Method to form semiconductor quantum dot (QD) thin films by igniting a flame at air-liquid interface: CdS and WO3 - Jadhav, Aarti H.; Patil, Sagar H.; Sathaye, Shivaram D.; Patil, Kashinath R. (Journal of Colloid and Interface Science, 2015)
We reveal an easy, inexpensive, efficient one step flame synthesis of semiconductor/metal oxide thin films at air-liquid interface, subsequently, transferred on suitable substrate. The method has been illustrated by the formation of CdS and Wo(3) QDs thin films. The features of the present method are (1) Growth of thin films consisting of 0.5-2.0 nm sized Quantum Dots (QDs)/(ultra-small nanoparticles) in a short time, at the air-liquid interface which can be suitably transferred by a well-known Blodgett technique to an appropriate substrate, (2) The method is suitable to apply layer by layer (LbL) technique to increase the film thickness as well as forming various compositions as revealed by AFM measurements. The films are characterized for their structure (SAED), morphology (TEM), optical properties (UV-Vis.) and photoluminescence (PL). Possible mechanism of formation of QDs thin film and effect of capping in case of COS QDs is discussed. (C) 2014 Elsevier Inc. All rights reserved.
Keywords: CdS; Flame synthesis; interface; Quantum Dots (QDs); thin film; WO3

Microbacterium enclense sp nov., isolated from sediment sample - Mawlankar, Rahul R.; Mual, Poonam; Sonalkar, Vidya V.; Thorat, Meghana N.; Verma, Ashish; Srinivasan, Krishnamurthi; Dastager, Syed Gulam (International Journal of Systematic and Evolutionary Microbiology, 2015)
A novel bacterium (strain NIO-1002(T)) belonging to the genus Microbacterium was isolated from a marine sediment sample in Chorao Island, Goa Province, India. Its morphology, physiology, biochemical features and 16S rRNA gene sequence were characterized. Cells of this strain were Gram-stain-positive, non-motile, non-spore-forming rods that formed yellow-pigmented colonies. It grew in 0-12 % (w/v) NaCl and at 25-37 degrees C, with optimal growth at 30 degrees C. Phylogenetic analysis based on 16S rRNA gene sequences indicated that strain NIO-1002(T) is associated with members of the genus Microbacterium, with highest sequence similarity with Microbacterium hominis CIP 105731(T) (98.1%) and Microbacterium testaceum KCTC 9103(T) (98.0 %). Within the phylogenetic tree, this novel strain shared a branching point with M. hominis CIP 105731(T). The DNA G+C content was 66.5 mol% and DNA DNA hybridization relatedness between NI-1002(T), M. hominis CIP 105731(T) and M. testaceum KCTC 9103(T) was 39.0 +/- 2.0 % and 41.0 +/- 2.0 %, respectively. The major fatty acids were ai-C-15:0, i-C-16:0 and al-C-17:0 and the diamino acid in the cell-wall peptidoglycan of NIO-1002(T) was lysine. Data obtained from DNA-DNA hybridization and chemotaxonomic phenotypic analysis support the conclusion that strain NIO-1002(T) represents a novel species within the genus Microbacterium. The name Microbacterium enclense sp. nov. is proposed, with NIO-1002(T) (=NCIM 5454(T)=DSM 25125(T)=CCTCC AB 2011120(T)) as the type strain.

Microbial selenium nanoparticles (SeNPs) and their application as a sensitive hydrogen peroxide biosensor - Prasad, Kumar Suranjit; Vaghasiya, Jayraj V.; Soni, Saurabh S.; Patel, Jitesh; Patel, Rinkesh; Kumari, Madhu; Jasmani, Falguni; Selvaraj, Kaliaperumal (Applied Biochemistry and Biotechnology, 2015)
The cell-free extract, a crude enzyme (cytosolic and membrane fraction) obtained from an environmental isolate, Bacillus pumilus sp. BAB-3706 worked as excellent in reducing as well as stabilizing agent and facilitated the formation of stable colloidal selenium nanoparticles (SeNPs). Resulting nanoparticles were characterized using UV-vis spectrophotometer, TEM, EDAX, FT-IR and XRD, respectively. A working electrode was modified by coating the surface of indium tin oxide (ITO) with colloidal SeNPs. Successive additions of H2O2 (100 to 600 mu M) in conventional three electrodes system, cyclic voltammeter with potential scan rate 25.0 mV/s, in 0.1 M phosphate buffer solution (PBS) yielded increase in current. A perpetual amperometric response at fixed potential (-1.0 V) and at selected time interval of 100 s showed different magnitude of current at every addition of H2O2. The linear range of detection of H2O2 was from 5 to 600 mM (R (2) = 0.9965), while the calculated limit of detection was found to be 3.00 mu M. The current study suggested that microbial SeNPs can be used for fabrication of low cost, sensitive H2O2 biosensor.
Keywords: Biosensor; EDAX; Hydrogen peroxide; Selenium nanoparticles; TEM; UV-vis spectroscopy

Micro-structural analysis of NiFe2O4 nanoparticles synthesized by thermal plasma route and its suitability for BSA adsorption - Bhosale, Shivaji V.; Kanhe, Nilesh S.; Bhoraskar, S. V.; Bhat, Suresh K.; Bulakhe, Ravindra N.; Shim, Jae-Jin; Mathe, Vikas L. (Journal of Materials Science-Materials in Medicine, 2015)
The paper presents the experimental studies pertaining to the adsorption of bovine serum albumin (BSA) on the nanoparticles of nickel ferrite (NiFe2O4) with a view of correlating the adsorption properties to their microstructure and zeta potentials. Physical properties of two kinds of nickel ferrites, one synthesized by thermal plasma route and the other by chemical co-precipitation method, are compared. Maximum adsorption (231.57 lg/mg) of BSA onto nickel ferrite nanoparticles, at body temperature (37 degrees C) was observed at pH-value of 5.58 for the thermal plasma synthesized particles showing its higher adsorption capacity than those synthesized by wet chemical means (178.71 mu g/mg). Under the same physical conditions the value of zeta potential, obtained for the former, was higher than that of the latter over a wide range of pH values (3.64-9.66). This is attributed to the differences in the specific surface energies of the two kinds of nanoparticles arising from the degree of crystallinity. The paper presents the experimental evidence for the single crystalline nature of the individual nanoparticles, with mean size of 32 nm, for the thermal plasma synthesized particles as evidenced from the high resolution transmission electron microscopy and electron diffraction analysis. The measurements also reveal the poor crystalline morphology in the chemically prepared particles (mean size of 28 nm) although the X-ray diffraction patterns are not much different. The atomic force microscopy images confirm that the surfaces of plasma synthesized nanoparticles possesses higher surface roughness than that of chemically synthesized one. Presence of adsorbed protein was confirmed by vibrational spectroscopy. The Langmuir adsorption model is found to fit into the experimental data better than the Freundlich adsorption model.

Mild regiospecific alcoholysis and aminolysis of epoxides catalyzed by zirconium(IV) oxynitrate - Shinde, Sandip S.; Said, Madhukar S.; Surwase, Trupti B.; Kumar, Pradeep (Tetrahedron Letters, 2015)
A regiospecific method for the ring-opening reaction of epoxides by the primary, secondary, tertiary alcohols, and aryl, aliphatic amines has been developed using non-toxic metal nitrate salt as a catalyst. The best results were obtained using zirconium(IV) oxynitrate among the various screened metal nitrate salts. The reported protocol works efficiently for styrene epoxide and aliphatic as well. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Alcoholysis; Aminolysis; Epoxide; Lewis acid; Zirconia

Modular synthesis of biaryl-substituted phosphine ligands: application in microwave-assisted palladium-catalyzed C-N cross-coupling reactions - Singh, Chandani; Rathod, Jayant; Jha, Vishwajeet; Panossian, Armen; Kumar, Pradeep; Leroux, Frederic R. (European Journal of Organic Chemistry, 2015)
Biaryl-substituted monophosphine-based ligands have been synthesized by transition-metal-free ARYNE cross-coupling reaction of aryllithiums with 1,2-dibromobenzene and subsequent regioselective functionalization through bromine-lithium interconversion. These ligands were employed in palladium-catalyzed C-N bond-forming reactions. The reaction was found to be general with wide substrate applicability. A wide variety of both primary and secondary amines were successfully coupled with an array of differently substituted halobenzenes under microwave irradiation to give the expected products in good to excellent yields. A number of biaryl-substituted phosphine ligands screened for the coupling reaction showed that steric bulk and the electronic properties of substituents on phosphorus play a crucial role in governing the catalytic activity of C-N cross-coupling reactions.
Keywords: Biaryls; Cross-coupling; Homogeneous catalysis; Microwave chemistry; Palladium; Phosphines; synthetic methods

Molecular docking and QSAR analyses for understanding the antimalarial activity of some 7-substituted-4-aminoquinoline derivatives - Shibi, I. G.; Aswathy, L.; Jisha, Radhakrishnan S.; Masand, Vijay H.; Divyachandran, A.; Gajbhiye, J. M. (European Journal of Pharmaceutical Sciences, 2015)
The quinoline moiety is one of the widely studied scaffolds for generating derivatives with various pharmacophoric groups due to its potential antimalarial activities. In the present study, a series of 7-substituted-4-aminoquinoline derivatives were selected to understand their antimalarial properties computationally by molecular modeling techniques including 2D QSAR, comparative molecular field analysis (CoMFA), comparative molecular similarity indices analysis (CoMSIA) and molecular docking. The 2D-QSAR model built with four descriptors selected by genetic algorithm technique and CoMFA model showed satisfactory statistical results (Q(2) = 0.540, R-ncv(2) = 0.881, F value = 157.09). A reliable CoMSIA model out of the fourteen different combinations has a Q(2) value of 0.638. The molecular docking studies of the compounds for 1CET as the protein target revealed that ten compounds showed maximum interactions with the binding site of the protein. The present study highlights the unique binding signatures of the ligands within the active site groove of the target and it explains the subtle differences in their EC50 values and their mechanism of inhibition. (C) 2015 Elsevier B.V. All rights reserved.

Molecular dynamics simulations of GPCR-cholesterol interaction: an emerging paradigm - Sengupta, Durba; Chattopadhyay, Amitabha (Biochimica Et Biophysica Acta-Biomembranes, 2015)
G protein-coupled receptors (GPCRs) are the largest class of molecules involved in signal transduction across cell membranes and represent major targets in the development of novel drug candidates. Membrane cholesterol plays an important role in GPCR structure and function. Molecular dynamics simulations have been successful in exploring the effect of cholesterol on the receptor and a general consensus molecular view is emerging. We review here recent molecular dynamics studies at multiple resolutions highlighting the main features of cholesterol-GPCR interaction. Several cholesterol interaction sites have been identified on the receptor that are reminiscent of nonannular sites. These cholesterol hot-spots are highly dynamic and have a microsecond time scale of exchange with the bulk lipids. A few consensus sites (such as the CRAC site) have been identified that correspond to higher cholesterol interaction. Interestingly, high plasticity is observed in the modes of cholesterol interaction and several sites have been suggested to have high cholesterol occupancy. We therefore believe that these cholesterol hot-spots are indicative of `high occupancy sites' rather than `binding sites'. The results suggest that the energy landscape of cholesterol association with GPCRs corresponds to a series of shallow minima interconnected by low barriers. These specific interactions, along with general membrane effects, have been observed to modulate GPCR organization. Membrane cholesterol effects on receptor structure and organization, that in turn influences receptor cross-talk and drug efficacy, represent a new frontier in GPCR research. This article is part of a Special Issue entitled: Lipid-protein interactions. Guest Editors: Amitabha Chattopadhyay and jean-Marie Ruysschaert. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Coarse-grain simulation; CRAC; GPCR; Lipid-receptor interaction; Membrane cholesterol; Receptor dimerization

Molecular mechanism underlying recruitment and insertion of lipid-anchored LC3 protein into membranes - Thukral, Lipi; Sengupta, Durba; Ramkumar, Amrita; Murthy, Divya; Agrawal, Nikhil; Gokhale, Rajesh S. (Biophysical Journal, 2015)
Lipid modification of cytoplasmic proteins initiates membrane engagement that triggers diverse cellular processes. Despite the abundance of lipidated proteins in the human proteome, the key determinants underlying membrane recognition and insertion are poorly understood. Here, we define the course of spontaneous membrane insertion of LC3 protein modified with phosphatidylethanolamine using multiple coarse-grain simulations. The partitioning of the lipid anchor chains proceeds through a concerted process, with its two acyl chains inserting one after the other. Concurrently, a conformational rearrangement involving the alpha-helix III of LC3, especially in the three basic residues Lys(65), Arg(68), and Arg(69), ensures stable insertion of the phosphatidylethanolamine anchor into membranes. Mutational studies validate the crucial role of these residues, and further live-cell imaging analysis shows a substantial reduction in the formation of autophagic vesicles for the mutant proteins. Our study captures the process of water-favored LC3 protein recruitment to the membrane and thus opens, to our knowledge, new avenues to explore the cellular dynamics underlying vesicular trafficking.

Molecular sieves and ultrasound-assisted synthesis of novel 1,3,4-oxadiazole-2-thiones derivatives as potential antifungal agents - Nikalje, Anna Pratima G.; Nimbalkar, Ms Urja D.; Tupe, Santosh; Vazquez, Julio A. Seijas; Tato, Maria Pilar Vazquez (19TH INTERNATIONAL ELECTRONIC CONFERENCE ON SYNTHETIC ORGANIC CHEMISTRY, 2015)
In the category of microorganism, fungi are considered as the special class of microbes responsible for opportunistic pathogenic infections in humans species. Due to the side effects of commercially available antifungal drugs and the emergence of new drug resistant fungal species in the past few years, has forced the researchers to search for novel and efficient antifungal drug molecules. The 1,3,4-oxadiazoles scaffold is associated with diverse biological activities. The multipurpose use of the Mannich bases in pharmaceutical chemistry promote us to prepare a new series of 5-(4-(benzyloxy)substituted phenyl)-3-((phenyl amino)methyl)-1,3,4oxadiazole-2(3H)-thione as antifungal agents. Herein, we report molecular sieves and ultrasound assisted synthesis of novel series of Mannich bases of the 5-substituted 1,3,4-oxadiazole-2-thiones by amino methylation with paraformaldehyde and substituted primary / secondary amines and their evaluation for antifungal activity. The structures of the newly synthesized compounds were determined by IR, NMR and Mass spectral study. The synthesized compounds exhibited interesting moderate to excellent antifungal activity against Candida albicans (NCIM 3557), Candida albicans(NCIM3471), Candida glabrata(NCIM3237), Cryptococcus neoformans (NCIM 3542), Cryptococcus neoformans(NCIM 3378), Aspergillus fumigates(NCIM 902), Aspergillus niger(NCIM 628) using Flucanazole as a standard reference drug. The synthesised compounds 6d, 6f,6g, 6h and 6j exhibited promising antifungal activity as antifungal agents.
Keywords: 1; 3; 4-oxadiazoles; Antifungal activity; Mannich reaction; Molecular sieves; Ultrasound -assisted

Multifaceted core-shell nanoparticles: superparamagnetism and biocompatibility - Sardar, Debasmita; Neogi, S. K.; Bandyopadhyay, Sanjoy; Satpati, Biswarup; Ahir, Manisha; Adhikary, Arghya; Jain, Ruchi; Gopinath, Chinnakonda S.; Bala, Tanushree (New Journal of Chemistry, 2015)
NicoreAgshell nanoparticles were synthesized by redox transmetallation reaction. Reduction potential match was encouraging to attempt the synthesis of the NicoreAushell system too. However, it could be achieved only after an effective surface modification on the Ni-core. Thorough characterization (UV-Vis spectroscopy, fluorescence spectroscopy, XRD, XPS, FTIR, TEM, and EDX) proved the necessity of surface modification and the success of synthesis of both types of core-shell structures. The chemical composition and topography were determined using STEM-HAADF analysis and EFTEM imaging. Fourier transform infrared (FTIR) spectroscopy confirmed the surface modification of Ni nanoparticles and the interactions involved between the ligands and metals (in the core and/or the shell) at various steps of the synthetic process. Even after the formation of the noble metal shell, the magnetic core was found to retain its superparamagnetic nature. In addition, the Au-shell protected the core from aerial oxidation and decreased toxicity as compared to pristine Ni nanoparticles as observed by MTT assay on normal cells (PBMCs).

Multifaceted thermodynamics of Pb-n (n=16-24) clusters: a case study - Susan, Anju; Kaware, Vaibhav; Joshi, Kavita (Journal of Physical Chemistry C, 2015)
Thermodynamic response of small clusters is a challenging area of exploration, both experimentally and theoretically. In this article, we study the thermodynamic behavior of small Pb clusters (size 16-24) using Born-Oppenheimer molecular dynamics. A new ground state structure is reported for Pb-20. Except for Pb-21, all clusters fragment at temperatures above T-m[bulk] and show no signs of melting. Characteristic behavior like restricted diffusion and solid solid transition is discussed in detail. Variation in the isomerization temperature of these clusters is explained using the bond length analysis. Root mean square bond length fluctuations (delta(rms)) along with distribution of atoms about center of mass of the cluster as a function of time and distance-energy (DE) plots are used to bring out the essential features of Pb cluster thermodynamics. Analysis carried out using these parameters, and their interpretation regarding state of the system, are discussed in detail. We highlight that it is not possible to define ``liquid state'' for these small clusters, in the conventional frame of understanding.

Multifunctional silica nanoparticles for pancreatic cancer specific drug delivery and bioimaging - Nigam, Preeti; Sarkar, Dhiman (Journal of Chemistry & Applied Biochemistry, 2015)
Mesoporous silica nanoparticles (MSN) have attracted increasing interest as drug carriers due to their biocompatibility and robustness. In this analysis we explored the potential of MSN as nanotheranostic platform for pancreatic cancer specific drug delivery and bioimaging. Pancreatic cancer is the most fatal cancer and due to its high mortality and low prognosis it is imperative to develop new methods for early diagnosis and therapy of this cancer. Though traditionally organic dyes, quantum dots and fluorescent agents are used for bioimaging but here we have utilized graphene quantum dots (GQDs) for bioimaging due to their superior biocompatibility and fluorescence properties. MSN were loaded with gemcitabine; the most preferred drug for pancreatic cancer. MSN and GQDs were characterized by SEM, TEM, FT-IR etc and the efficacy of nanoformulation was determined by MTT assay.

Myroides indicus sp nov., isolated from garden soil - Ram, Hari; Kumar, Alok; Thomas, Lebin; Dastager, Syed Gulam; Mawlankar, Rahul R.; Singh, Ved Pal (International Journal of Systematic and Evolutionary Microbiology, 2015)
A novel aerobic, non-motile, rod-shaped, catalase-and oxidase-positive bacterial strain, designated UKS3(T), was isolated from garden soil, and subjected to polyphasic taxonomic analysis. Strain UKS3(T) formed whitish, viscous colonies on nutrient agar and was Gram-staining negative. Phylogenetic analysis, based on 16S rRNA gene sequence, showed that maximum pairwise similarity occurs with representatives of the genus Myroides. The most closely related species include Myroides marinus JS-08(T) (92.7 % sequence similarity), Myroides phaeus MY15(T) (92.7 %), Myroides odoratus DSM 2801(T) (91.5 %) and Myroides odoratimimus CCUG 39352(T) (91.4 %). Strain UKS3(T) contained menaquinone-6 (MK-6) as the major respiratory quinone and iso-C-15 : 0 (40.2 %), anteiso-C-15 : 0 (9.4 %) and iso-C-17 : 0 3-OH (8.5 %) as major fatty acids. Phosphatidylethanolamine, phospholipids and three aminolipids were the major polar lipids. The DNA G + C content of strain UKS3(T) was 36.8 +/- 2.0 mol%. On the basis of phenotypic, chemotaxonomic and molecular analysis, strain UKS3(T) represents a novel species of the genus Myroides, for which the name Myroides indicus sp. nov., is proposed. The type strain is UKS3(T) (= DSM 28213(T) = NCIM 5555(T)).

Nanocrystalline Fe-Fe2O3 particle-deposited 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, 2015)
The size-controlled growth of nanocrystalline Fe-Fe2O3 particles (2-3 nm) and their concomitant dispersion on N-doped graphene (Fe-Fe2O3/NGr) could be attained when the mutually assisted redox reaction between NGr and Fe3+ ions could be controlled within the aqueous droplets of a water-in-oil emulsion. The synergistic interaction existing between Fe-Fe2O3 and NGr helped the system to narrow down the overpotential for the oxygen reduction reaction (ORR) by bringing a significant positive shift to the reduction onset potential, which is just 15 mV higher than its Pt-counterpart. In addition, the half-wave potential (E-1/2) of Fe-Fe2O3/NGr is found to be improved by a considerable amount of 135 mV in comparison to the system formed by dispersing Fe-Fe2O3 nanoparticles on reduced graphene oxide (Fe-Fe2O3/RGO), which indicates the presence of a higher number of active sites in Fe-Fe2O3/NGr. Despite this, the ORR kinetics of Fe-Fe2O3/NGr are found to be shifted significantly to the preferred 4-electron-transfer pathway compared to NGr and Fe-Fe2O3/RGO. Consequently, the H2O2% was found to be reduced by 78.3% for Fe-Fe2O3/NGr (13.0%) in comparison to Fe-Fe2O3/RGO (51.2%) and NGr (41.0%) at -0.30 V (vs. Hg/HgO). This difference in the yield of H2O2 formed between the systems along with the improvements observed in terms of the oxygen reduction onset and E-1/2 in the case of Fe-Fe2O3/NGr reveals the activity modulation achieved for the latter is due to the coexistence of factors such as the presence of the mixed valancies of iron nanoparticles, small size and homogeneous distribution of Fe-Fe2O3 nanoparticles and the electronic modifications induced by the doped nitrogen in NGr. A controlled interplay of these factors looks like worked favorably in the case of Fe-Fe2O3/NGr. As a realistic system level validation, Fe-Fe2O3/NGr was employed as the cathode electrode of a single cell in a solid alkaline electrolyte membrane fuel cell (AEMFC). The system could display an open circuit voltage (OCV) of 0.73 V and maximum power and current densities of 54.40 mW cm(-2) and 200 mA cm(-2), respectively, which are comparable to the performance characteristics of a similar system derived by using 40 wt% Pt/C as the cathode electrode.

