduction reaction of PNP in the presence of NPs as catalyst. The kapp values illustrated the reduction reaction follow the LangmuirHinshelwood (L-H) mechanism.

Large anion incorporation to improve the performance of large, paper based conducting polymer supercapacitors - Jain, B.; Krishnamoorthy, K. (Materials Today Energy, 2017)
Poly(3,4-ethylenedioxythiophene) (PEDOT) is a stable conducting polymer, hence its dispersion is widely used in commercial devices. However, PEDOT's charge storage properties are not impressive. Thus, improvement in charge storage properties of PEDOT will render the possibility of fabricating stable energy storage devices such as supercapacitors. A fundamentally different approach is required to achieve this objective. We envisioned that the charge storage property of PEDOT can be improved by trapping large anions. These ions would facilitate better ion transport into the PEDOT matrix from the electrolyte and increase the efficiency of supercapacitors. Furthermore, a large anion such as triiodide is relatively immobile in the polymer matrix, hence we hypothesize the ions to be trapped in the polymer. To test this hypothesis, triiodide trapped PEDOT based supercapacitors are fabricated on paper substrates. A 1 cm2 triiodide incorporated PEDOT based supercapacitor exhibited a specific capacitance of 486 F/g. On the other hand, PEDOT without triiodide incorporation exhibited a specific capacitance of 221 F/g. Indeed, a device with an area of 32 cm2 exhibited a specific capacitance of 476 F/g.
Keywords: Flexible Supercapacitors; Paper based Supercapacitors; polyphenols

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

Linking catalyst-coated isotropic colloids into ``active'' flexible chains enhances their diffusivity - Biswas, Bipul; Manna, Raj Kumar; Laskar, Abhrajit; Kumar, P. B. Sunil; Adhikari, Ronojoy; Kumaraswamy, Guruswamy (ACS Nano, 2017)
Active colloids are not constrained by equilibrium: ballistic propulsion, superdiffusive behavior, or enhanced diffusivities have been reported for active Janus particles. At high concentrations, interactions between active colloids give rise to complex emergent behavior. Their collective dynamics result in the formation of several hundred particle-strong flocks or swarms. Here, we demonstrate significant diffusivity enhancement for colloidal objects that neither have a Janus architecture nor are at high concentrations. We employ uniformly catalyst-coated, viz. chemo-mechanically, isotropic colloids and link them into a chain to enforce proximity. Activity arises from hydrodynamic interactions between enchained colloidal beads due to reaction-induced phoretic flows catalyzed by platinum nanoparticles on the colloid surface. This results in diffusivity enhancements of up to 60% for individual chains in dilute solution. Chains with increasing flexibility exhibit higher diffusivities. Simulations accounting for hydrodynamic interactions between enchained colloids due to active phoretic flows accurately capture the experimental diffusivity. These simulations reveal that the enhancement in diffusivity can be attributed to the interplay between chain conformational fluctuations and activity. Our results show that activity can be used to systematically modulate the mobility of soft slender bodies.
Keywords: active matter; Brownian motion; colloidal assembly; diffusivity; ice templating

Living in the polymer age - Kumaraswamy, Guruswamy (Resonance, 2017)

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

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

Magnetic reduced graphene oxide loaded hydrogels: highly versatile and efficient adsorbents for dyes and selective Cr(VI) ions removal - Halouane, Fatima; Oz, Yavuz; Meziane, Dalila; Barras, Alexandre; Juraszek, Jean; Singh, Santosh K.; Kurungot, Sreekumar; Shaw, Pankaj K.; Sanyal, Rana; Boukherroub, Rabah; Sanyal, Amitav; Szunerits, Sabine (Journal of Colloid and Interface Science, 2017)
The formation of composites of reduced graphene oxide (rGO) and magnetic nanoparticles (MP) has flourished in recent years as they combine the advantages of both nanomaterials. Most of these composite materials are prepared by in situ formation of MP onto rGO or by the post-adsorption onto rGO. We report here on a simple and highly controlled method for the fabrication of different magnetic 3D rGO-loaded hydrogels. Cellulose bound magnetic nanoparticles (MP@cellulose) were synthesized by chemical co-precipitation and loaded together with rGO into poly(ethylene glycol) dimethacrylate based hydrogels during their fabrication using photo-polymerization. The magnetic rGO-loaded hydrogels proved to be highly adaptable to different applications. The as-formed composites allowed for efficient dye removal with an adsorption capacity of 111.9 +/- 4 mg g(-1) in the case of methylene blue (MB). Integration of poly(ethyleneimine) (PEI) allowed for the selective capturing of Cr6+ ions with an adsorption capacity of 313 12 mg g-1. Most importantly, independent of the application, the magnetic rGO-loaded hydrogel can be regenerated without loss of its adsorption capacity. (C) 2017 Elsevier Inc. All rights reserved.