New butenolide cinnamate and other biological active chemical constituents from Polygonum glabrum - Said, Madhukar S.; Chinchansure, Ashish A.; Nawale, Laxman; Durge, Ankita; Wadhwani, Ashish; Kulkarni, Smita S.; Sarkar, Dhiman; Joshi, Swati P. (Natural Product Research, 2015)
Phytochemical investigation of the methanol extract of the aerial parts of Polygonum glabrum afforded one new natural product (-)-2-methoxy-2-butenolide-3-cinnamate (1) along with six known compounds, -hydroxyfriedalanol (2), 3-hydroxy-5-methoxystilbene (3), (-) pinocembrin (4), sitosterol-(6-O-palmitoyl)-3-O–d-glucopyranoside (5), (-) pinocembrin-5-methyl ether (6) and sitosterol-3-O–d-glucopyranoside (7). Compound 1 showed promising in vitro anti-HIV-1 activity against primary isolates HIV-1(UG070) (X4, subtype D) and HIV-1(VB59) (R5, subtype C) assayed using TZM-bl cell line with IC50 in the range of 15.68-22.43g/mL. The extract showed TI in the range of 19.19-27.37 with IC50 in the range of 10.90-15.55g/mL. Compounds 1, 3 and 4 exhibited in vitro anti-mycobacterium activity against Mycobacterium tuberculosis H37Ra with IC50 values of 1.43, 3.33 and 1.11g/mL in dormant phase and 2.27, 3.33 and 1.21g/mL in active phase, respectively. Compound 4 was found to be the most active antiproliferative with IC50 values of 1.88-11.00g/mL against THP-1, A549, Panc-1, HeLa and MCF7 cell lines.
Keywords: anti-HIV-1; anti-mycobacterium; antiproliferative; phytochemicals; Polygonaceae; Polygonum glabrum

New insights into in vitro amyloidogenic properties of human serum albumin suggest considerations for therapeutic precautions - Sharma, Neetu; Sivalingam, Vishwanath; Maurya, Sonalika; Prasad, Archana; Khandelwal, Puneet; Yadav, Subhash Chandra; Patel, Basant K. (Febs Letters, 2015)
Amyloid aggregates display striking features of detergent stability and self-seeding. Human serum albumin (HSA), a preferred drug-carrier molecule, can also aggregate in vitro. So far, key amyloid properties of stability against ionic detergents and self-seeding, are unclear for HSA aggregates. Precautions against amyloid contamination would be required if HSA aggregates were self-seeding. Here, we show that HSA aggregates display detergent sarkosyl stability and have self-seeding potential. HSA dimer is preferable for clinical applications due to its longer retention in circulation and lesser oedema owing to its larger molecular size. Here, HSA was homodimerized via free cysteine-34, without any potentially immunogenic cross-linkers that are usually pre-requisite for homodimerization. Alike the monomer, HSA dimers also aggregated as amyloid, necessitating precautions while using for therapeutics. (C) 2015 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.
Keywords: Drug carrier; HSA amyloid; Plasma expander; Sarkosyl; Self-seeding

N-Heterocyclic carbene catalyzed oxidative coupling of alkenes/alpha-bromoacetophenones with aldehydes: a facile entry to alpha,beta-epoxy ketones - Reddi, Rambabu N.; Prasad, Pragati K.; Sudalai, Arumugam (Angewandte Chemie-International Edition, 2015)
{A novel, N-heterocyclic carbene (NHC) catalyzed direct oxidative coupling of styrenes with aldehydes has been described for the synthesis of alpha,beta-epoxy ketones in good yields. This unprecedented regioselective oxidative coupling employs NBS/DBU/DMSO (DBU = 1,8-diazabicyclo [5.4. 0] undec-7-ene
Keywords: aldehydes; epoxidation; N-heterocyclic carbenes; Oxidation; synthetic methods

Nioella nitratireducens gen. nov., sp nov., a novel member of the family Rhodobacteraceae isolated from Azorean Island - Rajasabapathy, Raju; Mohandass, Chellandi; Yoon, Jung-Hoon; Dastager, Syed Gulam; Liu, Qing; Khieu, Thi-Nhan; Son, Chu Ky; Li, Wen-Jun; Colaco, Ana (Antonie Van Leeuwenhoek International Journal of General and Molecular Microbiology, 2015)
A novel Gram-negative, non-spore forming, rod-shaped aerobic bacterium, designated SSW136(T), was isolated from a surface seawater sample collected at Espalamaca (in Faial Island), Azores. Growth was found to occur from 10 to 37 A degrees C, pH 6.0-8.0, and with 2-11 % of NaCl. 16S rRNA gene sequence indicated that the strain SSW136(T) belongs to the family Rhodobacteraceae. Strain SSW136(T) exhibited 96.3, 95.9, 95.7 and 95.5 sequence similarity to the type strains Oceanicola litoreus M-M22(T), Roseovarius aestuarii SMK-122(T), Marivita geojedonensis DPG-138(T), and Pseudoruegeria aquimaris SW-255(T) respectively. Neighbour-joining and maximum-parsimony phylogenetic trees based on 16S rRNA gene sequences revealed that strain SSW136(T) was affiliated to the family Rhodobacteraceae and formed a separate branch. The G+C content was 63.5 mol%. The major respiratory quinone was found to be Q-10. The polar lipids of strain SSW136(T) consisted of phosphatidylcholine, phosphatidylethanolamine, phosphatidylglycerol, two unidentified aminolipids and three unidentified phospholipids. The major fatty acids were C-18:1 omega 7c (46.5 %), Cyclo-C-19:0 omega 8c (16.0 %) and C-16:0 (12.8 %). On the basis of the morphological, genotypic, chemotaxonomic characteristics and low DNA-DNA relatedness, strain SSW136(T) is proposed to represent a novel genus and novel species, Nioella nitratireducens gen. nov., sp. nov., in the family Rhodobacteraceae. The type strain is SSW136(T) (=KCTC 32417(T) = NCIM 5499(T)).
Keywords: Espalamaca; Nioella nitratireducens; Novel genus and species; Polyphasic taxonomy; Seawater

Non-templated ambient nanoperforation of graphene: a novel scalable process and its exploitation for energy and environmental applications - Jhajharia, Suman Kumari; Selvaraj, Kaliaperumal (Nanoscale, 2015)
Nano-perforation of 2D graphene sheets is a recent and strategically significant means to exploit such materials in modern applications such as energy production and storage. However, current options for the synthesis of holey graphene (hG) through nano-perforation of graphene involve industrially undesirable steps viz., usage of expensive/noble metal or silica nanoparticle templates and/or hazardous chemicals. This severely hampers its scope for large scale production and further exploitation. Herein, we report for the first time a scalable non-templated route to produce hG at ambient conditions. Nano-perforation is achieved with tunable pore size via the simple few layer co-assembly of silicate-surfactant admicelles along the surface of graphene oxide. A gentle alkali treatment and a reduction at optimized conditions readily yielded holey graphene with a remarkable capacitance (similar to 250 F g(-1)) and interesting adsorption abilities for pollutants. Density functional theory based computational studies reveal interesting insights on the template free nano-perforation at a molecular level. This simple rapid process not only excludes the need for expensive templates and harmful chemicals to yield hG at attractively ambient, chemically placid and industrially safer conditions, but also creates no hurdles in terms of scaling up.

Novel 2,6-diformyl-4-methyl phenol based chemosensor for Zn-II ion by ratiometric displacement of Cd-II ion and its application for cell imaging on human melanoma cancer cells - Mitra, Debarshan; Venkatathari, N.; Sabharwal, S. C.; Godbole, S. V.; Tyagi, A. K.; Das, Sangbrita (Journal of the Indian Chemical Society, 2015)
A new chelating ligand [4-methyl-2,6-bis-(pyridin-2-yl-hydrazonomethyl)-phenol] (1) was prepared by the condensation of 2-hydrazinylpyridine with 2,6-diformyl-p-cresol. Compound 1 exhibits weak fluorescence due to intramolecular photoinduced electron transfer (PET). The sensor (1) demonstrates Zn2+-specific emission enhancement due to ``PET off'' process through a 1 : 1 binding mode with the metal ion. The fluorescence quantum yield of the chemosensor 1 is only 0.020, and it increases more than 14-fold (0.280) in the presence of one equivalent of the zinc ion. Interestingly, the introduction of other metal ions causes the fluorescence intensity to remain either unchanged or weakened except for Cd2+. Ratiometric displacement of Cd2+ ion from the complex by Zn2+ ion supports the formation of more stable sensor-Zn2+ complex over the sensor-Cd2+ complex. The experimental findings have been correlated with theoretical results using B3LYP functional and 6-31G(d,p), LANL2DZ basis set for Cd2+ (2) and Zn2+ (3) complex, respectively, by Density Functional Theory (DFT) method. Moreover, the ability of probe 1 to sense Zn2+ within human melanoma cancer cells has been explored, and the Zn2+-probing process in living cells was reversible. [Mn-2(PHMP)(2)](ClO4)(2) (4) and [Ni-2(PHMP)(H2O)(5)](NO3)(3) (5) have been also synthesized and characterized crystallographically and spectroscopically to understand the ligating behavior of the ligand PHMP.
Keywords: Cd-II ion; Chemosensor; Density functional theory; human melanoma cancer cells; photoinduced electron transfer; Zn-II ion

Novel hybrid nocodazole analogues as tubulin polymerization inhibitors and their antiproliferative activity - Kale, Sangram S.; Jedhe, Ganesh S.; Meshram, Sachin N.; Santra, Manas K.; Hamel, Ernest; Sanjayan, Gangadhar J. (Bioorganic & Medicinal Chemistry Letters, 2015)
We describe the design, synthesis and SAR profiling of a series of novel combretastatin-nocodazole conjugates as potential anticancer agents. The thiophene ring in the nocodazole moiety was replaced by a substituted phenyl ring from the combretastatin moiety to design novel hybrid analogues. The hydroxyl group at the ortho position in compounds 2, 3 and 4 was used as the conformationally locking tool by anticipated six-membered hydrogen bonding. The bioactivity profiles of all compounds as tubulin polymerization inhibitors and as antiproliferative agents against the A-549 human lung cancer cell line were investigated Compounds 1 and 4 showed mu M IC50 values in both assays. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Anticancer; Colchicine; Nocodazole; Tubulin binding

Nucleophilic fluorination using imidazolium based ionic liquid bearing tert-alcohol moiety - Shinde, Sandip S.; Patil, Sunil N.; Ghatge, Amruta; Kumar, Pradeep (New Journal of Chemistry, 2015)

One-pot highly enantio- and diastereoselective synthesis of anti,anti vinylic 3-amino-1,2 diols via proline catalyzed sequential alpha-amination/benzoyloxyallylation of aldehydes - Ahuja, Brij Bhushan; Sudalai, Arumugam (RSC Advances, 2015)
The first direct asymmetric synthesis of anti, anti vinylic 3-amino-1,2-diols from aldehydes is described via a one-pot sequential L-proline catalyzed alpha-amination/benzoyloxyallylation protocol. The reaction proceeds with exceptionally high diastereoselectivity (>99%) as can be explained based on the Felkin-Ahn transition state model. Its effectiveness is proven unambiguously by demonstrating a short asymmetric synthesis of D-ribo-phytosphingosine tetraacetate (93% ee).

Organocatalytic [4+1]-annulation approach for the synthesis of densely functionalized pyrazolidine carboxylates - Lalwani, Komal G.; Aher, Ravindra D.; Sudalai, Arumugam (RSC Advances, 2015)
A novel one-pot [4+1]-annulation process for the asymmetric synthesis of densely functionalized pyrazolidine carboxylates is described. The in situ generated gamma-hydrazino-alpha,beta-unsaturated ester obtained via proline catalysis acts as a four-atom component, and Corey's sulfur ylide or ethyl bromoacetate acts as a one-atom carbon source to construct pyrazolidine carboxylate units in a highly enantio- and diastereoselective fashion.

Oxidant controlled regio- and stereodivergent azidohydroxylation of alkenes via I-2 catalysis - Prasad, P. K.; Reddi, R. N.; Sudalai, A. (Chemical Communications, 2015)
A novel, I-2 catalyzed regio-and stereodivergent vicinal azidohydroxylation of alkenes leading to 1,2-azidoalcohols in high yields (up to 92%) and excellent dr (up to 98%) has been developed. This unprecedented transformation employs NaN3 and DMF as N-and O-nucleophiles respectively. The role of DMF as the O-source in the reaction has been unequivocally proven by O-18 labelling studies.

Oxidation catalysis by large trisoctahedral gold nanoparticles: Mind the step! - Sreedhala, S.; Sudheeshkumar, V.; Vinod, C. P. (Catalysis Today, 2015)
To understand the origin of catalysis by gold and to probe the role of defects and interfaces, benchmark reactions namely CO oxidation and benzyl alcohol oxidation were carried out on supported trisoctahedral gold nanoparticles and on the inverse catalyst system. The sizes of these particles which are between 45 nm and 110 nm, are well beyond the quantum size regime and well above the optimum size range where gold is considered to be catalytically active. The periodic steps sites in contact with oxide support interface were able to promote the reaction. (C) 2014 Elsevier B.V. All rights reserved.
Keywords: CO oxidation; Defects; Gold catalysis; Inverse catalysta; Steps and kinks

Oxidative addition of the C-I bond on aluminum nanoclusters - Sengupta, Turbasu; Das, Susanta; Pal, Sourav (Nanoscale, 2015)
Energetics and the in-depth reaction mechanism of the oxidative addition step of the cross-coupling reaction are studied in the framework of density functional theory (DFT) on aluminum nanoclusters. Aluminum metal in its bulk state is totally inactive towards carbon-halogen bond dissociation but selected Al nanoclusters (size ranging from 3 to 20 atoms) have shown a significantly lower activation barrier towards the oxidative addition reaction. The calculated energy barriers are lower than the gold clusters and within a comparable range with the conventional and most versatile Pd catalyst. Further investigations reveal that the activation energies and other reaction parameters are highly sensitive to the geometrical shapes and electronic structures of the clusters rather than their size, imposing the fact that comprehensive studies on aluminum clusters can be beneficial for nanoscience and nanotechnology. To understand the possible reaction mechanism in detail, the reaction pathway is investigated with the ab initio Born Oppenheimer Molecular Dynamics (BOMD) simulation and the Natural Bond Orbital (NBO) analysis. In short, our theoretical study highlights the thermodynamic and kinetic details of C-I bond dissociation on aluminum clusters for future endeavors in cluster chemistry.

Oxidative and membrane stress-mediated antibacterial activity of WS2 and rGO-WS2 nanosheets - Navale, Govinda R.; Rout, Chandra Sekhar; Gohil, Kushal N.; Dharne, Mahesh S.; Late, Dattatray J.; Shinde, Sandip S. (RSC Advances, 2015)
Graphene-based materials have strong cytotoxic attributes against bacteria due to their unique physicochemical properties. We examined the antibacterial activities of nanosheets of the graphene analogue tungsten disulphide (WS2) and a composite of reduced graphene oxide-tungsten disulphide (rGO-WS2), comparing them with reduced graphene oxide (rGO) by a time and concentration dependent viability assay and growth curve studies against four bacterial strains: Gram negative Escherichia coli (E. coli) and Salmonella typhimurium (S. typhimurium), and Gram positive Bacillus subtilis (B. subtilis) and Staphylococcus epidermidis (S. epidermidis). The nanosheets of the rGO-WS2 composite caused a more significant retardation in bacterial growth and inhibitory effect on the tested bacterial strains than WS2, followed by rGO. The tested E. coli and B. subtilis strains were more susceptible than the other strains. A mechanistic study revealed that rGO and WS2 did not produce the superoxide anion (O-2(-)) or reactive oxygen species (ROS), but the nanocomposite of rGO-WS2 did produce both. However, all these materials did oxidize glutathione, which serves as a redox state mediator in bacteria. We conclude that the antimicrobial mechanism is due to the combined effect of initial cell deposition on the rGO-WS2 materials, the membrane stress due to direct contact with the nanosheets, and the produced superoxide anion-independent oxidation mechanisms. The beneficial aspects of the physicochemical properties of rGO-WS2, such as its size and conductivity, can be precisely customized to reduce its health and environmental risk factors.

Partial triples excitation to the fock space multi-reference singles and doubles: dipole moment of doublet radicals - Ravichandran, Lalitha; Vaval, Nayana; Pal, Sourav (Proceedings of the International Conference of Computational Methods in Sciences and Engineering 2010 (ICCMSE-2010), 2015)
We present the partial triples effect on the dipole moment of doublet radicals in Lagrangian formulation of Fockspace multi-reference coupled cluster response method(A FSMRCC). This specific scheme uses non-iterative triples, in addition to singles and doubles excitations(A FSMRCCSD(T*)), which accounts for the effects appearing at least at the third order in dipole moment. This method is applied to the ground states of small radicals.
Keywords: Dipole moment; Multi-reference; Triples

Pd loaded amphiphilic COF as catalyst for multi-fold Heck reactions, C-C couplings and CO oxidation - Mullangi, Dinesh; Nandi, Shyamapada; Shalini, Sorout; Sreedhala, Sheshadri; Vinod, Chathakudath P.; Vaidhyanathan, Ramanathan (Scientific Reports, 2015)
COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd-0 nanoparticles into it. An 18-20% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) < 0.05 mol%, average TON 1500) catalyzing simultaneous multiple site Heck couplings and C-C couplings using `non-boronic acid' substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100% conversion of CO to CO2 at 150 degrees C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable.

Pd-catalyzed benzylic C-H oxidation of cyclotriveratrylene - product diversity - Senthilkumar, B.; Gonnade, Rajesh G.; Ramana, C. V. (Organic & Biomolecular Chemistry, 2015)
The inner-rim functionalization of CTV has been examined by employing Pd-catalyzed benzylic oxidation. The outcome of the oxidation depends upon the solvent and co-oxidants employed. An interesting array of CTV derivatives has been synthesized with a simple change in the conditions.

Penicillin V acylase from pectobacterium atrosepticum exhibits high specific activity and unique kinetics - Avinash, Vellore Sunder; Ramasamy, Sureshkumar; Suresh, C. G.; Pundle, Archana (International Journal of Biological Macromolecules, 2015)
Penicillin V acylases (PVAs, E.C.3.5.11) belong to the Ntn hydrolase super family of enzymes that catalyze the deacylation of the side chain from phenoxymethyl penicillin (penicillin V). Penicillin acylases find use in the pharmaceutical industry for the production of semi-synthetic antibiotics. PVAs employ the N-terminal cysteine residue as catalytic nucleophile and are structurally and evolutionarily related to bile salt hydrolases (BSHs). Here, we report the cloning and characterization of a PVA enzyme from the Gram-negative plant pathogen, Pectobacterium atrosepticum (PaPVA). The enzyme was cloned and expressed in Escherichia coli attaining a very high yield (250 mg/l) and a comparatively high specific activity (430 IU/mg). The enzyme showed marginally better pH and thermo-stability over PVAs characterized from Gram-positive bacteria. The enzyme also showed enhanced activity in presence of organic solvents and detergents. The enzyme kinetics turned out to be significantly different from that of previously reported PVAs, displaying positive cooperativity and substrate inhibition. The presence of bile salts had a modulating effect on PaPVA activity. Sequence analysis and characterization reveal the distinctive nature of these enzymes and underscore the need to study PVAs from Gram-negative bacteria. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Cooperative; Enzyme kinetics; Gram-negative; Penicillin V acylase; Substrate inhibition

Perturbations in inter-domain associations may trigger the onset of pathogenic transformations in PrPC: insights from atomistic simulations - Menon, Sneha; Sengupta, Neelanjana (Molecular Biosystems, 2015)
Conversion of the predominantly alpha-helical cellular prion protein (PrPC) to the misfolded beta-sheet enriched Scrapie form (PrPSc) is a critical event in prion pathogenesis. However, the conformational triggers that lead to the isoform conversion (PrPC to PrPSc) remain obscure, and conjectures about the role of unusually hydrophilic, short helix H1 of the C-terminal globular domain in the transition are varied. Helix H1 is anchored to helix H3 via a few stabilizing polar interactions. We have employed fully atomistic molecular dynamics simulations to study the effects triggered by a minor perturbation in the network of these non-bonded interactions in PrPC. The elimination of just one of the key H1-H3 hydrogen bonds led to a cascade of conformational changes that are consistent with those observed in partially unfolded intermediates of PrPC, with pathogenic mutations and in low pH environments. Our analyses reveal that the perturbation results in the enhanced conformational flexibility of the protein. The resultant enhancement in the dynamics leads to overall increased solvent exposure of the hydrophobic core residues and concomitant disruption of the H1-H3 inter-domain salt bridge network. This study lends credence to the hypothesis that perturbing the cooperativity of the stabilizing interactions in the PrPC globular domain can critically affect its dynamics and may lead to structural transitions of pathological relevance.

Polarity issues in room temperature ionic liquids - Shukla, Shashi Kant; Kumar, Anil (Clean Technologies and Environmental Policy, 2015)
The study on ionic liquids has occupied an important place in chemical processes because of several beneficial properties. In order to use these ionic liquids as solvent media in chemical processes, it is essential to know their solvent properties. In this review, an attempt has been made to critically evaluate and discuss the polarity parameters of ionic liquids. The experimental polarity data on ionic liquids are not yet available for numerous ionic liquids. This review will serve as a guideline to investigate polarity issues of these materials and emerge with a simple, but still sound theoretical or semi-empirical models to account for the variation in polarity in the ionic liquid solutions.

Polybenzimidazole based polymeric ionic liquids (PILs): effects of controlled degree of N-quaternization on physical and gas permeation properties - Rewar, Anita S.; Bhavsar, Rupesh S.; Sreekumar, K.; Kharul, Ulhas K. (Journal of Membrane Science, 2015)
Polymeric ionic liquids (PILs) are gaining increasing attention as potential membrane materials to be employed for CO2 separation. With a goal to improve gas permeability, this work presents a series of film forming PlLs obtained by controlled degree of N-quaternization (DQ) of PBI-BuI using a bulky 4-tertbutylbenzyl group. Concurrent effects of variation in ionic content and bulky group substitution were analyzed for physical and gas permeation properties of the resulting PILs. Attempted structural variations leading to simultaneous increments in ionic content and bulky groups offered amorphous polymers with acceptable thermal stability and non-monotonous chain packing density. Enhancement in pure gas permeability coupled with appreciable selectivity for various gas pairs was in accordance with the packing density variations in the series. Gas permeability showed maxima at DQ of just 13%. This conveyed that effects of bulky group substitution in retarding chain packing are overcome by attractive ionic interactions at much lower DQ in these PILs ionic interactions are thus more predominant in governing chain packing and gas permeation properties. These PILs possessed 3.3-20 times higher CO2 permeability in comparison to their parent PBI-BuI, without a significant loss in selectivity. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Degree of quaternization; Gas permeation; Polybenzimidazole; Polymeric ionic liquid

Polybenzimidazole-based polymeric ionic liquids (PILs): effects of `substitution asymmetry' on CO2 permeation properties - Shaligram, Sayali V.; Wadgaonkar, Prakash P.; Kharul, Ulhas K. (Journal of Membrane Science, 2015)
Polymeric Ionic Liquids (PILs) are being considered as promising membrane materials for CO2 separation. Present work aims at investigating effects substitution asymmetry on imidazole moiety of two structurally different polybenzimidazoles (PBI-BuI and PBI-HFA) on physical, gas sorption and transport properties of the resulting film forming PILs possessing symmetric substitution, while keeping one of the N-substituent as methyl group. PILs were obtained with high degree of substitution. The halide anion of these PILs was exchanged with BF4-, Tf-2(N) over bar and HF (B) over bar anions. Effects of substituents, cationic backbone and type of anions on gas permeation properties of PILs using pure gases (He, H-2, N-2 and CO2) were examined at 20 atm upstream pressure and correlated with their physical properties. Combination of typical ionic liquid character (effective towards enhancing CO2 sorption) and looser chain packing (ease in gas diffusion) offered improved CO2 permeation characteristics. As an outcome, some of the PILs exhibited higher CO2 permeation than that of hydrogen, typically known as `reverse selectivity'. These asymmetrically substituted PILs enhanced not only the gas permeability, but also selectivity than their symmetrically substituted counterparts. (C) 2015 Elsevier B.V. All rights reserved.

Polyelectrolytes in dilute solution: viscometric access to coil dimensions and salt effects - Suresha, P. R.; Badiger, Manohar V.; Wolf, Bernhard A. (RSC Advances, 2015)
Copolymers of acrylamide (AM) and diallyldimethylammonium chloride (DADMAC), differing in molar masses M (52.3 to 227 kDa) and degrees of charging y (0.2 to 0.6), were studied with respect to their viscometric behavior in dilute aqueous solutions containing variable amounts of NaCl. Complementary measurements were performed on a Brookhaven 90 plus particle size analyzer. M dominates the intrinsic viscosities [eta]. For the viscometric interaction parameters B this is only true for large concentrations of extra salt. [eta] and B as a function of solvent salinity follow Boltzmann laws. Coil dimensions, determined either via dynamic light scattering or viscometry, agree well. For low salt contents of the solvent the radii decrease with rising polymer concentration, whereas they increase for high salt concentrations; at a characteristic salinity of the solvent they become independent. Zeta potentials grow from +20 to +40 mV as y goes up.

Pore surface engineering in porous, chemically stable covalent organic frameworks for water adsorption - Biswal, Bishnu P.; Kandambeth, Sharath; Chandra, Suman; Shinde, Digambar Balaji; Bera, Saibal; Karak, Suvendu; Garai, Bikash; Kharul, Ulhas K.; Banerjee, Rahul (Journal of Materials Chemistry A, 2015)
Herein, we have explored the possibility of a class of covalent organic frameworks (COFs) as water adsorbing materials. We have selected, synthesized 12 chemically stable functionalized Schiff base COFs and thoroughly studied their water uptake behaviour. Further, a deep understanding was developed with these COFs towards the effects of condensation pressure of water and hydrophilic/hydrophobic groups present in the COF pores on water absorption capacity and ultimately, their recyclability. Among all reported COFs, TpPa-1 shows the highest water uptake of 30 wt% (368 cm(3) g(-1); 17 mmol g(-1)) at P/P-0 = 0.3, which is also comparable with the recently reported carbon materials and few well known MOFs. This study also reveals that the overall water uptake of COFs can be tuned systematically based on chemical functionality and pore size in a wider window of relative pressures.

Possible mechanism of antifungal phenazine-1-carboxamide from pseudomonas sp against dimorphic fungi Benjaminiella poitrasii and human pathogen Candida albicans - Tupe, S. G.; Kulkarni, R. R.; Shirazi, F.; Sant, D. G.; Joshi, Swati P.; Deshpande, Mukund V. (Journal of Applied Microbiology, 2015)
AimInvestigation of antifungal mechanism of phenazine 1-carboxamide (PC) produced by a Pseudomonas strain MCC2142. Methods and ResultsAn antifungal metabolite produced by a Pseudomonas was purified and identified as PC. Human pathogenic fungi such as Candida albicans, Candidaglabrata, Cryptococcus neoformans, Fusarium oxysporum, Aspergillus fumigatus and Aspergillus niger were found to be inhibited by PC (MIC90 32-64gml(-1)). Addition of PC (20gml(-1)) during yeast (Y)-hypha (H) transitions inhibited germ tube formation by >90% and >99% in C.albicans National Collection of Industrial Microorganisms (NCIM) 3471 and nonpathogenic model Benjaminiella poitrasii, respectively. After exposure to PC (20gml(-1)), 75-80% yeast cells of B.poitrasii and C.albicans NCIM 3471 showed rhodamine 123 fluorescence indicating high intracellular reactive oxygen species (ROS) production. ROS further led to hyperpolarization of mitochondrial membrane, subsequently induction of apoptosis as evident by externalization of phosphatidylserine, DNA fragmentation, chromatin condensation and finally death in B.poitrasii. In C.albicans NCIM 3471, PC (20gml(-1)) induced apoptosis. ConclusionsThe antifungal effect of PC in B.poitrasii and C.albicans may be due to ROS-mediated apoptotic death. Significance and Impact of the StudyInhibition of Y-H transition of B.poitrasii and C.albicans by PC indicates that it may prove useful in the control of dimorphic human pathogens.
Keywords: Apoptosis; Candida albicans; dimorphism; phenazines; Pseudomonas sp; reactive oxygen species

Potential applications of glucosyltransferases in terpene glucoside production: impacts on the use of aroma and fragrance - Schwab, Wilfried; Fischer, Thilo C.; Giri, Ashok; Wuest, Matthias (Applied Microbiology and Biotechnology, 2015)
The detection of glucoconjugated forms of monoterpene alcohols in rose petals in the late 1960s opened the new field of nonvolatile aroma precursors in flavor research. It is now well established that odorless glycosides represent a significant pool of aroma precursors in plants where they act as preformed but inactivated defense or attractive chemicals. Technical improvements in the separation and identification of plant secondary metabolites have provided a multitude of chemical structures, but functional characterization of glycosyltransferases that catalyze their formation lags behind. As technical efforts and costs for DNA sequencing dramatically dropped during the last decade, the number of plant genome sequences increased significantly, thus providing opportunities to functionally characterize the glycosyltransferase gene families in plants. These studies yielded the first glycosyltransferase genes that encode efficient biocatalysts for the production of monoterpene glucosides. They have applications in the food, feed, chemical, cosmetic, and pharmaceutical industries as slow release aroma chemicals.

Preparation and characterization of self-photostabilizing UV-durable bionanocomposite membranes for outdoor applications - Kushwaha, Omkar S.; Avadhani, C. V.; Singh, R. P. (Carbohydrate Polymers, 2015)
Here, we report a durable and ultraviolet (UV) resistant nanocomposite membrane of chitosan (CS) with effective photostabilization ascribed to Zinc oxide (ZnO) nanoparticles. Zinc oxide nanoparticles were successfully dispersed in the solution of chitosan polymer. The nanocomposite films with the homogenous dispersion of ZnO nanoparticles in the chitosan matrix were obtained by solution casting method and the influence of ZnO nanoparticles as a photostabilizer was studied. The nanocomposite membranes were photoirradiated by polychromatic radiations with lambda > 300 nm using mercury vapour lamps in SEPAP instrument. The resulting nanocomposite material exhibited excellent UV-resistance in very low percentages of ZnO nanoparticles. The chitosan membranes showed fast degradation attributes than the nanocomposite membranes. ZnO nanoparticles effectively absorbed UV radiations, thus protecting polymer from radiation degradation. The neat and irradiated nanocomposites of chitosan and ZnO nanoparticles (CS/ZnO) were characterized by Fourier Transform Infrared Spectroscopy (FT-IR) spectroscopy for the chemical changes/degradation taking place. Chitosan nanocomposites were further characterized for tensile properties, contact angle measurements and surface morphology. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Bionanocomposite membrane; Chitosan; Contact angle measurement; Fourier transform infrared spectroscopy; Photostabilization; Zinc oxide nanoparticles

Preparation of Ag(Shell)-Au(Core) nanoparticles by anti-galvanic reactions: are capping agents the ``real heroes'' of reduction? - Sahu, Puspanjali; Bhagavatula L. V. Prasad (Colloids and Surfaces A-Physicochemical and Engineering Aspects, 2015)
The formation of Ag(shell)-Au(core) nanoparticles by the reduction of Ag+ ions on preformed Au NPs, mediated by the capping agents like dodecylamine is described. We clearly established that while monodisperse Ag(shell)-Au(core) structures can be formed in presence of weak surface binding ligands such as amines, strong binding ligands such as thiols, lead to formation of separate monometallic Au and Ag particles. Apart from highlighting the influence of metal-ligand binding strength on the formation of core-shell nanoparticle architectures, our study also provides an easy means to produce Ag( shell)-Au( core) structures. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Ag(shell)-Au(core) nanoparticles; Anti-Galvanic reactions

Production of polyunsaturated fatty acids in recombinant lipomyces starkeyi through submerged fermentation - Salunke, Devyani; Manglekar, Rupali; Gadre, Ramchandra V.; Nene, Sanjay; Harsulkar, Abhay M. (Bioprocess and Biosystems Engineering, 2015)
Long chain polyunsaturated fatty acids (LCPUFA) are known to play an important role in human health and nutrition. Considering the limitation of LCPUFA sources, it is necessary to search new avenues for their production. Oleaginous yeasts are an attractive target for harvesting single cell oil, mainly because of the ease of cultivation with cheaper raw material. Lipomyces starkeyi is one such oleaginous yeast, which can accumulate oil to the extent of 60 % of its biomass and where genetic transformation can be achieved. In our earlier work, Delta 15 desaturase gene (AEP37840) from flax was transformed into L. starkeyi. In the present work, we report optimization of medium for the production of omega-3 enriched oil from this transformed yeast. A basic medium containing 20 g/l glucose as a carbon source and 10 g/l yeast extract as a nitrogen source was used during fermentation. At regular time intervals, glucose was fed to maintain high C:N ratio (65:10) during fermentation. Under the most favorable conditions, dry biomass and total lipid content were 18 and 7.29 g/l, respectively. Prior to genetic transformation, L. starkeyi contained 56.03 mg/l DHA along with 71.4 mg/l EPA and 42.2 mg/l ALA. Genetic engineering of this yeast resulted in a strain that produced 1080 mg/l DHA (17.4 %) along with 74.28 mg/l EPA and 126.72 mg/l ALA possibly through modification of PUFA biosynthetic pathway. To the best of our knowledge, this is a first report of DHA enrichment and opens up avenues for LCPUFA production through L. starkeyi.
Keywords: Fermentation; LCPUFA; Lipid production; Oleaginous yeast

Proline-catalyzed alpha-aminooxylation of beta-amino aldehydes: access to enantiomerically pure syn- and anti-3-amino-3-aryl-1,2-alkanediols - Venkataramasubramanian, V.; Kiran, I. N. Chaithanya; Sudalai, Arumugam (Synlett, 2015)
A new synthetic method for enantioselective synthesis of syn 3-amino-3-aryl-1,2-alkanediols via praline catalyzed alpha-aminaoxn y ylation of beta-amino aldehydes des are described. This methodology is successfully applied to a concise and protecting group-free asymmetric synthesis of (-)-cytoxazone (+)-epi-cytoxazone and formal synthesis of N-thiolated 2-oxazolidinone.
Keywords: amino aldehydes; Asymmetric synthesis; catalysis; diastereoselectivity; Enantioselectivity; Natural product

Proline-catalyzed sequential syn-mannich and [4+1]-annulation cascade reactions to form densely functionalized pyrrolidines - Aher, Ravindra D.; Kumar, B. Senthil; Sudalai, Arumugam (Journal of Organic Chemistry, 2015)
A highly efficient one-pot [4 + 1]-annulation process for the asymmetric synthesis of densely functionalized pyrrolidine derivatives is described. The in situ generated syn-Mannich adduct obtained via proline catalysis acts as a four-atom component, and Coreys sulfur ylide or ethyl bromoacetate acts as a one-atom carbon source to construct pyrrolidine units in a highly enantio- and diastereoselective manner.

Propensity of self-assembled leucine-lysine diblock copolymeric alpha-helical peptides to remain in parallel and antiparallel alignments in water - Sarkar, Sujit; Pandey, Prithvi Raj; Roy, Sudip (Journal of Physical Chemistry B, 2015)
Molecular dynamics Simulation study of alpha-helical diblock copolypeptides: preassembled in parallel and antiparallel alignments in water are presented. The assembled peptide lamellar structures were not disrupted even: after performing three step simulation protocols. Primarily hydrogen bonds between peptide are responsible for the stability: The analysis of the trajectory also suggests that Water plays a significant role in favoring self assembly We have detected continuous hydrogen bonded network structure, which is further responsible for the stability Of the lamellar structures. We have performed a detailed analysis of the hydrogen bonded network structure and its length. Further, free energy calculations revealed that the degree of stability for both lamellae are similar. The present study provides structural insight into the stability of self-assembled structures of block copolypeptides.

Pt-nanoparticle functionalized carbon nano-onions for ultra-high energy supercapacitors and enhanced field emission behaviour - Suryawanshi, Sachin R.; Kaware, Vaibhav; Chakravarty, Disha; Walke, Pravin S.; More, Mahendra A.; Joshi, Kavita; Rout, Chandra Sekhar; Late, Dattatray J. (RSC Advances, 2015)
In the present work, we have investigated the charge storage capacitive response and field emission behaviour of platinum (Pt) nanoparticles decorated on carbon nano onions (CNOs) and compared them with those of pristine carbon nano onions. The specific capacitance observed for Pt-CNOs is 342.5 F g(-1), about six times higher than that of pristine CNOs, at a scan rate of 100 mV s(-1). The decoration with Pt nanoparticles, without any binder or polymer separator on the CNO, leading to enhanced supercapacitance is due to easy accessibility of Na2SO4 electrolyte in the active material. The Density Functional Theory (DFT) calculations of these systems reveal enhancement in the Density of States (DOS) near the Fermi energy (E-F) on account of platinum decoration on the CNOs. Furthermore, the field emission current density of similar to 0.63 mA cm(-2) has been achieved from the Pt-CNOs emitter at an applied electric field of similar to 4.5 V mu m(-1) and from the pristine CNOs sample current density of similar to 0.4 mA cm(-2) has been achieved at an applied electric field of similar to 6.6 V mu m(-1). The observed enhanced field emission behavior has been attributed to the improved electrical conductivity and increased emitting sites of the Pt-CNO emitter. The field emission current stability of the Pt-CNO emitter over a longer duration is found to be good. The observed results imply multifunctional potential of Pt-CNOs, as supercapacitor material in various next generation hybrid energy storage devices, and field emitters for next generation vacuum nano/microelectronic devices.

Pulsed laser-driven molecular self-assembly of cephalexin: aggregation-induced fluorescence and its utility as a mercury ion sensor - Singh, Pradeep Kumar; Prabhune, Asmita; Ogale, Satishchandra (Photochemistry and Photobiology, 2015)
A fluorescent self-assembly of cephalexin is obtained by pulsed laser irradiation process. An intense fluorescence emission is found in the self-assembled form due to occurrence of a typical aggregation-induced emission in cephalexin molecules. It is observed that fluorescence quenching of the self-assembled fluorescent nanostructures occurs in the presence of extremely low Hg++ ions concentrations (10(-7) M) as compared to other heavy metal ions e.g. Ferrous (Fe++), Manganese (Mn++), Magnesium (Mg++), Cobalt (Co++), Nickel (Ni++) and Zinc (Zn++) at the same concentrations.

Purification and characterization of an agglutinin from datura innoxia with antineoplastic activity - Singh, Ruby; Nawale, Laxman; Gaikwad, Sushama M.; Suresha, C. G. (National Science Day, At CSIR-NCL, 2015)
Lectins are carbohydrate binding proteins of non-immune origin. Due to their multivalency, lectins can be easily detected using agglutination. Lectins are reported to induce cytotoxicity or inhibition of growth in various cancer cells., hence good therapeutic startegy against cancer. Factors such as specificity, stability, assay rapidity, and costs combine to make lectins attractive diagnostic reagents. Datura innoxia belongs to family of Solanaceae.All parts of the plant are hallucinogenic, hypnotic and narcotic. Application: at low dose acts as pain killer, relieves asthma and rheumatism.

Qualitative and quantitative proteomic analysis of vitamin C induced changes in mycobacterium smegmatis - Mishra, Abhishek; Sarkar, Dhiman (Frontiers in Microbiology, 2015)
Vitamin C is a critical dietary nutrient in human which has a wide range of regulatory effects on gene expression and physiology of Mycobacterium tuberculosis that leads to a dormant drug-tolerant phenotype. In the presence of iron, vitamin C shows a high bactericidal activity even in the drug resistant phenotype of M. tuberculosis. The regulatory mechanisms underlying vitamin C induced adaptations are largely unknown due to lack of functional genomics data in this field. In this study, we attempt to characterize the direct effect of vitamin C treatment on the physiology of actively growing Mycobacterium smegmatis. The study chose M. smegmatis as it is a fast-growing bacterium and a non-pathogenic model system which shares many physiological features with the pathogenic M. tuberculosis including dormancy and its regulation. The proteomic adaptation of M. smegmatis on vitamin C treatment demonstrates the important changes in cellular and metabolic process such as reversal of tricarboxylic acid cycle, decrease in ATP synthesis, decrease in iron acquisition and storage, and induction of dormancy regulators WhiB3, PhoP, and Lsr2.
Keywords: dormancy; Mycobacterium smegmatis; proteomics; tuberculosis; vitamin C

Quantitative, automated, high content screening assay approach to anti-angiogenicdrug discovery - Nawale, Laxman; Sarkar, Dhiman (National Science Day, At CSIR-NCL, 2015)
Angiogenesisenhancescancer,maculardegeneration,etc.. Currentangiogenicassays--indirect,manual,timeconsuming,laborintensive,difficulttoquantify,andexpensive. Wedevelopedanautomated,quantitative,HighContentScreeningangiogenictubeformationassaywouldbenefitdrugdiscoveryforseveraltherapeuticareas. Humanendothelialcellswereseededwithpro-oranti-angiogeniccompoundsonaMatrigelTMlayerina96-wellplate.Afterangiogenictubesformation,thepositivecontrolsandthetestsampleswerefixed,fluorescentlylabeled,automaticallyimagedonCellomics’ArrayScan®HCSReader,andquantitativelyanalyzedon-the-flybytheTubeFormationBioApplicationsoftwaremodule. Multiplefeaturesrelevantforangiogenesisandangiogenictubeformationwereautomaticallymeasured. Thisrobustandreliableassaythusenabledthelarge-scale,quantitative,screeningandcharacterizationofcompoundsaffectingbothpro-andanti-angiogenicpathways.

Rapid characterization of oxidative deterioration in edible oil by optical photospectrometry - More, Pravin S.; Shelke, Anil V.; Late, Dattatray J. (Journal of Food and Dairy Technology, 2015)
This research work aimed to investigate the kinetic reaction of reused cooking oil and find the optimum conditions of its process. The feedstock was collected from the commercially available sunflower oil. Our investigation shows that the kinetic reaction of reused sunflower oil (auto-oxidation) obtained in terms of variation of absorption coefficient of unexposed sunflower as 0.05 while the exposed sunflower had 0.075. The optimum condition from optical absorption spectroscopy investigations were obtained as 0.267 for unexposed sunflower oil and 0.194 for exposed sunflower oil at room temperature. Furthermore, our FTIR spectroscopic results obtained are accurate and precise enough for such detection such as free fatty acid (FFA ~ 26%), acid ~ 53% and saponification ~ 192% get reduce in exposed oil was investigated.

Rapid conductometric sensor for the analysis of cyanide using imidazole based receptor - Paul, Anirban; Perween, Mosarrat; Saha, Sukdeb; Srivastava, Divesh N.; Das, Amitava (Physical Chemistry Chemical Physics, 2015)
A specific and efficient hydrogen bonding interaction between cyanide and the HN-H [imidazole] in an aqueous medium has been utilized for the selective recognition of cyanide under physiological conditions. The possibility of utilizing such an interaction for developing any practical device for the specific detection of cyanide in an aqueous environment has not been explored to date. We now report a simple dip and read conductometric sensor for cyanide ions using a tailored electrode in aqueous media. The purpose built reagent, 2-phenyl-1H-anthra-[2,3-d]-immidazole-5,10 dione was immobilized in a polyaniline matrix to fabricate this conductometric device. The homogeneous immobilization of the receptor in polyaniline was confirmed by FT-IR mapping. The proposed transduction mechanism is charge neutralization on the polyaniline moiety, which ultimately inhibits the protonation resulting in a decrease in the conductance of polyaniline. The sensor response was measured in three ranges of cyanide concentration (10(-10) M to 10(-8) M; 10(-8) M to 10(-6) M and 10(-6) M to 10(-3) M). Whereas the device is found insensitive in the first range, it acts as a detector in the second range and as a proportional sensor in the third range. The minimum detection limit of this device was found to be 10 nmol L-1 (2.6 ppt), which is significantly less than the WHO guideline values. The responses have been investigated under various conditions such as different pH and the electrochemical state of the polymer. The current device has been found to be better close to neutral pH and at a 400 mV vs. Ag/AgCl potential. The reproducibility and repeatability of the sensor was investigated and interference studies were performed.

Rational approach towards enhancing solar water splitting: a case study of Au-RGO/N-RGO-TiO2 - Bharad, Pradnya A.; Sivaranjani, Kumarsrinivasan; Gopinath, Chinnakonda S. (Nanoscale, 2015)
A rational approach was employed to enhance the solar water splitting (SWS) efficiency by systematically combining various important factors that helps to increase the photocatalytic activity. The rational approach includes four important parameters, namely, charge generation through simulated sunlight absorption, charge separation and diffusion, charge utilization through redox reaction, and the electronic integration of all of the above three factors. The complexity of the TiO2 based catalyst and its SWS activity was increased systematically by adding reduced graphene oxide (RGO) or N-doped RGO and/or nanogold. Au-N-RGO-TiO2 shows the maximum apparent quantum yield (AQY) of 2.46% with a H-2 yield (525 mu mol g(-1) h(-1)) from aqueous methanol, and overall water splitting activity (22 mu mol g(-1) h(-1); AQY = 0.1%) without any sacrificial agent under one sun conditions. This exercise helps to understand the factors which help to enhance the SWS activity. Activity enhancement was observed when there is synergy among the components, especially the simulated sunlight absorption (or one sun conditions), charge separation/conduction and charge utilization. Electronic integration among the components provides the synergy for efficient solar light harvesting. In our opinion, the above synergy helps to increase the overall utilization of charge carriers towards the higher activity.