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

Mapping architectural and transcriptional alterations in non-lesional and lesional epidermis in vitiligo - Singh, Archana; Gotherwal, Vishvabandhu; Junni, Paivi; Vijayan, Vinaya; Tiwari, Manisha; Ganju, Parul; Kumar, Avinash; Sharma, Pankaj; Fatima, Tanveer; Gupta, Aayush; Holla, Ananthaprasad; Kar, Hemanta K.; et al. (Scientific Reports, 2017)
In vitiligo, chronic loss of melanocytes and consequent absence of melanin from the epidermis presents a challenge for long-term tissue maintenance. The stable vitiligo patches are known to attain an irreversible depigmented state. However, the molecular and cellular processes resulting in this remodeled tissue homeostasis is unclear. To investigate the complex interplay of inductive signals and cell intrinsic factors that support the new acquired state, we compared the matched lesional and non-lesional epidermis obtained from stable non-segmental vitiligo subjects. Hierarchical clustering of genome-wide expression of transcripts surprisingly segregated lesional and non-lesional samples in two distinct clades, despite the apparent heterogeneity in the lesions of different vitiligo subjects. Pathway enrichment showed the expected downregulation of melanogenic pathway and a significant downregulation of cornification and keratinocyte differentiation processes. These perturbations could indeed be recapitulated in the lesional epidermal tissue, including blunting of rete-ridges, thickening of stratum corneum and increase in the size of corneocytes. In addition, we identify marked increase in the putrescine levels due to the elevated expression of spermine/spermidine acetyl transferase. Our study provides insights into the intrinsic self-renewing ability of damaged lesional tissue to restore epidermal functionality in vitiligo.

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

MCM-41-supported phosphotungstic acid-catalyzed cleavage of C-O bond in allyl aryl ethers - Sakate, Sachin S.; Kamble, Sumit B.; Chikate, Rajeev C.; Rode, Chandrashekhar V. (New Journal of Chemistry, 2017)
Removal of the protecting allyl group from allyl aryl ethers in the presence of other oxygen protecting groups was successfully achieved using a solid acid supported on the high surface area material MCM-41. The catalyst showed excellent activity in the presence of various electron withdrawing, electron donating, and oxidizable functional groups. The methodology is also very useful for the removal of protecting allyl groups of various natural products such as vanillin, isovanillin, and other oxygen functionalized aldehydes and ketones.

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

Metal-free, brønsted acid-catalyzed formal [3+2] annulation of quinone monoacetals with 2-naphthols - Jacob, Anu; Roy, Tony; Kaicharla, Trinadh; Biju, Akkattu T. (Journal of Organic Chemistry, 2017)
An operationally simple and metal-free cross-coupling of quinone monoacetals (QMAs) with 2-naphthols catalyzed by triflic acid is reported. This formal [3+2] annulation allowed the synthesis of diverse naphtho[2,1-b]benzofuranderivatives in moderate to good yields. Preliminary mechanistic studies reveal the initial nucleophilic substitution of QMAs with 2-naphthols in preference to the mixed acetal formation and subsequent [3,3] sigmatropic rearrangement.

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

MgFeCe ternary layered double hydroxide as highly efficient and recyclable heterogeneous base catalyst for synthesis of dimethyl carbonate by transesterification - Nivangune, N. T. (Catalysis Letters, 2017)
A series of Mg3:Fex + Ce1−x LDHs (3:1) were synthesized by co-precipitation method by varying molar ratio of Fe:Ce between 1:0 to 0:1 (LDH-1 to LDH-6). All synthesized LDHs were characterized by XRD, FT-IR, TEM, N2 sorption, benzoic acid titration and XPS in detail and evaluated for selective synthesis of dimethyl carbonate by transesterification of ethylene carbonate with methanol. It was demonstrated that the structural and basic properties of synthesized LDHs were strongly dependent on the Fe:Ce molar ratio (Ce concentration). The correlation between their physicochemical properties and catalytic performance was studied in detail. Among all synthesized LDHs the best result was obtained with LDH-3 (Fe:Ce = 0.85:0.15) where LDH structure remained intact, and showed high number of strong basic sites on LDH surface. LDH-3 was recycled 7 times while maintaining high catalyst activity and selectivity towards DMC. The obtained results elucidate the important role of Ce in modifying the basic properties of LDH in enhancing the catalytic activity for DMC synthesis. Graphical Abstract: [Figure not available: see fulltext.]. © 2017, Springer Science+Business Media, LLC.
Keywords: Dimethyl carbonate; ethylene carbonate; Mg–Fe–Ce Ternary Hydrotalcite; transesterification

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

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

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

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

Modular approach towards functionalized highly stable self-complementary quadruple hydrogen bonded systems - Rayavarapu, Suresh; Kheria, Sanjeev; Shinde, Dinesh R.; Gonnade, Rajesh G.; Sanjayan, Gangadhar J. (Organic & Biomolecular Chemistry, 2017)
Self-complementary quadruple hydrogen bonded systems have shown potential as key building blocks for developing various supramolecular polymers. Opportunities for the introduction of multiple functionalities would further augment, in principle, their application potential. Herein, we report a novel modular approach to simultaneously introduce two closely aligned side chains into AADD-type self-complementary quadruple hydrogen-bonding systems. Dithiane-tethered ureidopyrimidinone has been used as a reactive intermediate to efficiently attach closely aligned side chains by simply reacting with amines to form highly stable molecular duplexes. These duplexes featuring AADD-type arrays of hydrogen bonding codes are highly stable in non-polar solvents (K-dim > 1.9 x 10(7) M-1 in CDCl3) as well as in polar solvents (K-dim > 10(5) in 10% DMSO-d(6)/CDCl3). Another notable feature of these self-assembling systems is their insensitivity to prototropy-related issues owing to their prototropic degeneracy, which will enhance their application potential in supramolecular chemistry.