Rational drug design, synthesis and biological evaluation of dihydrofolate reductase inhibitors as antituberculosis agents - Tawari, Nilesh R.; Bag, Seema; Raju, Archana; Lele, Arundhati C.; Bairwa, Ranjeet; Ray, Mukti Kanta; Rajan, M. G. R.; Nawale, Laxman U.; Sarkar, Dhiman; Degani, Mariam S. (Future Medicinal Chemistry, 2015)
Background: A series of 2,4-diamino-s-triazines was designed, with potential for activity against Mycobacterium tuberculosis (Mtb) dihydrofolate reductase enzyme, on the basis of virtual screening results and structure-based drug design. Results: The compounds were evaluated against Mtb (H(37)Rv) and their cytotoxicity was assessed using VERO cell lines. Of particular note, two compounds were found to have the most promising antituberculosis activity (6b minimum inhibitory concentration: 1.76 mu M and 6i minimum inhibitory concentration: 1.57 mu M) along with low cytotoxicity (CC50 : > 300 mu M). The enzyme assay results of these two indicated significant inhibition of Mtb dihydrofolate reductase along with selectivity. Selected derivatives were tested against dormant tubercle bacilli in vivo and ex vivo indicating potential inhibition. Conclusion: This study provides promising antituberculosis dihydrofolate reductase inhibitors that can act as potential leads for further development.

Recent developments in solar H-2 generation from water splitting - Rajaambal, Sivaraman; Sivaranjani, Kumarsrinivasan; Gopinath, Chinnakonda S. (Journal of Chemical Sciences, 2015)
Hydrogen production from water and sunlight through photocatalysis could become one of the channels, in the not-so-distant future, to meet a part of ever growing energy demands. However, accomplishing solar water splitting through semiconductor particulate photocatalysis seems to be the `Holy Grail' problem of science. In the present mini-review, some of the critical strategies of semiconductor photocatalysis are focused with the aim of enumerating underlying critical factors such as visible light harvesting, charge carrier separation, conduction and their utilization that determine the quantum efficiency. We attempted to bring out the essential requirements expected in a material for facile water splitting by explaining important and new designs contributed in the last decade. The newly emerged designs in semiconductor architecture employing nanoscience towards meeting the critical factors of facile photocatalysis are elucidated. The importance of band gap engineering is emphasized to utilize potential wide band gap semiconductors. Assistance of metal nanostructures and quantum dots to semiconductors attains vital importance as they are exuberant visible light harvesters and charge carrier amplifiers. Benevolent use of quantum dots in solar water splitting and photoelectrochemical water splitting provides scope to revolutionize the quantum efficiency by its multiple exciton generation features. A list of drawbacks and issues that hamper the much needed breakthrough in photocatalysis of water splitting is provided to invite attention to address them and move towards sustainable water splitting.
Keywords: Hydrogen; nanomaterial; Photocatalysis; quantum dot; Semiconductor; visible light; water splitting

Recyclable ionic liquid iodinating reagent for solvent free, regioselective iodination of activated aromatic and heteroaromatic amines - Deshmukh, Amarsinh; Gore, Babasaheb; Thulasiram, Hirekodathakallu V.; Swamy, Vincent P. (RSC Advances, 2015)
This article describes a simple, efficient method for iodination of activated aromatic and heteroaromatic amines using recyclable 1-butyl-3-methylpyridinium dichloroiodate (BMPDCI) as an ionic liquid iodinating reagent, in the absence of any solvent. The main advantages are a simple efficient procedure, good yields and no need for any base/toxic heavy metals, or oxidizing agents. The ionic liquid was recovered and recycled in five subsequent reactions, without much loss of activity. This method was applied for the synthesis of the antiprotozoal drug iodoquinol and the antifungal drug clioquinol.

Reduced graphene oxide composite with oxidizable manganese/cobalt mixed oxide for p-cresol oxidation by using molecular oxygen - Jha, Ajay; Patil, Sagar H.; Solanki, Bhanu P.; Ribeiro, Ana P. C.; Castro, Carlos A. N.; Patil, Kashinath R.; Coronas, Alberto; Rode, Chandrashekhar V. (ChemPlusChem, 2015)
A composite of graphene oxide (GO) with mixed oxide (MnCo) was prepared by using a solvothermal method. During the synthesis, both the reduction of GO and growth of metal oxides took place simultaneously. The as-prepared composite material was highly selective for the liquid-phase oxidation of p-cresol to form p-hydroxybenzaldehyde in 71% yield within 1h. The composite material was characterised by SEM, X-ray photoelectron spectroscopy, high-resolution TEM and cyclic voltammetry (CV). A CV study revealed that the increase in the redox potential of the mixed oxide after being supported on GO, led to its higher activity of the catalyst for the oxidation reaction. The stability of the catalyst under the reaction conditions was studied by its successful reuse in three cycles.
Keywords: cyclic voltammetry; graphene; Oxidation; supported catalysts; transition metals

Reduction of graphene oxide by 100 MeV Au ion irradiation and its application as H2O2 sensor - Hareesh, K.; Joshi, R. P.; Shateesh, B.; Asokan, K.; Kanjilal, D.; Late, Dattatray J.; Dahiwale, S. S.; Bhoraskar, Vasant N.; Haram, Santosh K.; Dhole, Sanjay D. (Journal of Physics D-Applied Physics, 2015)
Graphene oxide (GO) synthesized from a modified Hummer's method was reduced (referred, rGO) by using 100 MeV Au ion species and its response to the sense H2O2 was investigated. The changes in the atomic composition and structural properties of rGO after irradiation were studied using x-ray diffraction, Fourier transform infrared spectroscopy and x-ray photoelectron spectroscopy. These results suggested that the removal of the oxygen-containing functional groups and the improvement of the electrochemical performance of reduced graphene oxide (rGO) after ion irradiation. Raman spectroscopic results revealed the increase in the disorder parameter (I-D/I-G) after Au ion irradiation and also the formation of a large number of small sp(2) domains due to the electronic energy loss of ion beam. The resultant rGO was investigated for H2O2 sensing using electrochemical techniques and it showed a good response.
Keywords: electronic energy loss; GO; ion beam irradiation; reduction

Regioselective and diastereoselective iodocyclization reaction of alkene-thioureas: an efficient approach to bicyclic beta-lactams - Garud, Dinesh R.; Sonawane, Amol D.; Auti, Jyoti B.; Rode, Navnath D.; Ranpise, Vinod R.; Joshi, Rohini R.; Joshi, Ramesh A. (New Journal of Chemistry, 2015)
Bicyclic beta-lactams, i.e. 3-thia-1-dethiacephams, were synthesized via a highly regioselective and diastereoselective iodocyclization reaction of alkene-thioureas with molecular iodine. Furthermore, the structure of 3-thia-1-dethiacepham was confirmed by a chemical method, the dehydrohalogenation reaction using DBU.

Relativistic equation-of-motion coupled-cluster investigation of the trends of single and double ionization potentials in the He and Be isoelectronic systems - Pathak, Himadri; Sahoo, B. K.; Sengupta, Turbasu; Das, B. P.; Vaval, Nayana; Pal, Sourav (Journal of Physics B-Atomic Molecular and Optical Physics, 2015)
We employ a four-component spinor relativistic equation-of-motion coupled-cluster (EOMCC) method within the single-and double-excitation approximation to calculate the single ionization potentials (IPs) and double ionization potentials (DIPs) of the He and Be isoelectronic sequences up to Ne. The obtained results are compared with the available results from the National Institute of Standards and Technology (NIST) database to test the performance of the EOMCC method. We also present intermediate results at different levels of approximations in the EOMCC framework to gain insight of the effect of electron correlation. Furthermore, we investigate the dependence of the IPs and DIPs of these ions on the ionic charge and observe that these follow parabolic trends. Similarities between the trends of IPs and DIPs in both the classes of considered systems are categorically demonstrated.
Keywords: coupled-cluster method; double ionization potentials; equation-of-motion theory

Relativistic extended coupled cluster method for magnetic hyperfine structure constant - Sasmal, Sudip; Pathak, Himadri; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Physical Review A, 2015)

Release of a guest by disassembling a capsule through a photo triggering process - Nithyanandhan, Jayaraj; Jagadesan, P.; Samanta, S. R.; Da Silva, J. P.; Ramamurthy, V. (Organic Letters, 2015)

Removal of methylene blue (MB) dye from water environment by processed Jowar Stalk [Sorghum bicolor (L.) Moench] adsorbent - Dod, Ramesh; Banerjee, Goutam; Saini, D. R. (Clean Technologies and Environmental Policy, 2015)
The present paper discusses the results of the study of adsorption of methylene blue on activated carbon, derived from cheap and abundantly available agro-residue of Jowar Stalk (JS) [Sorghum bicolor (L.) Moench] on suitable heat and acid treatment. The physico-chemical and morphological characteristics of processed carbon of JS origin were studied using X-ray diffraction, scanning electron microscopy, Brunauer, Emmett and Teller surface area, and Fourier transform infrared spectrophotometry analyses. The batch studies revealed optimum values of adsorption parameters such as pH, adsorbent dosage, agitation speed, grain size, temperature, and contact time as 7, 1.5 g l(-1), 200 rpm, finer than 75 A mu m, 30 A degrees C, and 7 h, respectively. The adsorption isotherm data were best described by Langmuir isotherm model with a maximum adsorption capacity of 176.05 mg MB g(-1) JS activated carbon at 30 A degrees C, which is higher than that available with adsorbents used by past researchers. In terms of cost-effectiveness, JS carbon shows its superiority over commercially available carbon.
Keywords: Adsorption; Isotherms; kinetics; Methylene blue; Processed Jowar Stalk [Sorghum bicolor (L.) Moench]

Reversal of H-bonding direction by N-sulfonation in a synthetic reverse-turn peptide motif - Vijayadas, Kuruppanthara N.; Kotmale, Amol S.; Thorat, Shridhar H.; Gonnade, Rajesh G.; Nair, Roshna V.; Rajamohanan, Pattuparambil R.; Sanjayan, Gangadhar J. (Organic & Biomolecular Chemistry, 2015)
This communication depicts an intriguing example of hydrogen-bonding reversal upon introduction of a sulfonamide linkage at the N-terminus of a synthetic reverse-turn peptide motif. The ready availability of two sulfonyl oxygen atoms, as hydrogen-bonding acceptors, combined with the inherent twisted conformation of sulfonamides are seen to act as switches that engage/disengage the hydrogen-bond at the sticky ends/termini.

Reversed reactivity of anilines with alkynes in the rhodium-catalysed C-H activation/carbonylation tandem - Midya, Siba Prasad; Sahoo, Manoj Kumar; Landge, Vinod Gokulkrishna; Rajamohanan, P. R.; Balaraman, Ekambaram (Nature Communications, 2015)
Development of multicatalytic approach consisting of two or more mechanistically distinct catalytic steps using a single-site catalyst for rapid and straightforward access of structurally complex molecules under eco-benign conditions has significance in contemporary science. We have developed herein a rhodium-catalysed C-H activation strategy which uses an unprotected anilines and an electron-deficient alkynes to C-C bonded products as a potential intermediate in contrast to the archetypical C-N bonded products with high levels of regioselectivity. This is followed by carbonylation of C-H bond activated intermediate and subsequent annulation into quinolines has been described. This rhodium-catalysed auto-tandem reaction operates under mild, environmentally benign conditions using water as the solvent and CO surrogates as the carbonyl source with the concomitant generation of hydrogen gas. The strategy may facilitate the development of new synthetic protocols for the efficient and sustainable production of chemicals in an atom-economic way from simple, abundant starting materials.

Reverse-hydroformylation: a missing reaction explored - Nandakumar, Avanashiappan; Sahoo, Manoj Kumar; Balaraman, Ekambaram (Organic Chemistry Frontiers, 2015)
Recent progress in transition-metal catalysed acceptor- and acceptorless-reverse hydroformylation of aldehydes for the conversion of olefins has been discussed. The aldehyde feedstock serves as a source for production of syngas and valuable alkenes.

Rh-catalyzed synthesis of coumarin derivatives from phenolic acetates and acrylates via C-H bond activation - Gadakh, Sunita K.; Dey, Soumen; Sudalai, Arumugarn (Journal of Organic Chemistry, 2015)
An efficient annulation strategy involving the reaction of phenolic acetates with acrylates in the presence of [Rh-2(OAc)(4)] as catalyst and formic acid as reducing agent, leading to the high yield synthesis of coumarin derivatives, has been developed. The addition of NaOAc as a base increased the yield of the products. The reaction is quite Successful for both electron rich as well as electron deficient phenolic acetates, affording coumarins with excellent regioselectivity, and proceeds via, C-H bond activation proven by deuterium incorporation studies.

Rhodium complex with unsymmetrical vicinal diamine ligand: excellent catalyst for asymmetric transfer hydrogenation of ketones - Deshpande, Sudhindra H.; Shende, Vaishali S.; Shingote, Savita K.; Chakravarty, Debamitra K.; Puranik, Vedavati G.; Chaudhari, Raghunath V.; Kelkar, Ashutosh A. (RSC Advances, 2015)
New unsymmetrical vicinal diamine ligands with systematic variation in the regio and stereo positions in the amine and sulphonamide groups were synthesized from cheap starting material such as norephedrine. Catalytic Asymmetric Transfer Hydrogenation (ATH) of aromatic alkyl ketones has been investigated using transition metal complexes and new derivatives of monotosylated unsymmetrical vicinal diamine ligands using sodium formate as the hydrogen source, in water and methanol. Chiral secondary alcohols were obtained with excellent enantioselectivity (>95% ee) and conversion of ketones (>95%) with [Rh(Cp*)Cl-2](2) and ligand 4 as a catalyst. Enantioselectivity was found to be slightly higher with the use of methanol as a solvent for ATH of ketones with sodium formate as the hydrogen source compared to water as a solvent and was found to be consistent with all the ketones investigated. The reaction mixture is homogeneous in methanol unlike in water, where substrate and product are insoluble in water and form separate phase, sodium formate being soluble in water. The activity and enantioselectivity obtained for ATH of ketones using [Rh(Cp*)Cl-2](2) and unsymmetrical vicinal diamine ligand as catalyst was comparable with the C2 symmetric benchmark ligands like TsDPEN ((1R, 2R)-N-(p-tolylsulfonyl)-1,2-diphenylethylene- diamine), and TsCYDN ((1R, 2R)-N-(p-tolylsulfonyl)-1,2-cyclohexyl, diamine) under similar reaction conditions. To the best of our knowledge, this is first example of the ATH of ketones with good activity and high enantioselectivity with [Rh(Cp*)Cl-2](2) and unsymmetrical vicinal diamine ligands as catalyst systems.

Rifampicin reduces advanced glycation end products and activates DAF-16 to increase lifespan in Caenorhabditis elegans - Golegaonkar, Sandeep; Tabrez, Syed S.; Pandit, Awadhesh; Sethurathinam, Shalini; Jagadeeshaprasad, Mashanipalya G.; Bansode, Sneha B.; Sampathkumar, Srinivasa-Gopalan; Kulkarni, Mahesh J.; Mukhopadhyay, Arnab (Aging Cell, 2015)
Advanced glycation end products (AGEs) are formed when glucose reacts nonenzymatically with proteins; these modifications are implicated in aging and pathogenesis of many age-related diseases including type II diabetes, atherosclerosis, and neurodegenerative disorders. Thus, pharmaceutical interventions that can reduce AGEs may delay age-onset diseases and extend lifespan. Using LC-MSE, we show that rifampicin (RIF) reduces glycation of important cellular proteins in vivo and consequently increases lifespan in Caenorhabditis elegans by up to 60%. RIF analog rifamycin SV (RSV) possesses similar properties, while rifaximin (RMN) lacks antiglycation activity and therefore fails to affect lifespan positively. The efficacy of RIF and RSV as potent antiglycating agents may be attributed to the presence of a p-dihydroxyl moiety that can potentially undergo spontaneous oxidation to yield highly reactive p-quinone structures, a feature absent in RMN. We also show that supplementing rifampicin late in adulthood is sufficient to increase lifespan. For its effect on longevity, rifampicin requires DAF-18 (nematode PTEN) as well as JNK-1 and activates DAF-16, the FOXO homolog. Interestingly, the drug treatment modulates transcription of a different subset of DAF-16 target genes, those not controlled by the conserved Insulin-IGF-1-like signaling pathway. RIF failed to increase the lifespan of daf-16 null mutant despite reducing glycation, showing thereby that DAF-16 may not directly affect AGE formation. Together, our data suggest that the dual ability to reduce glycation in vivo and activate prolongevity processes through DAF-16 makes RIF and RSV effective lifespan-extending interventions.
Keywords: advanced glycation end products; aging; Caenorhabditis elegans; DAF-16; Glycation; lifespan; rifampicin

Robustness screen in enantioselective catalysis enabled generation of enantioenriched heterocyclic scaffolds in one pot - Bagle, Pradip N.; Shinde, Valmik S.; Patil, Nitin T. (Chemistry-A European Journal, 2015)
Enantioselective catalysis has emerged as a powerful synthetic paradigm and has accelerated the development of new methods to make diverse chiral molecules. Generally, these reactions are very sensitive to the steric and electronic environment present in the catalyst as well as the substrates. With this scenario, the presence of an additional component in the reaction mixture is expected to add complexity in achieving the enantioselective variants. Herein, we report that various enantioenriched molecules could be obtained from multiple starting materials in one pot. The reaction of aminoaromatics A with alkynols B-1, B-2, B-3...B-n with a Au-I/chiral BrOnsted acid catalyst afforded AB(1)*, AB(2)*, AB(3)*...AB(n)*; while, the reaction of alkynols B with aminoaromatics A(1), A(2), A(3)...A(n) under the same reaction conditions gave A(1)B*, A(2)B*, A(3)B*...A(n)B*.
Keywords: chiral Bronsted acid; Enantioselectivity; Gold; molecular scaffolds; robustness screen

Role of lipid-mediated effects in beta(2)-adrenergic receptor dimerization - Prasanna, Xavier; Chattopadhyay, Amitabha; Sengupta, Durba (biochemical roles of eukaryotic cell surface macromolecules, 2015)

Role of N-terminal proline in stabilizing the Ant-Pro zipper motif - Kheria, Sanjeev; Nair, Roshna V.; Kotmale, Amol S.; Rajamohanan, Pattuparambil R.; Sanjayan, Gangadhar J. (New Journal of Chemistry, 2015)
Hetero-chiral hybrid peptides of the general sequence (L)alpha beta(D)(n)alpha beta(n) featuring proline (Pro, a constrained alpha-amino acid) and anthranilic acid (Ant, a constrained beta-amino acid) as building blocks, where n = 2, 4 etc., form a three-dimensional zipper-like architecture. These zipper peptides attain stable conformation by balancing the co-operative contribution of two competing non-covalent forces, namely hydrogen bonding and aromatic stacking. However, the selection of the N-terminal residue also stands to be one of the key contributors in stabilising the unusually long-range intramolecular hydrogen bond, featuring 26 atoms in the H-bonded ring observed at the termini. This article deals with the substitution alterations at the N-terminus of the zipper motif and their consequent influences on its structure and stability. In this study, the N-terminal Pro residue of the zipper motif was substituted with a flexible amino acid, alanine, and a constrained acyclic amino acid, 2-aminoisobutyric acid, to investigate the role of N-terminal proline in stabilizing the Ant-Pro zipper motif, and its stabilities were assessed by employing solution-state NMR and restrained MD simulation studies.

Role of tumor cell surface lysosome-associated membrane protein-1 (LAMP1) and its associated carbohydrates in lung metastasis - Agarwal, Akhil Kumar; Srinivasan, Nithya; Godbole, Rashmi K.; More, Shyam K.; Budnar, Srikanth; Gude, Rajiv P.; Kalraiya, Rajiv D. (Journal of Cancer Research and Clinical Oncology, 2015)
Expression of lysosome-associated membrane protein-1 (LAMP1) on the surface correlates with metastatic potential of B16 melanoma cells. Downregulation of their expression in high metastatic (B16F10) cells reduced their surface expression and metastatic potential. Present investigations explore if overexpression of LAMP1 on the surface of low metastatic (B16F1) cells augment their metastatic ability, and if so, how? B16F1 cells were transduced with lentiviral vector carrying mutant-LAMP1 (Y386A) (mutLAMP1). Surface expression of LAMP1 and carbohydrates was analyzed by flow cytometry, immunofluorescence and/or immunoprecipitation and Western blotting. Cell spreading and motility were assessed on components of extracellular matrix (ECM) (fibronectin) and basement membrane (BM) (matrigel), and galectin-3-coated coverslips/plates. Metastatic potential was assessed using experimental metastasis assay. Pre-incubation with anti-LAMP1 antibodies significantly reduced lung metastasis of B16F10 cells. Overexpression of mutLAMP1 significantly increased its surface expression on B16F1 cells, resulting in increased cellular spreading and motility on fibronectin and matrigel. LAMP1 is the major carrier of poly-N-acetyllactosamine (polyLacNAc) on B16F10 cells. However, significantly higher expression of mutLAMP1 had no effect on galectin-3 binding on cell surface or on spreading or motility of cells on galectin-3-coated coverslips/plates. These cells also failed to show any gain in metastatic ability. This could be because LAMP1 from these cells carried significantly lower levels of polyLacNAc in comparison with B16F10 cells. PolyLacNAc on B16F10 cells and galectin-3 on lungs are the major participants in melanoma metastasis. Although surface LAMP1 promotes interactions with organ ECM and BM, carbohydrates on LAMP1 play a decisive role in dictating lung metastasis.
Keywords: 6 branched N-oligosaccharides; beta 1; Cell surface LAMP1; Galectin-3; Motility; Organ-specific metastasis; Poly-N-acetyllactosamine

Rottlerin derivatives and other compounds from mallotus philippinensis fruits and their potential antimycobactrial activity - Bhardwaj, Rima; Chinchansure, Ashish A.; Kulkarni, Roshan R.; Arkile, Manisha A.; Sarkar, Dhiman; Joshi, Swati P. (Planta Medica Letters, 2015)
The methanolic extract of the fruits of Mallotus philippinensis afforded 13 compounds, 7,11-diketo-lanost-3-ol (1, as acetate), lanosta-8-ene-3β-ol (2, as acetate), pregnenolone (3, as acetate), trans-chalcone (4), kamalachalcone E (5), oleanolic acid (6), gallic acid (7), kaempferol (8), myricetin (9), 1-(5,7-dihydroxy-2,2,6-trimethyl-2 H-1-benzopyran-8-yl)-3-phenyl-2-propen-1-one (10), 4′-hydroxyisorottlerin (11), rottlerin (12), and shikimic acid (13). Compound 1 was isolated as a new natural product and its structure was elucidated by 1D and 2D nuclear magnetic resonance analyses including heteronuclear single quantum correlation, heteronuclear multiple-bond correlation, correlation spectroscopy, and nuclear Overhauser effect spectroscopy experiments. All of the isolated compounds were evaluated for their antimycobacterium activity against Mycobacterium tuberculosis H37Ra. Compounds 11 and 12 exhibited promising inhibitory activity with IC50 values of 0.89 ± 0.33 µg/mL (MIC 2.06 ± 0.41 µg/mL) and 7.59 ± 0.42 µg/mL (MIC 11.56 ± 0.35 µg/mL), respectively.

SBA-15-oxynitrides as a solid-base catalyst: effect of nitridation temperature on catalytic activity - Singh, Baljeet; Mote, Kaustubh R.; Gopinath, Chinnakonda S.; Madhu, Perunthiruthy K.; Polshettiwar, Vivek (Angewandte Chemie-International Edition, 2015)
Solid bases, such as SBA-15-oxynitrides, have attracted considerable interest for potential applications as catalysts in important industrial processes. Reported herein is that by simply tuning the temperature of nitridation (ammonolysis), the catalytic activity of these solid bases can be enhanced. Solid-state NMR spectroscopy and XPS studies provided the reasoning behind this change in activity.
Keywords: heterogeneous catalysis; Nanostructures; NMR spectroscopy; photoelectron spectroscopy; solid-state structures

Selective and sensitive sensing of free bilirubin in human serum using water-soluble polyfluorene as fluorescent probe - Senthilkumar, T.; Asha, S. K. (Macromolecules, 2015)
The adherence of serum protein on conjugated polymer is a major bottleneck in the application of the latter for selective sensing of small biomolecules in blood serum. In this report, we present new polyfluorenes with d-glucuronic acid appendage that is a nonreceptor for any serum protein, thereby providing a platform for selective sensing of free bilirubin in the clinically relevant range of <25 to >50 mu mol/L in human blood serum. The appended d-glucuronic acid formed noncovalent interactions with bilirubin, which in conjunction with favorable spectral overlap between the polymers and bilirubin facilitated efficient FRET process in aqueous solutions. Addition of bilirubin resulted in the quenching of the polyfluorene emission with simultaneous appearance of bilirubin emission exhibiting visual emission color change from blue to light green. The polymer remained stable in serum even under severe basic conditions and exhibited high selectivity with visual sensitivity only toward free bilirubin in human serum in the presence of crucial interferences such as hemoglobin, proteins, biliverdin, glucose, cholesterol, and metal ions. Nanomolar sensing of bilirubin could also be demonstrated successfully using one of the d-glucuronic acid appended polymer (PF-Ph-GlcA), which could sense similar to 150 nm of bilirubin in human serum. The combined role of energy transfer and noncovalent interaction highlights the potential of the new polymer design for highly selective sensing activity in complex biofluids.

Self-assembly directed template photopolymerization of perylenebisimide-poly (4-vinylpyridine): nano organization - Shinde, Shekhar; Asha, S. K. (Polymer, 2015)
A perylene bisimide derivative (PDP-UPBIAcry) having hydroxyl moieties at one termini and polymerizable acrylic units at the other termini was supramolecularly complexed with the pyridine units of Poly (4-vinyl pyridine) (P4VP), followed by photoinduced polymerization of the acrylic units to obtain lamellar organization in the <10 nm range. H-1 NMR studies including variable temperature (20 degrees C-70 degrees C) measurements were undertaken in DMSO-d(6) (anhydrous, extra dry) to understand the interaction between PDP-UPBIAcry and P4VP. The aromatic perylene protons of PDP-UPBIAcry registered an upfield chemical shift while the pyridine protons of P4VP exhibited small downfield shift in their 1:1 supramolecular complex. The hydrogen bonding interaction between pyridyl nitrogen and phenolic OH group was also traced in non-polar media like CDCl3 in model complexes of 4-vinyl pyridine (4VP) with PDP-UPBIAcry. Wide angle X-ray diffraction (WXRD) technique was used to study the bulk structure. Transmission electron microscopy (TEM) imaging revealed highly ordered layered assembly formed upon complexation. Observation from DFT energy minimization studies were correlated with X-ray diffraction data of the supramolecular complex [P4VP (PDP-UPBIAcry)](1.0) to understand the nature of packing of PDP-UPBIAcry that lead to the formation of highly ordered lamellar stacks alternating with P4VP. The higher ordering in the supramolecular polymer complex was also confirmed by the quenching of fluorescence and reduced fluorescence life times of thin solid films of the [P4VP Poly(PDP-UPBIAcry)](1.0) sample. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: hydrogen bonding; P4VP; Perylenebisimide

Self-templated chemically stable hollow spherical covalent organic framework - Kandambeth, Sharath; Venkatesh, V.; Shinde, Digambar B.; Kumari, Sushma; Halder, Arjun; Verma, Sandeep; Banerjee, Rahul (Nature Communications, 2015)
Covalent organic frameworks are a family of crystalline porous materials with promising applications. Although active research on the design and synthesis of covalent organic frameworks has been ongoing for almost a decade, the mechanisms of formation of covalent organic frameworks crystallites remain poorly understood. Here we report the synthesis of a hollow spherical covalent organic framework with mesoporous walls in a single-step template-free method. A detailed time-dependent study of hollow sphere formation reveals that an inside-out Ostwald ripening process is responsible for the hollow sphere formation. The synthesized covalent organic framework hollow spheres are highly porous (surface area similar to 1,500m(2) g(-1)), crystalline and chemically stable, due to the presence of strong intramolecular hydrogen bonding. These mesoporous hollow sphere covalent organic frameworks are used for a trypsin immobilization study, which shows an uptake of 15.5 mu mol g(-1) of trypsin.

Sequence and structure-based comparative analysis to assess, identify and improve the thermostability of penicillin G acylases - Panigrahi, Priyabrata; Chand, Deepak; Mukherji, Ruchira; Ramasamy, Sureshkumar; Suresh, C. G. (Journal of Industrial Microbiology & Biotechnology, 2015)
Penicillin acylases are enzymes employed by the pharmaceutical industry for the manufacture of semi-synthetic penicillins. There is a continuous demand for thermostable and alkalophilic enzymes in such applications. We have carried out a computational analysis of known penicillin G acylases (PGAs) in terms of their thermostable nature using various protein-stabilizing factors. While the presence of disulfide bridges was considered initially to screen putative thermostable PGAs from the database, various other factors such as high arginine to lysine ratio, less content of thermolabile amino acids, presence of proline in beta-turns, more number of ion-pair and other non-bonded interactions were also considered for comparison. A modified consensus approach designed could further identify stabilizing residue positions by site-specific comparison between mesostable and thermostable PGAs. A most likely thermostable enzyme identified from the analysis was PGA from Paracoccus denitrificans (PdPGA). This was cloned, expressed and tested for its thermostable nature using biochemical and biophysical experiments. The consensus site-specific sequence-based approach predicted PdPGA to be more thermostable than Escherichia coli PGA, but not as thermostable as the PGA from Achromobacter xylosoxidans. Experimental data showed that PdPGA was comparatively less thermostable than Achromobacter xylosoxidans PGA, although thermostability factors favored a much higher stability. Despite being mesostable, PdPGA being active and stable at alkaline pH is an advantage. Finally, several residue positions could be identified in PdPGA, which upon mutation selectively could improve the thermostability of the enzyme.
Keywords: Alkalistable; beta-lactam antibiotics; Consensus approach; Disulfide bridge; Ion pairs; Penicillin acylase; Thermostability

Shape-selective oriented cerium oxide nanocrystals permit assessment of the effect of the exposed facets on catalytic activity and oxygen storage capacity - Sreeremya, Thadathil S.; Krishnan, Asha; Remani, Kottayilpadi C.; Patil, Kashinath R.; Brougham, Dermot F.; Ghosh, Swapankumar (ACS Applied Materials & Interfaces, 2015)
The catalytic performance of a range of nanocrystalline CeO2 samples, prepared to have different morphologies, was measured using two accepted indicators; oxygen storage and diesel soot combustion. The same powders were characterized hi detail by HR-TEM, XRD, XPS, and Raman methods. The study demonstrates that activity is determined by the relative fraction of the active crystallographic planes, not by the specific surface area of the powders. The physical study is a step toward quantitative evaluation of the relative contribution to activity of the different facets. The synthetic protocol permits fabrication of CeO2 nanostructures with preferentially grown active planes, and therefore has potential in developing catalytic applications and in nanocompositing.
Keywords: ceria; chemical activities; crystal facets; nanocrystals; texture coefficient

Short enantioselective synthesis of ephedrine, amphetamine and their analogues via two stereocentered Co(III)-catalyzed hydrolytic kinetic resolution of racemic syn-benzyloxy epoxide - Lalwani, Komal G.; Sudalai, Arumugam (Tetrahedron Letters, 2015)
An efficient route for the synthesis of 6 drugs belonging to phenethylamine and amphetamine classes in excellent overall yields and high optical purity has been described. The strategy involves introduction of stereogenic centers by means of two-stereocentered Co(III)-catalyzed hydrolytic kinetic resolution (HKR) of racemic syn-benzyloxy epoxide followed by Pd-catalyzed regioselective cationic hydrogenation of amino alcohols as the key reactions. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Amphetamine; Cationic hydrogenation; Hydrolytic kinetic resolution; Phenethylamine; Stereogenic centers

Silicon incorporated morpholine antifungals: design, synthesis, and biological evaluation - Jachak, Gorakhnath R.; Ramesh, Remya; Sant, Duhita G.; Jorwekar, Shweta U.; Jadhav, Manjusha R.; Tupe, Santosh G.; Deshpande, Mukund V.; Reddy, D. Srinivasa (ACS Medicinal Chemistry Letters, 2015)
Known morpholine class antifungals (fenpropimorph, fenpropidin, and amorolfine) were synthetically modified through silicon incorporation to have 15 sila-analogues. Twelve sila-analogues exhibited potent antifungal activity against different human fungal pathogens such as Candida albicans, Candida glabrata, Candida tropicalis, Cryptococcus neoformans, and Aspergillus niger. Si la-analogue 24 (fenpropimorph analogue) was the best in our hands, which showed superior fungicidal potential than fenpropidin, fenpropimorph, and amorolfine. The mode of action of sila-analogues was similar to morpholines, i.e., inhibition of sterol reductase and sterol isomerase enzymes of ergosterol synthesis pathway.
Keywords: Antifungal drugs; Candida albicans; ergosterol biosynthesis; morpholines; sila-analogues

Simple method for the preparation of ultra-small palladium nanoparticles and their utilization for the hydrogenation of terminal alkyne groups to alkanes - Seth, Jhumur; Kona, Chandrababu Naidu; Das, Shyamsundar; Bhagavatula L. V. Prasad (Nanoscale, 2015)
A simple and convenient method for the preparation of ultra-small palladium nanoparticles (Pd-NPs) by a modified digestive ripening method is described. These nanoparticles catalyse the hydrogenation of the terminal alkyne groups to alkanes selectively, and show no effect on other labile protecting and internal alkyne or internal/external alkene groups present in the molecule.

Situ preparation of N-TiO2/graphene nanocomposite and its enhanced photocatalytic hydrogen production by H2S splitting under solar light - Bhirud, Ashwini P.; Sathaye, Shivaram D.; Waichal, Rupali P.; Ambekar, Jalindar D.; Park, Chan-J.; Kale, Bharat B. (Nanoscale, 2015)
Highly monodispersed nitrogen doped TiO2 nanoparticles were successfully deposited on graphene (N-TiO2/Gr) by a facile in-situ wet chemical method for the first time. N-TiO2/Gr has been further used for photocatalytic hydrogen production using a naturally occurring abundant source of energy i.e. solar light. The N-TiO2/Gr nanocomposite composition was optimized by varying the concentrations of dopant nitrogen and graphene (using various concentrations of graphene) for utmost hydrogen production. The structural, optical and morphological aspects of nanocomposites were studied using XRD, UV-DRS, Raman, XPS, FESEM, and TEM. The structural study of the nanocomposite shows existence of anatase N-TiO2. Further, the details of the components present in the composition were confirmed with Raman and XPS. The morphological study shows that very tiny, 7-10 nm sized, N-TiO2 nanoparticles are deposited on the graphene sheet. The optical study reveals a drastic change in absorption edge and consequent total absorption due to nitrogen doping and presence of graphene. Considering the extended absorption edge to the visible region, these nanocomposites were further used as a photocatalyst to transform hazardous H2S waste into eco-friendly hydrogen using solar light. The N-TiO2/Gr nanocomposite with 2% graphene exhibits enhanced photocatalytic stable hydrogen production i.e. similar to 5941 mu mol h(-1) under solar light irradiation using just 0.2 gm nanocomposite, which is much higher as compared to P25, undoped TiO2 and TiO2/Gr nanocomposite. The enhancement in the photocatalytic activity is attributed to `N' doping as well as high specific surface area and charge carrier ability of graphene. The recycling of the photocatalyst shows a good stability of the nanocomposites. This work may provide new insights to design other semiconductor deposited graphene novel nanocomposites as a visible light active photocatalyst.

Situ preparation of N-ZnO/graphene nanocomposites: excellent candidate as a photocatalyst for enhanced solar hydrogen generation and high performance supercapacitor electrode - Bhirud, Ashwini P.; Sathaye, Shivaram; Waichal, Rupali; Park, Chan-Jin; Kale, Bharat (Journal of Materials Chemistry A, 2015)
We have demonstrated a facile in situ wet chemical method to synthesize nanostructured nitrogen doped ZnO/Graphene (N-ZnO/GR) nanocomposites for the first time. Nitrogen doped ZnO over graphene (N-ZnO/GR) was studied using various concentrations of graphene. During the synthesis of N-ZnO/GR nanocomposites, in situ formation of graphene via GO reduction and formation of 4-9 nm N-ZnO have been demonstrated. The composite N-ZnO/GR absorbs in the visible region and this property is used for the photocatalytic reaction to transform hazardous H2S waste into eco-friendly hydrogen using solar light. The N-ZnO/GR nanocomposite with 0.3% graphene exhibits an enhanced photocatalytic stable hydrogen production rate i.e. similar to 5072 mu mol h(-1) under visible light irradiation. It is noteworthy that the N-ZnO/GR electrode exhibits a high specific capacitance of 555 F g(-1) and excellent cyclic performance with nearly 96.20% capacity retention after 2000 cycles at a current density of 10 A g(-1). These results indicate great potential applications of N-ZnO/GR in developing high hydrogen production and supercapacitors with high energy and power densities.

Sodium periodate mediated oxidative transformations in organic synthesis - Sudalai, Arumugam; Khenkin, Alexander; Neumann, Ronny (Organic & Biomolecular Chemistry, 2015)
The investigation of new oxidative transformations for the synthesis of carbon-heteroatom and heteroatom-heteroatom bonds is of fundamental importance in the synthesis of numerous bioactive molecules and fine chemicals. In this context, NaIO4, an exciting reagent, has attracted increasing attention enabling the development of these unprecedented oxidative transformations that are difficult to achieve otherwise. Thus, NaIO4 has been successfully explored as a versatile oxidant for a variety of fundamental organic transformations such as C-H activation, oxidative functionalization of alkenes and other interesting oxidative transformations and its application in the synthesis of bioactive natural products. This review summarizes recent developments in this area with NaIO4 as a versatile oxidant and brings out many challenges that still remain elusive for the future.

Sophorolipid assisted tunable and rapid gelation of silk fibroin to form porous biomedical scaffolds - Dubey, Parul; Nawale, Laxman; Sarkar, Dhiman; Nisal, Anuya; Prabhune, Asmita (RSC Advances, 2015)
Three dimensional polymer hydrogels, based on both natural and synthetic polymers, are increasingly being used as scaffolds and drug delivery vehicles for biomedical applications. Fibrous protein, silk fibroin (SF), obtained from the Bombyx mori silkworm is a promising candidate in this area. However, SF has a long gelation time of about a few weeks that can only be reduced by non-physiological treatments (e. g. high temperature, ultrasonication and low pH) or by addition of a chemical and non-biodegradable polymer and/or surfactant. We report here accelerated gelation of SF under physiological conditions using a biosurfactant, sophorolipid (SL) as a gelling agent. SL and SF are completely miscible and form a very clear solution upon mixing. Hence it is interesting to see that this clear solution gels in a time span of just a few hours. The hydrogels so formed have pore architecture, porosities and mechanical stability ideally suited for tissue culture applications. Here we also demonstrate that mouse fibroblast cells not only adhere to but also extensively proliferate on these SF-SL scaffolds.

Specific reagent for Cr(III): imaging cellular uptake of Cr(III) in Hct116 cells and theoretical rationalization - Ali, Firoj; Saha, Sukdeb; Maity, Arunava; Taye, Nandaraj; Si, Mrinal Kanti; Suresh, E.; Ganguly, Bishwajit; Chattopadhyay, Samit; Das, Amitava (Journal of Physical Chemistry B, 2015)
A new rhodamine-based reagent (L-1), trapped inside the micellar structure of biologically benign Triton-X 100, could be used for specific recognition of Cr(III) in aqueous buffer medium having physiological pH. This visible light excitable reagent on selective binding to Cr(III) resulted in a strong fluorescence turn-on response with a maximum at similar to 583 nm and tail of that luminescence band extended until 650 nm, an optical response that is desired for avoiding the cellular autofluorescence. Interference studies confirm that other metal ions do not interfere with the detection process of Cr(III) in aqueous buffer medium having pH 7.2. To examine the nature of binding of Cr(III) to L-1, various spectroscopic studies are performed with the model reagent L-1 which tend to support Cr(III)-eta(2)-olefin pi-interactions involving two olefin bonds in molecular probe L-1. Computational studies are also performed with another model reagent L-M to examine the possibility of such Cr(III)-eta(2)-olefin pi-interactions. Presumably, polar functional groups of the model reagent L-M upon coordination to the Cr(III) center effectively reduce the formal charge on the metal ion and this is further substantiated by results of the theoretical studies. This assembly is found to be cell membrane permeable and shows insignificant toxicity toward live colon cancer cells (Hct116). Confocal laser scanning microscopic studies further revealed that the reagent L-1 could be used as an imaging reagent for detection of cellular uptake of Cr(III) in pure aqueous buffer medium by Hct116 cells. Examples of a specific reagent for paramagnetic Cr(III) with luminescence ON response are scanty in the contemporary literature. This ligand design helped us in achieving the turn on response by utilizing the conversion from spirolactam to an acyclic xanthene form on coordination to Cr(III).

Spectral analysis of the emission current noise exhibited by few layer WS2 nanosheets emitter - Suryawanshi, Sachin R.; Kolhe, Pankaj S.; Rout, Chandra S.; Late, Dattatray J.; More, Mahendra A. (Ultramicroscopy, 2015)
Spectral analysis of the field emission (FE) current fluctuations has been carried out at the base pressure similar to 1 x 10(-8) mbar. The emission current stability investigated at preset value of 2 mu A is characterized by `step like fluctuation. The spectral analysis performed on a FFT (Fast Fourier Transform) analyzer revealed that the observed noise is of 1/f(alpha) type, with the value of alpha as similar to 1.05. The estimated value of alpha implies that the current fluctuations are mainly due the various processes occurring on atomic scale like adsorption, migration, and/or desorption of the residual gas species on the emitter surface. (C) 2014 Elsevier B.V. All rights reserved.
Keywords: Current fluctuations; field emission; Noise; WS2 nanosheets

Spectroscopic and ab initio investigation of 2,6-difluorophenylacetylene-amine complexes: coexistence of C-H center dot center dot center dot N and lone-pair center dot center dot center dot pi complexes and intermolecular coulombic decay - Mondal, Sohidul Islam; Dey, Arghya; Sen, Saumik; Patwari, G. Naresh; Ghosh, Debashree (Physical Chemistry Chemical Physics, 2015)
Binary complexes of 2,6-difluorophenylacetylene with methylamine, dimethylamine, trimethylamine and triethylamine were investigated using one colour resonant two photon ionization and infrared-optical double resonance spectroscopic techniques combined with high level ab initio calculations. All four amines form C-Ac-H center dot center dot center dot N hydrogen-bonded complexes. Additionally trimethylamine and triethylamine form complexes characterized by Lp center dot center dot center dot pi interactions, due to the electron deficient nature of the phenyl ring of 2,6-difluorophenylacetylene. The Lp center dot center dot center dot pi interacting structure of the 2,6-difluorophenylacetylenetrimethylamine complex is about 1.5 kJ mol(-1) higher in energy than the C-Ac-H center dot center dot center dot N hydrogen-bonded structure, which is the global minimum. Energy decomposition analysis indicates that the electrostatics and dispersion interactions favour the formation of C-Ac-H center dot center dot center dot N and Lp center dot center dot center dot pi complexes, respectively. Interestingly the C-Ac-H center dot center dot center dot N hydrogen-bonded complex of 2,6-difluorophenylacetylene-triethylamine showed a smaller shift in the acetylenic C-H stretching frequency than the 2,6-difluorophenylacetylene-trimethylamine complex. The observed fragmentation of the binary complexes of 2,6-difluorophenylacetylene with the four amines following resonant two-photon ionization can be explained on the basis of the intermolecular coulombic decay process.