Molecular control of the band edge movement and the recombination process in donor-acceptor hemicyanine-sensitized solar cells - Karjule, Neeta; Kavungathodi, Munavvar Fairoos Mele; Nithyanandhan, Jayaraj (Journal of Physical Chemistry C, 2017)
The presence of downward shift in the band edge and the recombination reactions in the hemicyanine-sensitized solar cell reduces the open-circuit potential (V-oc) and the short-circuit current density (J(sc), which in turn decreases the dye cell performance. Choosing either an electrolyte possessing minimum overpotentials or a systematic dye design which can efficiently suppress the diffusion of charged species toward the TiO2 can improve the overall power conversion efficiency (PCE). Here, a series of donor acceptor (D-A) hemicyanine dyes were synthesized utilizing a planar heterotriangulene (HT) or triphenylamine (TPA) donor and alkyl-functionalized indolium carboxylic acid acceptor unit. By introducing strong HT donor instead of TPA, the photophysical, and electrochemical properties of D-A dyes are significantly modulated. The strong donor nature of HT and effective passivation of surface by hydrophobic alkyl chains close to the anchoring group for NC3 dye exhibits an average PCE of 4.34% with a V-oc of 0.416 V, J(sc) of 20.04 mA cm(-2), and fill factor (ff) of 52.03% under simulated AM 1.5G illumination (100 mW cm-2) without 3 alpha,7 alpha-adihydroxy-5 beta-cholic acid coadsorbent (CDCA). The intrinsic dipole of the hemicyanine dye and the presence of Li+ ions in iodide/triiodide redox couple without tert-butylpyridine (TBP) additive induces a downward shift in conduction band edge (E-CB) of TiO2. By rational molecular design, the extend of shift in E-CB is controlled and enhanced the V-oc. Electrochemical impedance spectroscopy (EIS) studies revealed the high charge transfer resistance (R-ct) and long lifetime (tau) of injected electrons in HT-based dyes than that of TPA derivatives, which provide insight into the passivation of Li+ and I- ions by current D-A dye design possessing alkyl functionalities to increase both the J(sc) and V-oc.

Molecular dynamics simulation and experimental study on the growth of methane hydrate in presence of methanol and sodium chloride - Choudhary, Nilesh; Kushwaha, Omkar Singh; Bhattacharjee, Gaurav; Chakrabarty, Suman; Kumar, Rajnish (Energy Procedia, 2017)
The plugging of processing and transportation lines by gas hydrate formation is a challenging problem for safe exploitation of oil and gas. The existence of water soluble third component (like methanol and sodium chloride) in the aqueous phase influence the gas hydrate formation thermodynamically also possibly affects the kinetics of hydrate growth. Inorganic salt and organic molecule (alcohols) at high concentration in the aqueous phase have been used as thermodynamic inhibitors to effectively prevent the hydrate formation. This study utilizes molecular dynamics as well as an experimental method to investigate the mechanism of the hydrate formation and the effect of additives. The MD simulation showed that at moderate temperature and pressure, a low concentration (1 wt %) of methanol and NaCl enhances methane hydrate growth kinetics. Significant numbers of methanol molecules were observed inside the gas hydrate cages whereas Na⁺/Cl⁻ ions leach out during hydrate formation.

Molecular motifs for additives that retard PEO crystallization - Shrivastava, Sudhakar Dinesh; Eldho, Kavalakal Mathai; Rajamohanan, P. R.; Ajithkumar, Thalasseril G.; Vanka, Kumar; Kumaraswamy, Guruswamy (Polymer Engineering & Science, 2017)
We investigate the influence of several bifunctional phenol additives (resorcinol: RES, hydroquinone: HYD, p-hydroxybenzoic acid: PHBA, and p-nitrophenol: PNP) on the crystallization of matrix polymer, polyethyleneoxide. We employ solid state Nuclear Magnetic Resonance spectroscopy (NMR), Differential Scanning Calorimetry (DSC), optical microscopy, and Small Angle X-ray Scattering (SAXS) to investigate crystallization of the additivated PEO and compare with Density Functional Theory (DFT) calculations of additive-PEO interactions. Additive-polymer interactions are a function of the functional groups on the additive. Temperature-dependent spherulitic growth rate measurements from optical microscopy and SAXS lamellar long spacings indicate a distinct trend in the effect of additives on PEO crystallization. Change in PEO crystallization is most pronounced with PNP, followed by PHBA and finally RES and HYD. This trend correlates qualitatively with the binding energies of additive-PEO interactions from DFT studies. Our results suggest that DFT calculations might be a useful screening tool to evaluate the influence of additives on polymer crystallization. POLYM. ENG. SCI., 2016. © 2016 Society of Plastics Engineers