Spin-coatable, photopatternable magnetic nanocomposite thin films for MEMS device applications - Kandpal, Manoj; Sharan, C.; Palaparthy, V.; Tiwary, N.; Poddar, P.; Rao, V. Ramgopal (RSC Advances, 2015)
Magnetic nanomaterials' (especially metals) air stability and compatibility with standard micro-fabrication technologies are often a concern for development of MEMS-based magnetic devices. In this paper, we report an air-stable, photo-patternable and spin-coatable magnetic thin film preparation process for MEMS applications. This magnetic nanocomposite thin film was prepared by incorporating carbon capped ferromagnetic cobalt nanoparticles of dimension 20-80 nm into the SU-8 matrix. TEM, XRD and EDAX analyses were done, to investigate the crystal structure, dispersion and phase stability of the films. The SQUID magnetometry and MFM measurements of the film confirmed its magnetic response at room temperature and the retention of its magnetic properties over a period of time. The material compatibility for MEMS device applications was demonstrated through fabrication of a suspended circular membrane of radius similar to 250 mu m, having four U-shaped beams, of dimension similar to 270 x 50 mu m each. Three conventional lithography steps and a sacrificial release layer of similar to 1 mm thick oxide was used for the fabrication. The membrane was characterized by evaluating its spring constant and resonant frequency. The spring constant and resonant frequencies were estimated to be similar to 4.2 N m(-1) and similar to 29 kHz respectively. Finally, we demonstrated the actuation of the magnetic membrane by an off-chip generated magnetic field, for its possible use as a MEMS device.

Spirochromone-chalcone conjugates as antitubercular agents: synthesis, bio evaluation and molecular modeling studies - Mujahid, Mohammad; Perumal, Yogeeswari; Sriram, D.; Basavanag, U. M. V.; Dıaz-Cervantes, Erik; Cordoba-Bahena, Luis; Robles, Juvencio; Gonnade, Rajesh Ghanshyam; Karthikeyan, Muthukumarasamy; Vyas, Renu; Krishnan, M. Muthu (RSC Advances, 2015)
A new series of spirochromone annulated chalcone conjugates were synthesized and evaluated for their antitubercular activity against Mycobacterium tuberculosis H37Rv strain. These compounds were subjected to molecular modeling studies using docking and chemoinformatics based approaches. The docking simulations were performed against a range of known receptors for chalcone derived compounds to reveal MTB phosphotyrosine phosphatase B [MtbPtpB] protein as the most probable target based on the high binding affinity scores. Five compounds exhibit significant inhibition, showing minimum inhibitory concentration values i.e. MIC values ranging from 3.13–12.5 μg mL−1. Further analysis of the synthesized compounds with known and in-house developed chemoinformatics tools unequivocally established their potential as anti-tubercular compounds. QSAR modeling revealed a quantitative relationship between biological activities and frontier molecular orbital energies of synthesized compounds. The predictive model can be employed further for virtual screening of new compounds in this series.

Star telechelic poly(L-lactide) ionomers - Kulkarni, Amruta; Lele, Ashish K.; Sivaram, Swaminathan; Rajamohanan, P. R.; Velankar, Sachin; Chatterji, Apratim (Macromolecules, 2015)
Poly(L-lactide) (PLA), a biodegradable and biorenewable polymer, has many excellent properties that are equivalent to those of petroleum-derived plastics such as polystyrene, aromatic polyesters, etc. However, a major disadvantage of PLA which limits its processability is its poor melt elasticity. In this work we explore the possibility of improving the viscoelastic properties of PLA melt by incorporating ionic groups on the polymer. Specifically, we demonstrate the synthesis of star telechelic PLA anionomers by a three-step procedure involving synthesis of Star PIA, converting the hydroxyl end groups into carboxylic acid end groups, and finally converting these into ionic groups. Rheology data showed a dramatic increase in the elasticity of the star telechelic ionomer melts relative to the Star PLA melts. The viscoelasticity of star telechelic ionomers melts could be modulated by varying the number of ionic groups per molecule.

Starch (Tapioca) to carbon dots: an efficient green approach to an on-off-on photoluminescence probe for fluoride ion sensing - Basu, Aniruddha; Suryawanshi, Anil; Kumawat, Begraj; Dandia, Anshu; Guin, Debanjan; Ogale, Satishchandra B. (Analyst, 2015)
Photoluminescent carbon dots of 4-5 nm size were prepared from starch (Tapioca Sago) through a solution method under mild conditions. The as-prepared carbon dots were used as photoluminescence probes for highly anion selective fluoride ion detection in aqueous solutions. A ready-to-use device is also demonstrated.

Stepwise isolation of low-valent, low-coordinate Sn and Pb mono- and dications in the coordination sphere of platinum - Braunschweig, Holger; Celik, Mehmet Ali; Dewhurst, Rian D.; Heid, Magdalena; Hupp, Florian; Sen, Sakya S. (Chemical Science, 2015)
Synthetic access to low-coordinate Pb mono- and dications is in general impeded due to their poor solubility and highly electrophilic nature. However, the electrophilicity of these cations can be tamed by attaching them to electron-rich transition metals. Following this principle we have isolated low-valent Pb mono- ([(Cy3P)(2)Pt-PbCl](2)[AlCl4](2), 8a) and dications ([(Cy3P)(2)Pt(Pb)][AlCl4](2), 11) in the coordination sphere of platinum. The same approach then has been implemented for the isolation of analogous low-valent Sn mono- (7a) and dications (10). An energy decomposition analysis (EDA-NOCV) was performed to investigate the nature of Pt-Pb and Pb-Cl bonding in [(Cy3P)(2)Pt(PbCl2)] (2), 8a and 11. The results show that the Pt-Pb bonds in 8a and 11 are electron-sharing in nature, whereas that of the precursor 2 is a dative bond. The breakdown of attractive interactions in 2, 8a and 11 reveals that the ionic interactions in the analyzed Pt-Pb and Pb-Cl bonds are always stronger than the covalent interactions, except for the Pb-Cl bond in 8a. The calculated D3 dispersion energies show that dispersion interactions play a key role in the thermodynamic stability of 2, 8a and 11.

Structure mediation in substrate binding and post-translational processing of penicillin acylases: Information from mutant structures of Kluyvera citrophila penicillin G acylase - Chand, Deepak; Varshney, NishantKumar; Ramasamy, Sureshkumar; Panigrahi, Priyabrata; Brannigan, James A.; Wilkinson, Anthony J.; Suresh, C. G. (Protein Science, 2015)
Penicillin acylases are industrially important enzymes for the production of 6-APA, which is used extensively in the synthesis of secondary antibiotics. The enzyme translates into an inactive single chain precursor that subsequently gets processed by the removal of a spacer peptide connecting the chains of the mature active heterodimer. We have cloned the penicillin G acylase from Kluyvera citrophila (KcPGA) and prepared two mutants by site-directed mutagenesis. Replacement of N-terminal serine of the beta-subunit with cysteine (Ser beta 1Cys) resulted in a fully processed but inactive enzyme. The second mutant in which this serine is replaced by glycine (Ser beta 1Gly) remained in the unprocessed and inactive form. The crystals of both mutants belonged to space group P1 with four molecules in the asymmetric unit. The three-dimensional structures of these mutants were refined at resolutions 2.8 and 2.5 angstrom, respectively. Comparison of these structures with similar structures of Escherichia coli PGA (EcPGA) revealed various conformational changes that lead to autocatalytic processing and consequent removal of the spacer peptide. The large displacements of residues such as Arg168 and Arg477 toward the N-terminal cleavage site of the spacer peptide or the conformational changes of Arg145 and Phe146 near the active site in these structures suggested probable steps in the processing dynamics. A comparison between the structures of the processed Serb1Cys mutant and that of the processed form of EcPGA showed conformational differences in residues Arg alpha 145, Phe alpha 146, and Phe beta 24 at the substrate binding pocket. Three conformational transitions of Arg alpha 145 and Phe alpha 146 residues were seen when processed and unprocessed forms of KcPGA were compared with the substrate bound structure of EcPGA. Structure mediation in activity difference between KcPGA and EcPGA toward acyl homoserine lactone (AHL) is elucidated.
Keywords: acyl homoserine lactone; autocatalytic processing; conformational changes; KcPGA_Ser beta 1Cys; KcPGA_Ser beta 1Gly; Ntn hydrolase

Structure-induced catalytic activity of Co-Zn double-metal cyanide complexes for terpolymerization of propylene oxide, cyclohexene oxide and CO2 - Sebastian, Joby; Darbha, Srinivas (RSC Advances, 2015)
The application of Co-Zn double-metal cyanide (DMC) complexes as catalysts for selective terpolymerization of propylene oxide, cyclohexene oxide and CO2 producing polycarbonates is reported for the first time. DMC complexes were prepared with and without using a co-complexing agent. The catalyst with monoclinic/rhombohedral crystal structure and strong Lewis acidity, prepared without using a co-complexing agent showed higher initial activity than that with a cubic structure prepared using a co-complexing agent. Interestingly, no induction period in the terpolymerization reaction was observed. The terpolymer has 75.5 mol% of carbonate fraction in its composition and an average molecular weight of 22 700 and polydispersity index of 2.97. It is characterized by a T-g of 55 degrees C. This structure-induced catalytic activity of DMC can open up new avenues for its applications in other reactions. The influence of process parameters on the catalytic activity of DMC was investigated.

Study of molecular vibration by coupled cluster method: bosonic approach - Banik, Subrata; Pal, Sourav; Prasad, M. Durga (Proceedings of the International Conference of Computational Methods in Sciences and Engineering 2010 (ICCMSE-2010), 2015)
The vibrational coupled cluster method in bosonic representation is formulated to describe the molecular anharmonic vibrational spectra. The vibrational coupled cluster formalism is based on Watson Hamiltonian in normal coordinates. The vibrational excited states are described using coupled cluster linear response theory (CCLRT). The quality of the coupled cluster wave function is analyzed. Specifically, the mean displacement values of the normal coordinates <qi> and expectation values of the square of the normal coordinates <q(i)(2)> of different vibrational states are calculated. A good agreement between the converged full CI results and coupled cluster results is found for the lower lying vibrational states.</q(i)(2)></qi>
Keywords: CCLRT; Expectation values; Watson Hamiltonian

Study of the nucleation and growth of antibiotic labeled Au NPs and blue luminescent Au-8 quantum clusters for Hg2+ ion sensing, cellular imaging and antibacterial applications - Khandelwal, Puneet; Singh, Dheeraj K.; Sadhu, Subha; Poddar, Pankaj (Nanoscale, 2015)
Herein, we report a detailed experimental study supported by DFT calculations to understand the mechanism behind the synthesis of cefradine (CFD - an antibiotic) labeled gold nanoparticles (Au NPs) by employing CFD as both a mild reducing and capping agent. The analysis of the effect of growth conditions reveals that a higher concentration of HAuCl4 results in the formation of an increasing fraction of anisotropic structures, higher temperature leads to the formation of quasi-spherical particles instead of anisotropic ones, and larger pH leads to the formation of much smaller particles. The cyclic voltammetry (CV) results show that when the pH of the reaction medium increases from 4 to 6, the reduction potential of CFD increases which leads to the synthesis of nanoparticles (in a pH 4 reaction) to quantum clusters (in a pH 6 reaction). The MALDI-TOF mass spectrometry results of supernatant of the pH 6 reaction indicate the formation of [Au-8(CFD)(2)S-6] QCs which show fluorescence at ca. 432 nm with a Stokes shift of ca. 95 nm. The blue luminescence from Au-8 QCs was applied for sensing of Hg2+ ions on the basis of an aggregation-induced fluorescence quenching mechanism and offers good selectivity and a high sensitivity with a limit of detection ca. 2 nM which is lower than the detection requirement of 10 nM by the U.S. EPA and 30 nM by WHO for drinking water. We have also applied the sensing probe to detect Hg2+ ions in bacterial samples. Further, we have investigated the antibacterial property of as-synthesized Au NPs using MIC, growth curve and cell survival assay. The results show that Au NPs could reduce the cell survival very efficiently rather than the cell growth in comparison to the antibiotic itself. The scanning electron microscopy study shows the degradation and blebbing of the bacterial cell wall upon exposure with Au NPs which was further supported by fluorescence microscopy results. These Au NPs did not show reactive oxygen species generation. We believe that the bacterial cytotoxicity is due to the direct contact of the Au NPs with bacterial cells.

Study on fused/cast AZS refractories for deployment in vitrification of radioactive waste effluents - Sengupta, Pranesh; Mishra, Raman K.; Soudamini, N.; Sen, D.; Mazumder, S.; Kaushik, Chetan P.; Ajithkumar, Thalasseril G.; Banerjee, K. (Journal of Nuclear Materials, 2015)
Fused/cast Al2O3-ZrO2-SiO2 (FC-AZS)' is being considered as `glass contact refractory' within ceramic melters, to be used for nuclear waste immobilization. Microstructural analyses reveal random distributions of baddeleyite (ZrO2) within aluminosilicate (Al2SiO5) matrix. Al-27 and Si-29 NMR data suggest that within aluminosilicate matrix Al occurs in both 4- and 6-fold co-ordinations whereas Si prefers a 4-fold environment. Polydispersity of pores has been studied with small-angle neutron scattering (SANS) technique. Corrosion rates of FC-AZS within 6 M HNO3, simulated wastes (500 h exposure), and borosilicate melt (975 degrees C, 800 h exposure) are found to be 0.38 x 10(3) mu my(-1), 0.13 x 10(3) mu my(-1) and 4.75 x 10(3) mu my(-1) respectively. A comparison of chemical interaction data clearly suggests that FC-AZS exhibits better chemical durability than AZC refractory (Al2O3-ZrO2-Cr2O3, also used for similar purpose). Thermal cycling studies indicate that FC-AZS retains structural integrity (including compressive strength and density) even up to 20 cycles. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Interaction between refractory material and hazardous liquid; Nuclear waste immobilization; Vitrification melter

Supported imidazole as heterogeneous catalyst for the synthesis of cyclic carbonates from epoxides and CO2 - Sankar, Meenakshisundaram; Ajithkumar, Thalasseril G.; Sankar, Gopinathan; Manikandan, Palanichamy (Catalysis Communications, 2015)
Imidazole anchored onto a silica matrix, by means of a propyl linkage, is found to be an effective heterogeneous catalyst for the synthesis of cyclic carbonates from epoxides and CO2 in near quantitative yield. The versatility of this catalyst is demonstrated by using different substrates (epichlorohydrin, propylene oxide, butylene oxide and styrene oxide) for this cycloaddition reaction. These CO2 insertion reactions were typically carried out in the temperature range of 343 to 403 K at 0.6 MPa CO2 pressure under solvent-free conditions. Several spectroscopic methods were used to characterize the catalyst and study the integrity of the fresh and spent catalysts. (C) 2014 Elsevier B.V. All rights reserved.
Keywords: Anchored imidazole; CO2 utilization; cyclic carbonates; epoxides

Surface site modulations by conjugated organic molecules to enhance visible light activity of ZnO nanostructures in photocatalytic water splitting - George, Leena; Sappati, Subrahmanyam; Ghosh, Prasenjit; Devi, R. Nandini (Journal of Physical Chemistry C, 2015)
Surface modification of ZnO nanoparticles is identified as a method of modulating surface sites advantageously. ZnO nanoparticles of two different sizes are surface modified with a conjugated organic moiety to enable electron conduction and transfer. Enhanced H-2 evolution from water-methanol mixtures was observed in the composite systems compared to pristine ZnO under visible light irradiation without any cocatalyst. The system is also marginally active in water splitting in pure water without any sacrificial agents. Photophysical characterization indicates that even though reducing size into the nanoregime affects the band gap detrimentally, modifications by simple conjugated organic molecules assist in enhanced visible light activity. The experimental observations are corroborated with computational studies, which also point to a localization of valence band maximum of the interface on the organic moiety and conduction band minimum on ZnO.

Surface-tuned Co3O4 nanoparticles dispersed on nitrogen-doped graphene as an efficient cathode electrocatalyst for mechanical rechargeable zinc-air battery application - Singh, Santosh K.; Dhavale, Vishal M.; Kurungot, Sreekumar (ACS Applied Materials & Interfaces, 2015)
The most vital component of the fuel cells and metal air batteries is the electrocatalyst, which can facilitate the oxygen reduction reaction (ORR) at a significantly reduced overpotential. The present work deals with the development of surface-tuned cobalt oxide (Co3O4) nanoparticles dispersed on nitrogen-doped graphene as a potential ORR electrocatalyst possessing some unique advantages. The thermally reduced nitrogen-doped graphene (NGr) was decorated with three different morphologies of Co3O4 nanoparticles, viz., cubic, blunt edged cubic, and spherical, by using a simple hydrothermal method. We found that the spherical Co3O4 nanoparticle supported NGr catalyst (Co3O4-SP/NGr-24h) has acquired a significant activity makeover to display the ORR activity closely matching with the state-of-the-art Pt supported carbon (PtC) catalyst in alkaline medium. Subsequently, the Co3O4-SP/NGr-24h catalyst has been utilized as the air electrode in a Zn-air battery, which was found to show comparable performance to the system derived from PtC. Co3O4-SP/NGr-24h catalyst has shown several hours of flat discharge profile at the discharge rates of 10, 20, and 50 mA/cm(2) with a specific capacity and energy density of similar to 590 mAh/g(-zn) and,840 Wh/kg(-zn), respectively, in the primary Zn-air battery system. In conjunction, Co3O4-SP/NGr-24h has outperformed as an air electrode in mechanical rechargeable Zn-air battery as well, which has shown consistent flat discharge profile with minimal voltage loss at a discharge rate of 50 mA/cm(2). The present results, thus demonstrate that the proper combination of the tuned morphology of Co3O4 with NGr will be a promising and inexpensive material for efficient and ecofriendly cathodes for Zn-air batteries.
Keywords: electrocatalyst; mixed facets; oxygen reduction reaction; rechargeable zinc-air battery; surface morphology

Surfactant assisted formation of ruthenium nanochains under mild conditions and their catalytic CO oxidation activity - Sreedhala, S.; Vinod, C. P. (Chemical Communications, 2015)
Spontaneous formation of ruthenium nanochains is accomplished in aqueous medium under mild conditions using a seed mediated protocol with cetyl trimethylammonium bromide (CTAB) as the capping agent. They are formed due to the random self-assembly of Ru seeds of similar to 3.5 nm size. These 1D nanostructures exhibit better catalytic activity towards the oxidation of CO relative to the similar to 3.5 nmseeds and 6 nm Ru nanospheres. The synthesis strategy adopted here is found to be simple, facile and environmentally friendly.

Swarm and swim motilities of salmonella enterica serovar typhimurium and role of osmoregulated periplasmic glucans - Dharne, Mahesh S.; Kannan, Porteen; Murphy, Charles; Smith, Allen; Bhagwat, Arvind A. (Microbiol Discov, 2015)

Switching closed-shell to open-shell phenalenyl: toward designing electroactive materials - Pariyar, Anand; Vijaykumar, Gonela; Bhunia, Mrinal; Dey, Suman Kr.; Singh, Santosh K.; Kurungot, Sreekumar; Mandal, Swadhin K. (Journal of the American Chemical Society, 2015)
Open-shell phenalenyl chemistry started more than half a century back, and the first solid-state phenalenyl radical was realized only 15 years ago highlighting the synthetic challenges associated in stabilizing carbon-based radical chemistry, though it has great promise as building blocks for molecular electronics and multifunctional materials. Alternatively; stable closed-shell phenalenyl has tremendous potential as it can be utilized, to create an in situ open-shell state by external spin injection. In the present study, we have designed a closed-shell phenalenyl-based iron(III) complex, Fe-III(PLY)(3) (PLY-H = 9-hydroxyphenalenone) displaying an excellent electrocatalytic property as cathode material for one compartment membraneless H2O2 fuel cell. The power density output Of Fe-III(PLY)(3) is nearly 15-fold higher than the structurally related model compound Fe-III(acac)(3) (acac = acetylacetonate) and nearly 140-fold higher than an earlier reported mononuclear Fe(III) complex; Fe-III(Pc)Cl (Pc = pthalocyaninate), highlighting the role of switchable closed-shell phenalenyl moiety for electron-transfer process in designing electroactive materials.

Synthesis and antifungal potential of 1,2,3-triazole and 1,2,4-triazole thiol substituted strobilurin derivatives - Chaudhary, Preeti M.; Tupe, Santosh G.; Jorwekar, Shweta U.; Sant, Duhita G.; Deshpande, Sunita R.; Maybhate, Shailaja P.; Likhite, Anjali P.; Deshpande, Mukund V. (Indian Journal of Chemistry Section B-Organic Chemistry Including Medicinal Chemistry, 2015)
beta-Methoxyacrylate group is an important pharmacophore of commercially used strobilurin fungicides. In the present study, a total of seventeen 1,2,4-triazole thiols 8a-h and 1,2,3-triazole substituted 10a-i strobilurin derivatives have been synthesized. 1,2,4-Triazole thiol substituted strobilurin derivatives 8a-h have been found to inhibit the growth of plant pathogens such as Fusarium oxysporum, Magnaporthe grisea, Drechslera oryzae and human pathogens Aspergillus fumigatus and different strains of Cryptococcus neoformans, with MIC in the range of 16-256 mu g/mL. In case of Candida albicans tested strain, the MIC is > 256 mu g/mL. p-Chlorophenyl substituted 1,2,4-triazole thiol strobiulrin derivative 8e is the most potent inhibitor with MIC of 16-64 mu g/mL against most of the tested pathogens. Antifungal action of the compounds is due to inhibition of mitochondrial respiration. In the resazurin reduction assay, EC50 for inhibition of RZ reduction in D. oryzae by azoxystrobin and 8e are 3.42 +/- 0.03 mu g/mL and 3.63 +/- 0.21 mu g/mL, respectively; while in case of C. neoformans, EC50,, of azoxystrobin and 8e are between 0.65-0.85 mu g/mL. In a non-pathogenic model Benjaminiella poitrasii, though the MIC for all the synthesized compounds 8a-h and 10a-i are > 256 mu g/ml, yeast to hypha transition is inhibited in the range of 21-75% at 4 mu g/mL concentration while EC50 for inhibition of RZ reduction by azoxystrobin and 8e are 31.5 +/- 0.4 mu g/mL and 17.95 +/- 0.7 mu g/mL, respectively. The 50% germ tube formation inhibition in case of C. albicans is observed at 108.49 mu g/mL. 1,2,4-Triazole thiol substituted strobilurin derivatives hold promise for the control of pathogenic fungi in agriculture and health care.
Keywords: 1; 2; 3-triazole strobilurin; 4-triazole thiol strobilurin; antifungal; Strobilurin; Y-H transition inhibition

Synthesis and evaluation of thieno[2,3-d]pyrimidin-4(3H)-ones as potential antitubercular agents - Borate, Hanumant B.; Annadate, Ritesh A.; Vagh, Sandip S.; Pisal, Mahesh M.; Deokate, Sagar B.; Arkile, Manisha A.; Jadhav, Nandadeep J.; Nawale, Laxman U.; Sarkar, Dhiman (MedChemComm, 2015)
A number of thieno[2,3-d]pyrimidin-4(3H)-ones were designed, synthesized and screened against Mycobacteria as a part of our program to develop new antitubercular agents. It was observed that some of the compounds have significant antimycobacterial activity against Mycobacterium tuberculosis H37Ra (ATCC 25177) and Mycobacterium bovis BCG (ATCC 35743). The active compounds were studied for cytotoxicity against four cell lines and were found to be non-cytotoxic. The results showed that compounds 13b and 29e were found to exhibit very good antimycobacterial activity (MIC in the range of 6-8 mu M) and the thienopyrimidinones as a class have potential to be developed as antitubercular agents.

Synthesis, characterization of thiolated karaya gum and evaluation of effect of pH on its mucoadhesive and sustained release properties - Bahulkar, Swati S.; Munot, Neha M.; Surwase, Sachin S. (Carbohydrate Polymers, 2015)
Present study aims at synthesis and characterization of thiolated gum karaya by reacting karaya gum with 80% thioglycolic acid resulting in esterification and immobilization of thiol groups on polymeric backbone. Immobilized thiol groups were found to be 5.026 mM/g determined by Ellman's method. It was characterized by FTIR, DSC and XRD. Directly compressible tablets prepared using thiolated gum displayed more disintegration time, swelling and mucoadhesion with increase in pH of medium simulating gastric and intestinal environment than plain gum. Controlled drug release for more than 24h by Fickian diffusion following Korsemeyer-Peppas model was observed with Metoprolol Succinate as a model drug as compared to plain gum which released more than 90% of the drug within 2 h. Synthesized thiomer showed no cytotoxicity determined using HepG2 cell line. According to these results, thiolated gum karaya seems to be promising excipient for the development of mucoadhesive drug delivery systems. (C) 2015 Elsevier Ltd. All rights reserved.

Synthesis, DNA interaction and anticancer activity of 2-anthryl substituted benzimidazole derivatives - Sontakke, Vyankat A.; Kate, Anup N.; Ghosh, Sougata; More, Piyush; Gonnade, Rajesh G.; Kumbhar, Navanath M.; Kumbhar, Anupa A.; Chopade, Balu Ananda; Shinde, Vaishali S. (New Journal of Chemistry, 2015)
2-Anthryl benzimidazole derivatives (5-7) with hydrogen, carboxyl and benzoyl substituents at the 5th position have been synthesized using a silica supported periodic acid catalyst. The DNA cleavage activity of 5-7 was studied in the presence of light using pBR322 plasmid DNA and was shown to vary with substitution at the 5th position of benzimidazole derivatives. DNA binding studies using ethidium bromide displacement assay demonstrated the non-intercalative binding mode of 5-7. The anticancer activity of these target molecules was tested against MCF-7 and HL-60 cell lines, and they exhibited remarkable activity in the micromolar range. Cellular uptake and morphological changes were confirmed by fluorescence and confocal microscopy. A molecular docking study was carried out to explore the DNA binding mechanism of 5-7.

Synthesis of GdB6 nanostructures using nanosecond (Nd: YAG) laser: field emission investigation - Suryawanshi, S. R.; Late, Dattatray J.; More, Mahendra A.; Singh, Anil K.; Sinha, S. (2015 28th International Vacuum Nanoelectronics Conference (IVNC), 2015)
We herein report field emission characteristics of GdB6 nanostructures grown directly on a pellet via laser processing (laser fluence similar to 6 J/cm(2)). The laser processed GdB6 pellet was characterized by X-ray diffraction, which revealed no change in phase upon laser processing. The values of the turn-on field required to draw emission current density of 1 mu A/cm(2) is found to be similar to 2.95 V/mu m, for the laser processed GdB6 emitter. Furthermore, the Fowler-Nordheim (F-N) plot exhibits non-linear behavior over the entire range of applied field and the field enhancement factor (beta) calculated from slope of the F-N plot (low field region) was found to be similar to 543. The emission current stability over a period of 3h was observed to be fairly good. The observed results demonstrate that laser processing can be efficiently used to make GdB6 nanostructure emitter having potential for practical applications.

Synthesis of N, F and S co-doped graphene quantum dots - Kundu, Sumana; Yadav, Ram Manohar; Narayanan, T. N.; Shelke, Manjusha V.; Vajtai, Robert; Ajayan, Pulickel M.; Pillai, Vijayamohanan K. (Nanoscale, 2015)
Graphene quantum dots (GQDs) are a promising category of materials with remarkable size dependent properties like tunable bandgap and photoluminescence along with the possibility of effective chemical functionalization. Doping of GQDs with heteroatoms is an interesting way of regulating their properties. Herein, we report a facile and scalable one-step synthesis of luminescent GQDs, substitutionally co-doped with N, F and S, of similar to 2 nm average size by a microwave treatment of multi-walled carbon nanotubes in a customized ionic liquid medium. The use of an ionic liquid coupled with the use of a microwave technique enables not only an ultrafast process for the synthesis of co-doped GQDs, but also provides excellent photoluminescence quantum yield (70%), perhaps due to the interaction of defect clusters and dopants.

Synthesis of novel N-cyclopentenyl-lactams using the aube reaction - Shinde, Madhuri V.; Ople, Rohini S.; Sangtani, Ekta; Gonnade, Rajesh G.; Reddy, D. Srinivasa (Beilstein Journal of Organic Chemistry, 2015)
A novel and convenient method utilizing the Aube reaction to access a new class of compounds that are similar to carbocyclic nucleosides is reported. The azido alcohol derived from Vince lactam undergoes the Aube reaction with various cyclic ketones to give cyclopentenyl-substituted lactams. Upon dihydroxylation, this affords the N-cyclopentenyl-lactam compounds in racemic form. Given the numerous uses of nucleosides and related compounds, we were interested in the synthesis of carbocylic nucleoside mimics. The attempts and results are described herein.
Keywords: Aube reaction; Biological activity; carbocyclic nucleosides; cyclopentenylated lactams; cyclopentylated lactams

Synthesis, optoelectronic, and transistor properties of BODIPY- and cyclopenta[c]thiophene-containing pi-conjugated copolymers - Debnath, Sashi; Singh, Saumya; Bedi, Anjan; Krishnamoorthy, Kothandam; Zade, Sanjio S. (Journal of Physical Chemistry C, 2015)
Three new low-band-gap copolymers were synthesized by fusing dipyrromethene difluoroborane (BODIPY) as the acceptor (A) and thiophene-capped 5,5-bis(hexyloxymethyl)-5,6-dihydro-4H-cyclopenta[c]-thiophene (CPT) as the donor (D). The BODIPY unit was copolymerized through the `alpha' positions (1 and 7 positions) in P1 and through the `beta' positions (2 and 6 positions) in P2 and P3. The additional acetylene unit between D and A in P3 enhanced the conjugation by minimizing the possible steric hindrance compared to that in P2, whereas P1 exhibited a more red-shifted absorption than P2 and P3 because of the more effective conjugaion through the `alpha' positions of BODIPY. Importantly, the optical band gaps (E-g(opt)) obtained from the onset of the absorption spectra are 1.28, 1.71, and 1.57 eV for P1, P2, and P3, respectively. P1 has the lowest band gap for any CPT-containing polymer. In the best transistor devices, a mobility improvement by 4 orders of magnitude from 3.22 x 10(-6) cm(2) V-1 s(-1) for P2 to 0.01 cm(2) V-1 s(-1) for P1 was achieved. DFT calculations alongside measured charge-transport properties indicated that appreciable alterations in the optoelectronic properties of the polymers were achieved through minor changes in their structural features. The polymers were further characterized by thin-film X-ray diffraction, atomic force microscopy, and spectroelectrochemistry to investigate their material and electrochemical properties.

Tailor made ionic liquids: catalyst and media for organic transformations - Chandra, Prakash; Shinde, Sandip S.; Biradar, Ankush V. (Current Organic Chemistry, 2015)
Ionic liquids are considered as one of the safe, green and environmentally benign solvents/catalysts for many organic reactions. Particularly, imidazolium based ionic liquids attracted much attention in basic as well as applied research. The major role of these ionic liquids is the replacement of the existing corrosive solvents, which are largely used in most of the organic processes and make these processes more eco-friendly. Recent report reveals the importance of imidazolium based ionic liquids, supported on silica gel or polystyrene in catalysis. The solid supports have well versed properties such as easy anchoring of ionic liquid, chemically and mechanically very stable and inert in nature. These ionic liquids can be tailored either by covalent attachment or simple deposition of the ionic liquid on the surface of the support. Both approaches showed enhanced reactivity and selectivity for various reactions. In this review, we made an attempt to review the recent reports related to synthesis and applications of tailor made ionic liquids and their use as catalyst in Aldol, Friedel-Crafts alkylation, hydroformylation, nucleophilic substitution and biomass transformation reactions.
Keywords: Green solvent; heterogeneous catalyst; organic transformation; sustainable process; task-specific ionic liquids

Target cum flexibility: synthesis of indolo[1,2-b]isoquinoline derivatives via cobalt-catalyzed [2+2+2] cyclotrimerization - Swami, Anuradha; Ramana, Chepuri V. (Synlett, 2015)
A modular approach for the synthesis of small molecules having the unnatural 6,11-dihydroindolo[1,2-b]isoquinoline tetracyclic core has been documented. An acid-catalyzed Friedel-Crafts-type C2-alkylation of N-propargyl indole with a suitably activated alkynol has been used to prepare the key indole-derived diynes. The cobalt-catalyzed [2+2+2] cyclotrimerization of these diynes has been studied with various internal/terminal alkynes and with nitriles.
Keywords: 2-b]-isoquinoline; cobalt; Indole; indolo[1; Pyridine; [2+2+2] cyclotrimerization

Targeting a chemorefractory COLO205 (BRAF V600E) cell line using substituted benzo[alpha]phenoxazines - Pal, Sanjima; Konkimalla, V. Badireenath; Kathawate, Laxmi; Rao, Soniya S.; Gejji, Shridhar P.; Puranik, Vedavati G.; Weyhermueller, Thomas; Salunke-Gawali, Sunita (RSC Advances, 2015)
Mutational activations of the oncogene BRAF (especially BRAF V600E) result in a poor prognosis for colon cancer patients and are associated with chemoresistance rendering them refractory to treatment. The development of novel bioactive compounds with specific targeting abilities under such conditions is an urgent need in drug discovery. In this report we synthesize and characterize three fluorescent benzo[alpha]phenoxazine compounds (10R-benzo[alpha]phenoxazine-5-one, 1B; R = Cl, 2B; R = CH3, 3B; R = H) and their anticancer activities are evaluated in a COLO205 cell line. All three compounds with a log P value around 2 were cell permeable. However, 2B and 3B showed specific cytotoxicity in a malignant COLO205 cell line with a BRAF mutation (V600E) in comparison to a non-malignant wild-type BRAF HEK293T cell line. From further cell-based assays (cell cycle analysis, DNA fragmentation and caspase activation), we conclude that 2B and 3B treatment-induced selective cell death by inducing cell cycle arrest at the G0/G1 phase and caspase-mediated apoptosis (activation of the intrinsic and extrinsic pathways) are present only in BRAF V600E COLO205 cells. Further studies in the drug discovery pipeline might help develop these benzo[alpha]phenoxazines as promising chemotherapeutics for such refractory mutated cancers.

Targeting dormant tuberculosis bacilli: results for molecules with a novel pyrimidone scaffold - Joshi, Rohit R.; Barchha, Avinash; Khedkar, Vijay M.; Pissurlenkar, Raghuvir R. S.; Sarkar, Sampa; Sarkar, Dhiman; Joshi, Rohini R.; Joshi, Ramesh A.; Shah, Anamik K.; Coutinho, Evans C. (Chemical Biology & Drug Design, 2015)
Our inability to completely control TB has been due in part to the presence of dormant mycobacteria. This also renders drug regimens ineffective and is the prime cause of the appearance of drug-resistant strains. In continuation of our efforts to develop novel antitubercular agents that especially target dormant mycobacteria, a set of 55 new compounds belonging to the pyrimidone class were designed on the basis of CoMFA and CoMSIA studies, and these were synthesized and subsequently tested against both the dormant and virulent BCG strain of M.tuberculosis. Some novel compounds have been identified which selectively inhibit the dormant tuberculosis bacilli with significantly low IC50 values. This study reports the second molecule after TMC-207, having the ability to inhibit tuberculosis bacilli exclusively in its dormant phase. The synthesis was accomplished by a modified multicomponent Biginelli reaction. A classification model was generated using the binary QSAR approach - recursive partitioning (RP) to identify structural characteristics related to the activity. Physicochemical, structural, topological, connectivity indices, and E-state key descriptors were used for generation of the decision tree. The decision tree could provide insights into structure-activity relationships that will guide the design of more potent inhibitors.
Keywords: Antitubercular activity; dormant tuberculosis bacilli; pyrimidones; recursive partitioning

Temperature-dependent raman spectroscopy of titanium trisulfide (TiS3) nanoribbons and nanosheets - Pawbake, Amit S.; Island, Joshua O.; Flores, Eduardo; Ramon Ares, Jose; Sanchez, Carlos; Ferrer, Isabel J.; Jadkar, Sandesh R.; van der Zant, Herre S. J.; Castellanos-Gomez, Andres; Late, Dattatray J. (ACS Applied Materials & Interfaces, 2015)
Titanium trisulfide (TiS3) has recently attracted the interest of the 2D community because it presents a direct bandgap of similar to 1.0 eV, shows remarkable photoresponse, and has a predicted carrier mobility up to 10000 cm(2) V-1 s(-1). However, a study of the vibrational properties of TiS3, relevant to understanding the electron-phonon interaction that can be the main mechanism limiting the charge carrier mobility, is still lacking. In this work, we take the first steps to study the vibrational properties of TiS3 through temperature-dependent Raman spectroscopy measurements of TiS3 nanoribbons and nanosheets. Our investigation shows that all the Raman modes linearly soften (red shift) as the temperature increases from 88 to 570 K due to anharmonic vibrations of the lattice, which also includes contributions from the lattice thermal expansion. This softening with the temperature of the TiS3 modes is more pronounced than that observed in other 2D semiconductors, such as MoS2, MoSe2, WSe2, and black phosphorus (BP). This marked temperature dependence of the Raman spectra could be exploited to determine the temperature of TiS3 nanodevices by using Raman spectroscopy as a noninvasive and local thermal probe. Interestingly, the TiS3 nanosheets show a stronger temperature dependence of the Raman modes than the nanoribbons, which we attribute to lower interlayer coupling in the nanosheets.
Keywords: 2D semiconductors; layered materials; Raman spectroscopy; thermal effect; TiS3 nanoribbons; TiS3 nanosheets

Temporal protein expression pattern in intracellular signalling cascade during T-cell activation: a computational study - Ganguli, Piyali; Chowdhury, Saikat; Bhowmick, Rupa; Sarkar, Ram Rup (Journal of Biosciences, 2015)
Various T-cell co-receptor molecules and calcium channel CRAC play a pivotal role in the maintenance of cell's functional responses by regulating the production of effector molecules (mostly cytokines) that aids in immune clearance and also maintaining the cell in a functionally active state. Any defect in these co-receptor signalling pathways may lead to an altered expression pattern of the effector molecules. To study the propagation of such defects with time and their effect on the intracellular protein expression patterns, a comprehensive and largest pathway map of T-cell activation network is reconstructed manually. The entire pathway reactions are then translated using logical equations and simulated using the published time series microarray expression data as inputs. After validating the model, the effect of in silico knock down of co-receptor molecules on the expression patterns of their downstream proteins is studied and simultaneously the changes in the phenotypic behaviours of the T-cell population are predicted, which shows significant variations among the proteins expression and the signalling routes through which the response is propagated in the cytoplasm. This integrative computational approach serves as a valuable technique to study the changes in protein expression patterns and helps to predict variations in the cellular behaviour.
Keywords: Boolean model; co-receptors and CRAC channel; synchronous and asynchronous simulation; T-cell signalling pathway; temporal gene expression patterns

Thermodynamic and kinetic characterization of transmembrane helix association - Pawar, Aiswarya B.; Deshpande, Sneha A.; Gopal, Srinivasa M.; Wassenaar, Tsjerk A.; Athale, Chaitanya A.; Sengupta, Durba (Physical Chemistry Chemical Physics, 2015)
The transient dimerization of transmembrane proteins is an important event in several cellular processes and computational methods are being increasingly used to quantify their underlying energetics. Here, we probe the thermodynamics and kinetics of a simple transmembrane dimer to understand membrane protein association. A multi-step framework has been developed in which the dimerization profiles are calculated from coarse-grain molecular dynamics simulations, followed by meso-scale simulations using parameters calculated from the coarse-grain model. The calculated value of Delta G(assoc) is approx. -20 kJ mol(-1) and is consistent between three methods. Interestingly, the meso-scale stochastic model reveals low dimer percentages at physiologically-relevant concentrations, despite a favorable Delta G(assoc). We identify generic driving forces arising from the protein backbone and lipid bilayer and complementary factors, such as protein density, that govern self-interactions in membranes. Our results provide an important contribution in understanding membrane protein organization and linking molecular, nano-scale computational studies to meso-scale experimental data.

Titanium superoxide - a stable recyclable heterogeneous catalyst for oxidative esterification of aldehydes with alkylarenes or alcohols using TBHP as an oxidant - Dey, Soumen; Gadakh, Sunita K.; Sudalai, A. (Organic & Biomolecular Chemistry, 2015)
Titanium superoxide efficiently catalysed the oxidative esterification of aldehydes with alkylarenes or alcohols, under truly heterogeneous conditions, to afford the corresponding benzyl and alkyl esters in excellent yields. Mechanistic studies have established that this ``one pot'' direct oxidative esterification process proceeds through a radical pathway, proven by a FTIR spectral study of a titanium superoxide-aldehyde complex as well as spin trapping experiments with TEMPO. The intramolecular version of this protocol has been successfully demonstrated in the concise synthesis of 3-butylphthalide, an anti-convulsant drug.

Tolbutamide induces conformational change and promotes albumin glycation - Bansode, Sneha B.; Batkulwar, Kedar B.; Warkad, Shrikant D.; Jana, Asis K.; Sengupta, Neelanjana; Kulkarni, Mahesh J. (RSC Advances, 2015)
Tolbutamide is a first generation sulfonylurea drug used for the treatment of type II diabetes. In the present study, the effect of tolbutamide on albumin conformation was investigated using BSA as a model protein. The binding of tolbutamide induced a conformational change in albumin, which was confirmed by thioflavin T assay, ANS assay, and CD spectroscopy. Computer simulations suggested that the binding of tolbutamide increases the solvent accessibility of lysine residues, the hotspots of glycation. Furthermore, the change in conformation of albumin facilitates increased glycation, which was observed by AGE specific fluorescence and the results were corroborated by mass spectrometric analysis. This study suggested that tolbutamide enhances albumin glycation by inducing conformational change in BSA and hence could be a potential risk factor if used for a prolonged period.

Total synthesis and structural revision of mycalol, an anticancer natural product from the marine source - Seetharamsingh, B.; Rajamohanan, P. R.; Reddy, D. Srinivasa (Organic Letters, 2015)
The total synthesis of an anticancer (anaplastic thyroid) natural lipid mycalol has been accomplished for the first time. Synthesis of originally proposed structure necessitated the revision of structure in which the position of acetate group moved from C20 to C19 and a change in stereochemistry of the glycerol unit.

Towards comprehension of complex chemical evolution and diversification of terpene and phenylpropanoid pathways in Ocimum species - Singh, Priyanka; Kalunke, Raviraj M.; Giri, Ashok P. (RSC Advances, 2015)
Ocimum species present a wide array of diverse secondary metabolites possessing immense medicinal and economic value. The importance of this genus is undisputable and exemplified in the ancient science of Chinese and Indian (Ayurveda) traditional medicine. Unlike several other plant species of Artemisia, Salvia, Catharanthus, Taxus, Mentha, etc. that are largely exploited, detailed characterization and identification of important metabolites from Ocimum species remained unexplored. Till date, most of the analyzed Ocimum species are predominantly rich in either phenylpropanoids or terpenoids. Metabolite data suggests domination of a unique set of signature compounds in all species. However, molecular pathways leading to the production, accumulation and metabolism of these compounds are poorly understood. The past few years have witnessed an upsurge in our understanding of the complex and intricately woven secondary metabolic pathways. Such information is generated through systematic analysis and correlation of metabolite profiling with transcriptomics data sets from different Ocimum species. The present review is aimed at integrating our current knowledge to understand the active secondary metabolic pathways, the key players in flux regulation including external stimuli, differential gene expression, transcription factors, microRNAs, enzyme promiscuity, etc. Extensive analysis of available data identifies events that may have contributed to evolve Ocimum species rich with a specific set of metabolites, thus, shedding light on pathway diversification. We believe that a better understanding of the multi-level regulation of intermediates and metabolites will help us harness the inherent diversity of Ocimum species optimally.

Tuning magnetic behavior of nanoscale cobalt sulfide and its nanocomposite with an engineering thermoplastic - Rumale, Narendra; Arbuj, Sudhir S.; Umarji, Govind; Shinde, Manish; Mulik, Uttam P.; Joy, Pattayil Alias; Amalnerkar, Dinesh P. (Journal of Electronic Materials, 2015)
Nanocomposites containing magnetic nanoparticles embedded in a polymer matrix with good thermal stability (up to 200A degrees C) are technologically important. We report an environmentally benign solid-solid approach for synthesis of cobalt sulfide and its nanocomposite using a thermally stable matrix of polyphenylene sulfide. Physicochemical characterizations reveal the formation of nanoclusters of the hexagonal phase CoS. Even though bulk CoS is nonmagnetic, magnetization studies exhibit anomalous magnetic behavior for phase-pure nanoscale CoS and its nanocomposites.
Keywords: Nanocomposite; polyphenylene sulfide; Solid-solid reaction; superparamagnetic

Two phase flow boiling pressure drop in small channels - Sardeshpande, Madhavi V.; Shastri, Parikshit; Ranade, Vivek V. (IUTAM Symposium on multiphase flows with phase change: challenges and opportunities, 2015)
Two-phase pressure drop, flow instability and boiling regime identifications are an essential step in the design of a variety of plant in the power and process industries. Despite the wide spread applications, significant experimental data on flow boiling in small channel is not available. In the present work, experimental set-up was designed for studying boiling flows in 19 mm ID tube and identifies flow regimes at various mass and heat flux conditions by varying inlet fluid temperature. The steady-state pressure data was collected and flow regimes identified using pressure drop and pressure fluctuations inside the channel. (C) 2015 The Authors. Published by Elsevier B.V.
Keywords: flow boiling; flow instability; pressure drop; regime identification

Understanding visceral leishmaniasis disease transmission and its control - a study based on mathematical modelling - Subramanian, Abhishek; Singh, Vidhi; Sarkar, Ram Rup (Mathematics, 2015)

Unraveling the success and failure of mode coupling theory from consideration of entropy - Nandi, Manoj Kumar; Banerjee, Atreyee; Sengupta, Shiladitya; Sastry, Srikanth; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2015)
We analyze the dynamics of model supercooled liquids in a temperature regime where predictions of mode coupling theory (MCT) are known to be valid qualitatively. In this regime, the Adam-Gibbs (AG) relation, based on an activation picture of dynamics, also describes the dynamics satisfactorily, and we explore the mutual consistency and interrelation of these descriptions. Although entropy and dynamics are related via phenomenological theories, the connection between MCT and entropy has not been argued for. In this work, we explore this connection and provide a microscopic derivation of the phenomenological Rosenfeld theory. At low temperatures, the overlap between the MCT power law regime and AG relation implies that the AG relation predicts an avoided divergence at T-c, the origin of which can be related to the vanishing of pair configurational entropy, which we find occurring at the same temperature. We also show that the residual multiparticle entropy plays an important role in describing the relaxation time. (C) 2015 AIP Publishing LLC.