Molybdenum oxide-mediated facile aliphatic nucleophilic fluorination - Said, Madhukar S.; Khandare, Leena; Shinde, Sandip S. (Tetrahedron Letters, 2017)

MoO3-rGO nanocomposites for electrochemical energy storage - Khandare, Lina; Late, Dattatray J. (Applied Surface Science, 2017)
We have synthesized the one dimensional (1D) MoO3 nanorods and MoO3-rGO nanocomposite by using sonochemical dispersion method at low temperature. The obtained products were characterized by using Raman spectroscopy, FT-IR, SEM, TEM and HR-TEM. We have demonstrated the electrochemical properties of MoO3 nanorods and MoO3-rGO nanocomposites. The specific capacitance for MoO3 nanorods and MoO3-rGO nanocomposite was calculated to be 3.3 F/g and 22.83 F/g at current density of 0.3 A/g respectively. The nanocomposite of MoO3-rGO shows the better electrochemical performance as compared to pristine MoO3 nanorods sample due to improvement in the conductivity. Our result suggests that the MoO3-rGO nanocomposites material has great potential for electrochemical energy storage and related applications. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Energy storage; Nanocomposites; Nanorods; Storage (materials); Temperature

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

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

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

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

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

New and efficient enantioselective synthesis of both enantiomers of the calcium channel blocker bepridil - Mujahid, Mohammad; Subramanian, Jambu; Nalla, Viswanadh; Sasikumar, Murugesan; Kunte, Sunita Sharad; Muthukrishnan, Murugan (New Journal of Chemistry, 2017)
A concise and efficient enantioselective synthesis of both enantiomers of bepridil, a calcium channel blocker, is reported. Jacobsen's hydrolytic kinetic resolution method was utilized to resolve racemic 2-(isobutoxymethyl) oxirane. The incorporation of the succinimide moiety by the Mitsunobu reaction, which was investigated in detail, occurred without any loss of enantioselectivity. Using this strategy, both enantiomers of the target molecule were obtained in good yield and with high enantiopurity (ee > 99%).

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

New insight into sugarcane industry waste utilization (press mud) for cleaner biobutanol production by using c. acetobutylicum nrrl b-527 - Nimbalkar, Pranhita R.; Khedkar, Manisha A.; Gaikwad, S. G.; Chavan, Pramod V.; Bankar, Sandip B. (Applied Biochemistry and Biotechnology, 2017)
In the present study, press mud, a sugar industry waste, was explored for biobutanol production to strengthen agricultural economy. The fermentative production of biobutanol was investigated via series of steps, viz. characterization, drying, acid hydrolysis, detoxification, and fermentation. Press mud contains an adequate amount of cellulose (22.3%) and hemicellulose (21.67%) on dry basis, and hence, it can be utilized for further acetone-butanol-ethanol (ABE) production. Drying experiments were conducted in the temperature range of 60–120 °C to circumvent microbial spoilage and enhance storability of press mud. Furthermore, acidic pretreatment variables, viz. sulfuric acid concentration, solid to liquid ratio, and time, were optimized using response surface methodology. The corresponding values were found to be 1.5% (v/v), 1:5 g/mL, and 15 min, respectively. In addition, detoxification studies were also conducted using activated charcoal, which removed almost 93–97% phenolics and around 98% furans, which are toxic to microorganisms during fermentation. Finally, the batch fermentation of detoxified press mud slurry (the sample dried at 100 °C and pretreated) using Clostridium acetobutylicum NRRL B-527 resulted in a higher butanol production of 4.43 g/L with a total ABE of 6.69 g/L. © 2017 Springer Science+Business Media New York Author keywords
Keywords: Acetone; Acetone butanol ethanols; Acidic pre treatments; Agriculture; Biobutanol; cellulose; Clostridium acetobutylicum; Detoxification; Drying; Drying Fermentation; FermentationSpoilage; Fermentative production; Pre-treatment; Press mud; Press mud Pretreatment; Response surface methodology; Sugar industry; Sulfur determination

New pyrene cored small organic molecule with a flexible alkyl spacer: a potential solution processable blue emitter with bright photoluminescence - Valsange, Nitin G.; Wong, F. L.; Shinde, Durgaprasad; Lee, C. S.; Roy, V. A. L.; Manzhos, Sergei; Feron, K.; Chang, Samuel; Katoh, Ryuzi; Sonar, Prashant; Wadgaonkar, Prakash P. (New Journal of Chemistry, 2017)
A new pyrene cored small organic molecule viz. 1,3,6,8-tetrakis(4-((5-(9H-carbazol-9-yl) pentyl)oxy) phenyl)pyrene (PY-II) was designed and synthesized. The carbazole moiety with an alkyl spacer was introduced at 1, 3, 6 and 8 positions of the pyrene core to improve the charge transport properties and solution processability. PY-II exhibited excellent solubility in common organic solvents and high thermal stability up to 345 degrees C. The photoluminescence quantum yield (PLQY) of PY-II in solution was found to be 0.9 with bright blue emission near 450 nm which is just appropriate for the human eye. The solution processed non-doped OLED device fabricated using PY-II as an emissive layer afforded a pure blue emission with CIE coordinates of 0.16 and 0.16, a power efficiency of 0.17 lm W-1, a maximum current efficiency of 0.41 cd A(-1) and a maximum brightness of 202 cd m(-2).

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

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

Nitrogen-doped graphene with a three-dimensional architecture assisted by carbon nitride tetrapods as an efficient metal-free electrocatalyst for hydrogen evolution - Gangadharan, Pranav K.; Unni, SreeKuttan M.; Kumar, Nandha; Ghosh, Prasenjit; Kurungot, Sreekumar (Chemelectrochem, 2017)
Current polymer membrane-based electrolyzers use Pt as a cathode catalyst for efficient reduction of water. The high cost of Pt-based catalysts forces researchers to develop alternative electrocatalysts. Here, a simple strategy has been proposed to synthesize a metal-free electrocatalyst for the hydrogen evolution reaction (HER) by high-temperature annealing of graphene oxide-coated melamine foam. The prepared catalyst possesses both structural and functional advantages with its three-dimensional (3D) interconnected arms of carbon nitride (CNx) backbone wrapped with nitrogen-doped graphene (N-RGO) sheets (CNx@N-RGO). CNx@N-RGO faces only a 193 mV overpotential to achieve a current density of 10mAcm(-2), which is far superior to the previously reported Pt-free systems. Along with the high exchange current density 34.7 x 10(-6)A cm(-2) and low Tafel slope of 54 mV dec(-1), CNx@N-RGO follows a Volmer-Heyrovsky mechanism for the HER. DFT calculations show that the synergy between CNx and N-RGO facilitates good electrical coupling between the two moieties and provides optimal binding to H+ ions on the catalyst that, in turn, results in efficient reduction of hydrogen ions.
Keywords: carbon nitride; Density functional theory; electrocatalyst; hydrogen evolution reaction; nitrogen doped graphene

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

Novel interaction study of Th(IV) and Zr(IV) with 4-sulfonatocalix[6]arene: experimental and theoretical investigation - Rathod, N.V. (Polyhedron, 2017)
Calixarenes based ligands are well known in the extraction of heavy metal ions. The modifications at lower as well as upper rim increase the new possibilities of metal extraction in terms of quantum and selectivity of metal. In comparison to calix[4]arene, complexing nature of calix[6]arene is less studied due to its large size and flexible nature. In the present study, 4-sulfonatocalix[6]arene (SCX6) is synthesized and an attempt has been made to understand its complexation behavior with Th(IV) and Zr(IV) metal ions. The effect of different solvents has been examined along with calculation of binding constants for better complexation possibilities. Though in general, its complexation proves to be at 1:1 stoichiometry with respect to ligand and metal, the specific metals show its characteristic modes of interaction with the ligand. This has been understood through IR spectroscopic analysis and density functional theory based first principle studies. 1H NMR spectra of SCX6 and its complexes with Th(IV) and Zr(IV) metal ions was established. IR, UV–Vis, fluorescence spectroscopic studies provided a systematic understanding about the binding behavior of these two metals including interference possibilities from other metals.
Keywords: 4-Sulfonatocalix[6]arene; DFT; metal complexation; Th(IV) Zr(IV)

Nucleotide dependent switching in Rho GTPase: conformational heterogeneity and competing molecular interactions - Kumawat, Amit; Chakrabarty, Suman; Kulkarni, Kiran (Scientific Reports, 2017)
Ras superfamily of GTPases regulate myriad cellular processes through a conserved nucleotide (GTP/ GDP) dependent switching mechanism. Unlike Ras family of GTPases, for the Rho GTPases, there is no clear evidence for the existence of "sub-states" such as state 1 & state 2 in the GTP bound form. To explore the nucleotide dependent conformational space of the Switch I loop and also to look for existence of state 1 like conformations in Rho GTPases, atomistic molecular dynamics and metadynamics simulations on RhoA were performed. These studies demonstrate that both the nucleotide-free state and the GDP bound "OFF" state have very similar conformations, whereas the GTP bound "ON" state has unique conformations with signatures of two intermediate states. The conformational free energy landscape for these systems suggests the presence of multiple intermediate states. Interestingly, the energetic penalty of exposing the non-polar residues in the GTP bound form is counter balanced by the favourable hydrogen bonded interactions between the gamma- phosphate group of GTP with the highly conserved Tyr34 and Thr37 residues. These competing molecular interactions lead to a tuneable energy landscape of the Switch I conformation, which can undergo significant changes based on the local environment including changes upon binding to effectors.

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

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

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

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

Organocatalytic Enantioselective Vinylogous Michael-Aldol Cascade for the Synthesis of Spirocyclic Compounds - Jain, B. (Electrochimica Acta, 2017)
Nanoscopic spheres of poly(3,4-ethylenedioxythiophene) from its poly(styrene sulfonate) stabilised dispersion was converted to nanofibers by acid treatment. The nanofibers showed a conductivity of 1800 S/cm. The specific capacitance of nanofiber based supercapcitors increased by 10 times compared to nanospeheres. The specific capacitance and power density were found to be 288 F/g and 9491 W/kg.

Organocatalyzed efficient one-pot synthesis, biological evaluation, and molecular docking studies of 4,4-(Arylmethylene)bis-(3-methyl-1-phenyl-1H-pyrazol-5-ols) - Mahajan, Pravin S.; Nikam, Mukesh D.; Khedkar, Vijay; Jha, Prakash; Badadhe, Pravin V.; Gill, Charansingh H. (Journal of Heterocyclic Chemistry, 2017)
The synthesis of 4,4-(arylmethylene)bis-(3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives catalyzed by ?-proline is a simple, versatile, and efficient method. In vitro antioxidant, anti-inflammatory, and antimicrobial activities of compounds 4a, 4b, 4c, 4d, 4e, 4f, 4g, 4h, 4i, 4j were studied. Furthermore, to rationalize the observed anti-inflammatory activity data, molecular docking study has been performed against COX-2 enzyme which revealed a good binding affinity for these molecules and could provide an insight into the various bonded and non-bonded interactions guiding their binding affinity.

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

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

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

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

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

Palladium supported ionic liquid phase catalyst (Pd@SILP-PS) for room temperature Suzuki-Miyaura cross-coupling reaction - More, S.; Jadhav, S; Salunkhe, R.; Kumbhar, A. (Molecular Catalysis, 2017)
A new Pd-SILP based on amino functionalized imidazolium ionic liquid immobilized on Merrifield resin (Pd@SILP-PS) has been synthesized. The catalyst was characterized by different techniques like FT-IR, SEM-EDS, TEM, TGA-DTA and XPS. The catalyst has shown to be highly active in Suzuki-Miyaura cross-coupling reaction of various aryl halides and aryl boronic acids in ethanol at room temperature. The activity of catalyst and the nature of product were highly dependent on the type of the solvent used, as well as the substituents present on the aryl halides. The protic polar solvent ethanol gave desired cross-coupling product in good to excellent yields at room temperature. However the aprotic polar solvent THF gave homocoupling product. The catalyst showed at least five times recyclability without a decrease in product yield.
Keywords: Immobilization; Ionic liquid; Palladium; SILP; Suzuki-Miyaura reaction

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

Partially bio-based poly(amide imide)s by polycondensation of aromatic diacylhydrazides based on lignin-derived phenolic acids and aromatic dianhydrides: synthesis, characterization, and computational studies - Kuhire, Sachin S.; Sharma, Pragati; Chakrabarty, Suman; Wadgaonkar, Prakash P. (Journal of Polymer Science Part A-Polymer Chemistry, 2017)
Two new bio-based diacylhydrazide monomers, namely, 4,4-(propane-1,3-diylbis(oxy))bis(3-methoxybenzohydrazide) and 4,4-(propane-1,3-diylbis(oxy))bis(3,5-dimethoxybenzohydrazide) were synthesized starting from lignin-derived phenolic acids, namely, vanillic acid and syringic acid. A series of poly(amide imide)s was synthesized by polycondensation of these diacylhydrazide monomers with commercially available aromatic dianhydrides. Poly(amide imide)s showed inherent viscosity in the range 0.44-0.56 dLg(-1) and exhibited good solubility in organic solvents. Poly(amide imide)s could be cast into transparent, flexible, and tough films from their N,N-dimethylacetamide solutions. Poly(amide imide)s showed 10% weight loss in the temperature range 340-364 degrees C indicating their good thermal stability. Glass transition temperature (T-g) of poly(amide imides)s were measured by DSC and DMA which were in the range 201-223 degrees C and 214-248 degrees C, respectively. The T-g values of poly(amide imide)s were dependent on the number methoxy substituents on aromatic rings of diacylhydrazide monomers. Molecular dynamics simulation studies revealed that chain rigidity is the dominant factor for observed trends in T-g. (c) 2017 Wiley Periodicals, Inc.
Keywords: Biobased Polymers; Computational studies; Glass-transaction temperature; lignin; Monomers; Plant oils; Polyimide; Reneable resources; Renewable resources; Step-growth polymers; structure-property relations; Sustanaible Polymers; Thermal night; Thermosetting resins; Vanillin

Perspective article: flow synthesis of functional materials - Sebastian, Victor; Khan, Saif A.; Kulkarni, Amol A. (Journal of Flow Chemistry, 2017)
Continuous-flow synthesis of specific functional materials is now seen as a reliable synthesis approach that gives consistent product properties. This perspective article aims to survey recent work in some of the relevant areas and to identify new domains where flow synthesis of functional materials can be better than the conventional synthesis methods. It also emphasizes the need for developing high-throughput integrated synthesis and screening systems for almost all functional materials so that laboratory-scale recipes can be transformed into reliable manufacturing processes. New areas relevant to functional materials which have remained unexplored in flow synthesis are also highlighted.

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

Photocatalytic degradation of pharmaceuticals pollutants using N-doped TiO 2 photocatalyst: identification of CFX degradation intermediates - Shetty, Rohit; Chavan, Vilas B.; Kulkarni, Prashant Shripad; Kulkarni, Bhaskar D.; Kamble, Sanjay P. (Indian Chemical Engineer, 2017)
The N-doped TiO2 photocatalyst was synthesized by the sol–gel method and characterized in detail in terms of its morphology, structure and composition. The prepared N-doped TiO2 exhibited polycrystalline structure having particle sizes of around 50–120 nm and rod-shaped geometry. The N-doped TiO2 was subsequently used for the photocatalytic degradation (PCD) of pharmaceutical micropollutants, namely ciprofloxacin HCl (CFX), naproxen (NPX) and paracetamol (PARA) and it was found that the rate of degradation of CFX and NPX is higher than that of PARA. To verify the beneficial effect of N-doped TiO2 for PCD of CFX, similar experiments were carried out using commercially available Aeroxide P-25 TiO2. It was observed that N-doped TiO2 was more efficient than Aeroxide® P-25 TiO2. It was also found that the PCD of CFX in the presence of N-doped TiO2 was highly efficient under the solar radiation as compared with artificial radiation. The effect of various operating parameters, such as adsorption of CFX, pH of the aqueous solution, effect of co-existing ions on PCD of CFX, was investigated using artificial radiation and optimum conditions were established. The intermediates formed during the PCD of CFX were identified using liquid chromatography tandem mass chromatography (LC-MS/MS). The presented results demonstrate that N-doped TiO2 photocatalyst shows excellent photocatalytic activity in the visible region for the degradation of pharmaceutical pollutants.

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

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

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

Placental proteomics provides insights into pathophysiology of pre-eclampsia and predicts possible markers in plasma - Mary, Sheon; Kulkarni, Mahesh J.; Malakar, Dipankar; Joshi, Sadhana Ramchandra; Mehendale, Savita S.; Giri, Ashok P. (Journal of Proteome Research, 2017)
Pre-eclampsia is a hypertensive disorder characterized by the new onset of hypertension >140/90 mmHg and proteinuria after the 20th week of gestation. The disorder is multi-factorial and originates with abnormal placentation. Comparison of the placental proteome of normotensive (n=25) and pre-eclamptic (n=25) patients by gel-free proteomic techniques, identified a total of 2145 proteins in the placenta of which 180 were differentially expressed (>1.3 fold, p<0.05). Gene ontology enrichment analysis of biological process suggested that the differentially expressed proteins belonged to various physiological processes such as angiogenesis, apoptosis, oxidative stress, hypoxia, placental development, which are implicated in the pathophysiology of pre-eclampsia. Some of the differentially expressed proteins were monitored in the plasma by multiple reaction monitoring (MRM) analysis, which showed an increase in Apolipoprotein AI and AII in gestational week 26-30th (2-fold, p<0.01) while haptoglobin and hemopexin decreased in gestational week 26-30th and 40th week/at delivery (1.8 fold, p<0.01) in pre-eclamptic patients. This study provides a proteomic insight into the pathophysiology of pre-eclampsia. Identified candidate proteins can be evaluated further for the development of potential biomarkers associated with pre-eclampsia pathogenesis.

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

Plasmonic behavior of ionic liquid stabilized gold nanoparticles in molecular solvents - Thawarkar, Sachin; Thombare, Balu; Khupse, Nageshwar D. (New Journal of Chemistry, 2017)
In this paper, we have demonstrated the facile synthesis of stable gold nanoparticles (AuNPs) using imidazolium ionic liquids (ImILs) as a stabilizer as well as a surfactant and their surface plasmon resonance (SPR) in different molecular solvents with varying dielectric properties. The preparation of AuNPs capped with N,N'-dialkyl ImILs of different chain lengths (denoted as [C-4, C-n-im]Br, n = carbon number of the alkyl chain) has been investigated. With one long alkyl chain (n >= 14), these AuNPs could be stably dispersed in solution over a month. The amphiphilic nature of the imidazolium salt dictates the stability and dispersion of these AuNPs in organic or aqueous solvents. Alkyl chain lengths (n >= 14) and the amount of ImILs have insignificant effect on the size of AuNPs and they possess an average size of 5 nm. These ionic liquid stabilized AuNPs were exploited to examine their optical properties when exposed to various solvent systems by measuring the change in the SPR spectrum. It was seen that the position of the SPR band of AuNPs is greatly influenced by the solvents under consideration. The shift in the SPR absorption band is observed to be in the range of 520 nm to 605 nm for AuNP@[C-4,C-16-im]Br from nonpolar to highly polar solvents. The considerable discovery presented here is that the lambda(SPR) of the SPR shifts to the blue with the increase of carbon atom in the alcohol chain from methanol to 1-decanol. Also for polyethylene glycols (PEGs), the lambda(SPR) shifts to the blue with the increase in molecular weight from PEG 200 to PEG 600. In above both cases, the variation in SPR of AuNPs is observed according to the dielectric properties of the medium in addition to the steric factor of alcohols and PEGs during their interaction with AuNP surfaces.

Poly(ether urethane)s from aromatic diisocyanates based on lignin-derived phenolic acids - Kuhire, Sachin; Nagane, Samadhan S.; Wadgaonkar, Prakash (Polymer International, 2017)

Polyhydroxyalkanoates as biomaterials - Bhagyashri, S.; Gadgil, Thorat; Killi, Naresh; Rathna, Gundloori V. N. (MedChemComm, 2017)
Polyhydroxyalkanoates (PHAs) are biopolymers synthesized by bacteria under unbalanced growth conditions. These biopolymers are considered as potential biomaterials for future applications because they are biocompatible, biodegradable, and easy to produce and functionalize with strong mechanical strength. Currently, PHAs are being extensively innovated for biomedical applications due to their prerequisite properties. The wide range of biomedical applications includes drug delivery systems, implants, tissue engineering, scaffolds, artificial organ constructs, etc. In this article we review the utility of PHAs in various forms (bulk/nano) for biomedical applications so as to bring about the future vision for PHAs as biomaterials for the advancement of research and technology.
Keywords: Biomedical Applications; Cancer-therapy; Drug-delivery Systems; In-vitro; Molecular-weight; Poly(Ester Urethane)S; poly(ethylene glycol); Regenerative Medicine; Tissue Engineering Applications; Vitro Antibiotic Release

Polymer and graphene layer to increase dye regeneration and suppress back electron transfer in dye sensitized solar cells - Sudhakar, Vediappan; Arulkashmir, Arulraj; Krishnamoorthy, Kothandam (Chemical Communications, 2017)
Dye regeneration was improved by using an optimum quantity of graphene, which was dispersed in a polymer that suppresses back electron transfer. Using this approach, DSSCs with an efficiency of 10.4% have been fabricated.

Polymorphism, isostructurality and physicochemical properties of glibenclamide salts - Suresh, Kuthuru; Khandavilli, U. B. Rao; Gunnam, Anilkumar; Nangia, Ashwini (CrystEngComm, 2017)
Novel salts of glibenclamide (GBA), namely glibenclamide-sodium (GBA-Na), glibenclamide-potassium (GBA-K) and glibenclamide-ammonium (GBA-NH4) were crystallized under different conditions to obtain their polymorphs, and their aqueous solubility and hydration stability studies are reported. The GBA-Na salt is dimorphic (forms I and II)and also exists as hydrate GBA-Na-H2O (form III). The GBA-K salt exists in anhydrous and hydrate forms (GBA-K, forms I and II). Crystal structure analysis of GBA-Na forms I and II showed differences in geometry of the central metal atom and ligand orientation. This kind of polymorphism of sulfonyl urea salts appears to be novel in the Cambridge Structural Database (CSD). The iso-structurality of GBA-Na form I with GBA-NH4 and GBA-K form I salts is discussed. The potassium salts of GBA exhibited higher solubility compared to pure GBA. Specifically GBA-K salt forms I and II showed higher solubility by 77 fold in the water and 33 fold in phosphate buffer (pH 7) compared to the other salts. Dynamic vapor sorption (DVS) showed reversible water sorption without hysteresis for all salts, except for GBA-K form II which transformed to form I after a sorption and desorption cycle as confirmed by PXRD.

Porous porphyrin organic polymer (PPOP) for visible light triggered hydrogen production - Mukherjee, Gargi; Thote, Jayshri; Aiyappa, Harshitha Barike; Kandambeth, Sharath; Banerjee, Subhrashis; Vanka, Kumar; Banerjee, Rahul (Chemical Communications, 2017)
A visible light active porphyrin-based porous organic polymer having high chemical stability and surface area has been synthesized and its ability to influence the photocatalytic activity of large band gap-TiO2 nanoparticles has been tested. The resultant composite shows improved photocatalytic activity as compared to the parent precursors. This study provides insights into the photosensitizing ability of the polymer in addition to its ability to firmly harbor nanoparticles onto its surface.

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

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

Probing the solute-solvent interactions in the binary mixtures of ionic liquids with water and alcohols by conductance, viscosity and IR spectroscopy - Jain, Preeti; Kumar, Anil (Journal of Molecular Liquids, 2017)
The molar conductance and viscosities of the bisulfate ([HSO4](-)) and ethylsulfate ([EtSO4](-))-based imidazolium ionic liquids in various molecular solvents have been measured at 298.15 K as a function of concentration of ionic liquids (1 x 10(-4) to 0.1 mol L-1). It is shown that the anions have considerable effect on the molar conductance and association constant of the [HSO4](-) and [EtSO4](-)-based imidazolium ionic liquids. Higher molar conductance of the [HSO4](-)-based imidazolium ionic liquids in polar protic solvents (water and methanol) is noted as compared to the [EtSO4](-)-based imidazolium ionic liquids, though the [HSO4](-)-based imidazolium ionic liquids possess higher association constant in water than in methanol. The intermolecular interactions in the pure and binary mixture of [HSO4](-) and [EtSO4](-)-based imidazolium ionic liquids have been investigated by IR spectroscopy. The C-2-H stretching vibration frequency of the imidazolium ring reveals the H-bonding between cations and anions of pure ionic liquids and their solutions. The transport properties (limiting molar conductance, transport number, ionic mobility and diffusion coefficient) of cations and anions correlate well with the hydrodynamic radius in their aqueous solutions. The study shows that the energy barrier for charge transfer is minimal as compared to the fluidity of the aqueous solution of the studied ionic liquids obtained from the Arrhenius equation. (C) 2017 Elsevier B.V. All rights reserved.