UV-assisted size sampling and antibacterial screening of lantana camara leaf extract synthesized silver nanoparticles - Singh, Pradeep Kumar; Bhardwaj, Kirti; Dubey, Parul; Prabhune, Asmita (RSC Advances, 2015)
Green route synthesized silver nanoparticles are extremely toxic to multidrug resistant bacteria and have widespread applications in biomedical science. If the silver reducing weed extract possesses antimicrobial properties then it can additionally contribute to the medicinal activity. Herein, we present a synthesis of silver nanoparticles by using the weed plant Lantana camara's leaf extract. This study shows an easy, quick and cost-effective route to silver nanoparticle synthesis. Size controlled synthesis of Ag-0 nanoparticles is studied and discussed based on optical absorption, photoluminescence, dynamic light scattering (DLS), zeta potential, infrared spectroscopy, X-ray diffraction measurements, FE-SEM and TEM analysis. The synthesis of silver nanoparticles via this green approach shows very high antibacterial activity against E coli (Gram -ve) and S. aureus (Gram +ve) bacteria at a very low concentration (50 ppm Ag nanoparticles). Use of such eco-friendly nanoparticles may open a door for a new range of bactericidal agents.

Vanadium in borosilicate glass - Sengupta, Pranesh; Dey, Krishna K.; Halder, Rumu; Ajithkumar, Thalasseril G.; Abraham, Geogy; Mishra, Raman K.; Kaushik, Chetan P.; Dey, Goutam K. (Journal of the American Ceramic Society, 2015)
Understanding the role of V2O5 within borosilicate glass matrices is important for the development of novel matrices toward immobilization of sulfate containing high-level nuclear wastes. Present investigation shows, within sodium barium borosilicate glass matrix V2O5 can be homogeneously added up to 5mol% and beyond which it separates out into three phases, for example, (i) silica (ii) Barium (Ba) - Vanadium (V) oxide, and (iii) glass matrix. Si-29 MAS NMR (Nuclear Magnetic Resonance) studies of the samples show that below 5mol% V2O5 addition, silicate network is dominantly constituted of Q(2) and Q(3) structural units, whereas above this, the network gets more polymerized through formation of Q(3) and Q(4) units. In case of borate network, B-11 MAS NMR investigations revealed that the concentration of BO4 [(0B, 4Si)] unit increases gradually up to 5mol% and then it decreases at the cost of BO4 [(1B, 3Si)], BO3 (symmetric) and BO3 (asymmetric) units. Micro-Raman analyses of the samples showed that with additions of V2O5 in diluted concentrations, amorphous silicate network remained unaltered, whereas some amplification in signals corresponding to ring-type metaborate and VO5 units exists. It is therefore apparent from both MAS-NMR and micro-Raman studies that with V2O5 additions within the solubility limit (5mol%), borate network gets depolymerized leading to decrease in hardness from an average value of 5.0-4.2GPa.

Vapour-liquid-solid growth of one-dimensional In2Se3 nanostructures and their promising field emission behaviour - Suryawanshi, Sachin R.; Bankar, Prashant K.; More, Mahendra A.; Late, Dattatray J. (RSC Advances, 2015)
Single crystalline ultra long In2Se3 nanowires have been grown by employing a single step facile thermal evaporation route under optimized conditions on Au/Si wafers, and morphology dependent field emission investigations on the In2Se3 nanostructure at the base pressure -1 x 10(-8) mbar are explored. In addition, structural and morphological analysis of as-synthesized In2Se3 nanostructures has been carried out using XRD, SEM and TEM. A plausible explanation of the vapor-solid-liquid (VLS) growth mechanism based on the experimental results and reported literature has been presented. Furthermore, field emission measurements demonstrate remarkably enhanced emission behaviour, which is explained on the basis of the field enhancement factor and aspect ratio of the nanostructures. The synthesized In25e3 nanowire emitter delivers a very high current density of -1.2 mA cm(-2) at an applied electric field of -6.33 cm(-1). The present results demonstrate In2Se3 as an important candidate for potential applications in nano/micro-electronic devices.

Viridians group streptococci in patients undergoing tooth extraction - Dhotre, Shree V.; Dharne, Mahesh S.; Potdar, S.; Suklikar, J.; Suryawanshi, Namdev; Nagoba, Basavraj (European Journal of General Medicine, 2015)
The aerobic microflora of the oral cavity consists of viridians group of streptococci (VGS). The present study was carried out with an objective to evaluate the prevalence of VGS in patients undergoing tooth extraction and to study their antibiotic susceptibility pattern. Samples of subgingival dental plaques for microbiological studies were collected from 80 patients undergoing tooth extraction. The isolated streptococci were identified along with their antibacterial susceptibilities by automated Vitek 2 (bioMérieux) system in accordance with CLSI standards. A total of 260 VGS strains belonging to 05 phenotypic groups, namely mutans, salivarius, anginosus, sanguinus and mitis groups; along with few strains of Granulicatella like G. adiacens and G. elegans. Altogether a total of 15 species were isolated from the subgingival plaque of 80 patients undergoing tooth extraction. Among the 15 antibiotics tested, highest resistance was observed to lincosamides (36.2%) followed by macrolides (29.7%), tetracyclines (17.7%), cephems (15.1%), fluoroquinolones (14.4%), oxazolidinones (13.5%), streptogramins (12.7 %) and penicillins (7.9%). However, all the 260 VGS strains were found susceptible to vancomycin and linezolid. In the subgingival plaque of patients undergoing tooth extraction, approximately 70% of streptococci belonged to three VGS groups, i.e. mitis, sanguinis and mutans groups. Streptococci of salivarus and anginosus groups were isolated sporadically (5%). Highest resistance was observed to lincosamides and macrolides (29.7%). Multiple antibiotic resistance was observed in mitis and salivarius group.

Vitellibacter nionensis sp nov., isolated from a shallow water hydrothermal vent - Rajasabapathy, Raju; Mohandass, Chellandi; Yoon, Jung-Hoon; Dastager, Syed Gulam; Liu, Qing; Thi-Nhan Khieu; Chu Ky Son; Li, Wen-Jun; Colaco, Ana (International Journal of Systematic and Evolutionary Microbiology, 2015)
A novel, Gram-stain-negative, non-motile, rod-shaped yellow bacterium, designated VBW088(T) was isolated from a shallow water hydrothermal vent in Espalamaca in the Azores. Phylogenetic analysis based on 16S rRNA gene sequences showed that strain VBW088(T) clustered with three type strains of species of the genus Vitellibacter and exhibited a sequence similarity of 97.3% with Vitellibacter soesokkakensis RSSK-12(T). However, strain VBW088(T) and V. soesokkakensis RSSK-12(T) exhibited low DNA-DNA relatedness (12.7 +/- 3.5 %). Strain VBW088(T) was positive for catalase and oxidase. Growth occurred at 10-37 degrees C, with the optimum at 80 degrees C, and at pH 6.0-8.0 (optimum pH 6.0) and in up to 5% (w/v) NaCl with optimum growth at 1-2% (w/v) NaCl. The major fatty acids (>10%) were iso-C-15:0 (33.5%) and iso-C-17:0 3-OH (32.0%). The polar lipids detected in strain VBW088(T) consisted of phosphatidylethanolamine, one unidentified aminolipid and three unidentified phospholipids. The DNA G+C content of strain VBW088(T) was 36.7 mol%. On the basis of phylogenetic inference, DNA-DNA relatedness, chemotaxonomic analysis and physiological data, the isolate represents a novel species of the genus Vitellibacter, for which the name Vitellibacter nionensis sp. nov. is proposed, with the type strain as VBW088(T). (=KCTC 32420(T)=MCC 2354(T)).

Void fraction measurement using electrical capacitance tomography and high speed photography - Sardeshpande, Madhavi V.; Harinarayan, Sagar; Ranade, Vivek V. (Chemical Engineering Research & Design, 2015)
Gas-liquid flows are encountered in variety of industrial applications including boilers, distillation towers, chemical reactors, oil pipelines, nuclear reactors etc. The measurement of two-phase flow parameters such as flow regime and void fraction is considerably important and play an important role in characterization of the hydrodynamic behavior of such gas-liquid two phase systems. The void fraction is a dimensionless quantity and is often termed as ``holdup or fraction'' in two-phase flows. According to industrial applications; it is essential to develop measurement technique for void fraction measurement which can work in hot and opaque systems. Therefore, an attempt was made here to establish electrical capacitance tomography (ECT) facility for measuring void fraction and flow regimes as well as develop suitable data processing methodologies. In the present work, focus was to measure void fraction using ECT technique and compares it with conventional and high speed photography technique. Therefore, that will give guidelines of using ECT technique for hot and opaque systems like boiling flows. (C) 2014 The Institution of Chemical Engineers. Published by Elsevier BM. All rights reserved.
Keywords: ECT; Flow regimes; Two phase flow; Void fraction

Water-dispersible ascorbic-acid-coated magnetite nanoparticles for contrast enhancement in MRI - Sreeja, V.; Jayaprabha, Kunnoth N.; Joy, Pattayil Alias (Applied Nanoscience, 2015)

Water-promoted diels-alder reaction in quaternary ammonium salts - Nagare, Amit S.; Manna, Arpan; Sonawane, Pramod D.; Kumar, Anil (Journal of Physical Organic Chemistry, 2015)
{Prevailing classification of salts based on their effect in solubility and stability of proteins in aqueous solution predicts that tetraalkylammonium salts, guanidinium chloride (GnCl), LiClO4 act as salting-in (S/I) and LiCl, NaCl act as salting-out (S/O) in aqueous conditions. In the same context the behaviour of GnCl, LiClO4 and LiCl are contradictory in polar solvents like ethylene glycol and formamide. In these solvents, expected salt effect shows just opposite nature from their usual expectation. However, in the aqueous solution salts like tetraalkylammonium halide (R4NX
Keywords: Delta G(solvation); Diels-Alder reaction; k(s); kinetic study; solubility; tetraalkylammonium salts; viscosity

Well-defined palladium(II) complexes for ligand enabled C(sp3)-alkynylation - Landge, Vinod Gokulkrishna; Sahoo, Manoj Kumar; Midya, Siba Prasad; Jaiswal, Garima; Balaraman, Ekambaram (Dalton Transactions, 2015)
The first example of ligand-enabled C(sp3)-alkynylation of 8-methylquinoline is reported. The reaction is catalysed by well-defined Pd(II) complexes. The present C(sp3)-alkynylation has a broad substrate scope as well as functional group tolerance and proceeds efficiently under mild conditions.

Zinc inhibits glycation induced structural, functional modifications in albumin and protects erythrocytes from glycated albumin toxicity - Tupe, Rashmi; Kulkarni, Amruta; Adeshara, Krishna; Sankhe, Neena; Shaikh, Shamim; Dalai, Sayli; Bhosale, Siddharth H.; Gaikwad, Sushama M. (International Journal of Biological Macromolecules, 2015)
The present work aims to investigate the concentration and time dependant effect of zinc on the in vitro non enzymatic modifications of albumin by diabetic levels of glucose. Further, preventive and curative effect of zinc was studied by adding zinc before and after initiation of glycation respectively. Glycation of albumin was done at different concentrations of zinc (125, 250 and 500 mu M) at different time intervals (21,28 and 35 days) with appropriate controls. The antiglycation potential of zinc was assessed by estimating different markers of albumin glycation (fructosamines, carbonyls, bound sugar, AGEs), structural modifications (free amino, thiol group, beta amyloid, native PAGE, ANS binding, fluorescence lifetime decay and CD analysis) and functional properties (antioxidant activity, hemolysis). Zinc at highest concentration (500 mu M) significantly reduced modifications of albumin which was comparable to aminoguanidine and also protected secondary and tertiary structure of albumin after 28 days of incubation. Zinc exhibited significant protective effect on erythrocytes by inhibiting hemolysis. Thus the present study indicate preventive mode of albumin glycation inhibition by zinc. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Albumin; Erythrocytes; Glycation

10000-Fold enhancement in proton conduction by doping of cesium ions in a proton-conducting zwitterionic metal-organic framework - Shalini, Sorout; Aggarwal, Shubhangi; Singh, Santosh K.; Dutt, Malvika; Ajithkumar, Thallaseril G.; Vaidhyanathan, Ramanathan (European Journal of Inorganic Chemistry, 2016)
Developing metal-organic framework (MOF)-based proton-conducting electrolytes for fuel-cell applications is an important target that has drawn a lot of attention. A key approach involves the selective replacement of the guest species within the pores to enhance performance. The modular and crystalline nature of the MOF permits controlled introduction of such species and characterization of their compositions with high precision, a task which is very difficult to achieve in amorphous polymers. Herein, we partially replaced the protons of a zwitterionic pyridinol in Mg(terephthalate)(pyridinol) MOF 1 with Cs+ ions, which brought about a 10000-fold increase in the proton conductivity (10(-6) to 10(-2) S cm(-1)). Interestingly, Li+ ions could not be loaded, whereas Cs+ ions with smaller hydrated ionic radii could be loaded, and the loading was controlled as a function of time. The Cs+ loading nearly halved the activation energy (from 0.35 for 1 to 0.19 eV for _Cs). The highest conductivities were realized for an optimal loading of Cs+ ions, which was found to be about 10 % in this case.

1000-fold enhancement in proton conductivity of a MOF using post-synthetically anchored proton transporters - Shalini, Sorout; Dhavale, Vishal M.; Eldho, Kavalakal Mathai; Kurungot, Sreekumar; Ajithkumar, Thalasseril G.; Vaidhyanathan, Ramanathan (Scientific Reports, 2016)
Pyridinol, a coordinating zwitter-ionic species serves as stoichiometrically loadable and non-leachable proton carrier. The partial replacement of the pyridinol by stronger hydrogen bonding, coordinating guest, ethylene glycol (EG), offers 1000-fold enhancement in conductivity (10(-6) to 10(-3) Scm(-1)) with record low activation energy (0.11 eV). Atomic modeling coupled with C-13-SSNMR provides insights into the potential proton conduction pathway functionalized with post-synthetically anchored dynamic proton transporting EG moieties.

1D alignment of PEDOT in a buckypaper for high-performance solid supercapacitors - Soni, Roby; Anothumakkool, Bihag; Kurungot, Sreekumar (Chemelectrochem, 2016)
A flexible solid-state supercapacitor is prepared from carbon nanotube (CNT)-based buckypaper after forming a thin layer of polyethylenedioxythiophene (PEDOT) on the surface of the CNTs in the paper. A highly conducting PEDOT phase is obtained by interfacial polymerization, in which polymerization is confined at the interface of two immiscible liquids. The hydrophilic interaction between the functionalized CNTs and the oxidizing agent (iron perchlorate, Fe(ClO4)(3)), which is located in the aqueous phase, and the restricted interaction of the oxidizing agent with the EDOT monomer in the organic layer at the immiscible interface play a vital role in establishing a uniform and aggregate-free growth pattern of PEDOT on CNT. By carefully optimizing the amount of polymer in the paper, an electrode with a sheet resistance of 3.4(-1) and equivalent series resistance of 0.95 can be prepared. A thin and flexible solid-state supercapacitor device with an overall thickness of 210m is made by using this paper as the electrodes and poly(vinyl alcohol)/lithium chloride as the gel electrolyte. The power density and energy density of the electrode are 9.94Wcm(-3) and 8.85mWhcm(-3), respectively. The device also delivers a high volumetric capacitance of 18Fcm(-3) and areal capacitance of 354mFcm(-2). The demonstrated strategy is scalable and hence the process can be conveniently applied to prepare large-area PEDOT-modified buckypapers in a short time.
Keywords: Carbon; Energy storage; nanotubes; polymerization; Supercapacitors

3-Aminothiophenecarboxylic acid (3-Atc)-induced folding in peptides - Ingole, Tukaram S.; Kotmale, Amol S.; Gawade, Rupesh L.; Gonnade, Rajesh G.; Rajamohanan, Pattuparambil R.; Sanjayan, Gangadhar J. (New Journal of Chemistry, 2016)
This paper describes the consequences of incorporating a constrained heterocyclic aromatic b-amino acid 3-aminothiophenecarboxylic acid (3-Atc) into peptides containing beta-turn forming elements such as Pro-Gly motif and the effect on the secondary structural architecture of the entire peptide backbone. Conformational investigations of oligomers comprising an alpha,beta,alpha peptide sequence were carried out by single-crystal X-ray diffraction, solution-state NMR, nOe-restrained MD simulation and circular dichroism studies. The results suggested that these peptide sequences assume helical architecture. The helical folding in the oligomers was found to be devoid of inter-residual H-bonding, instead found to be stabilized by a co-operative effect of 6-membered H-bonding within the 3-Atc unit and conformational restrictions of individual amino acids in the peptide backbone.

3D Polyaniline architecture by concurrent inorganic and organic acid doping for superior and robust high rate supercapacitor performance - Gawli, Yogesh; Banerjee, Abhik; Dhakras, Dipti; Deo, Meenal S.; Bulani, Dinesh; Wadgaonkar, Prakash P.; Shelke, Manjusha; Ogale, Satishchandra (Scientific Reports, 2016)

Additive mediated syn-anti conformational tuning at nucleation to capture elusive polymorphs: remarkable role of extended pi-stacking interactions in driving the self-assembly - Gawade, Rupesh L.; Chakravarty, Debamitra K.; Kotmale, Amol; Sangtani, Ekta; Joshi, Pranaya V.; Ahmed, Awais; Mane, Manoj V.; Das, Susanta; Vanka, Kumar; Rajamohanan, Pattuparambil R.; Puranik, Vedavati G.; Gonnade, Rajesh G. (Crystal Growth & Design, 2016)
Understanding the process of prenucleation clustering at supersaturating stage is of significant importance to envisage the polymorphism in crystalline materials. Preferential formation of a thermodynamically stable crystal form suggests energetically favored patterns of interactions which control molecular aggregation during nucleation. Introduction of additives during crystallization is sometimes used as a suitable strategy to obtain metastable polymorphs in cases where it is not easy to capture the same by conventional crystallization methods. Comparative analysis of energy relationships and intermolecular interactions between thermodynamically stable and metastable crystal forms provides valuable clues about the nature of growth synthons at prenucleation clustering and preferential crystallization of the thermodynamic form. Conformationally flexible sulfonamide/sulfoester derivatives constituting electron rich and electron deficient aromatic rings were synthesized to study the interplay between pi-stacking and hydrogen bonding synthons. We have identified and characterized the thermodynamically stable and metastable elusive polymorphs of aromatic sulfonamides 1 and 2 and sulfoesters 3 and 4. However, these compounds eluded polymorphism during crystallisation from various common solvents/conditions and only produced thermodynamically stable crystals forms (form I crystals). Surprisingly, exploitation of pyrazinamide as an additive in different stoichiometric ratios during crystallization gave elusive polymorphs [three for 1 (form 1II, form 1III, and form 1IV) and one each for 2 (form 2II), 3 (form 3II), and 4 (form 4II)]. Molecules in stable crystal forms of these compounds are linked via extended chains of parallel displaced pi...pi stacking interactions that seem to play a vital role in driving the self-assembly of molecules and subsequently governing the nucleation process. In contrast, molecules in metastable polymorphs are devoid of such extended pi-stacking assemblies. Interestingly, differential scanning calorimetry, hot stage microscopy, and X-ray crystallographic studies confirmed the thermal crystal-to-crystal transition of all three metastable polymorphs of 1 (form 1II, form 1III, and form 1IV) to its thermodynamically stable crystal form (form 1I). Conformational analysis of molecule 1 using density functional theory calculations also validated higher stability for syn conformation (observed in Form 1I crystals) over anti and midway conformations (seen in metastable polymorphs). Melt crystallization of form 1I crystals of 1 on the larger face (001) of delta-pyrazinamide and lattice matching analysis (GRACE) revealed that the layered arrangement of molecules of delta-pyrazinamide (on 001 face) during heterogeneous nucleation acts as a template (heteroepitaxy) to provide a preferential site for the nucleation of new metastable polymorphs by selectively inhibiting the most preferred crystal form from growing into the nucleus. Solution state one- and two-dimensional (NOESY) H-1 NMR, scanning electron microscopy, and a Cambridge Structural Database survey were conducted to substantiate the role of additives during crystallization.

Adsorptive removal of diuron on biomass ashes: a comparative study using rice husk ash and bagasse fly ash as adsorbents - Deokar, Sunil K.; Singh, Diksha; Modak, Sweta; Mandavgane, Sachin A.; Kulkarni, Bhaskar D. (Desalination and Water Treatment, 2016)
This study describes the use of two types of biomass ashes (BMAs) as adsorbents for diuron removal. Two BMAs, namely rice husk ash (RHA) and bagasse fly ash (BFA), were used in this study, and their adsorption behavior and adsorption mechanism were compared based on various characteristics, such as surface area, pore diameter, and volume. It was found that the particle size and the composition of these BMAs, especially the content of carbon and silica, primarily affect the adsorption kinetics and capacity. Compared with RHA, BFA has more carbon content (47.37%), and therefore shows higher adsorption capacity (43.48mol/g). In addition, BFA has larger external surface area and exhibited faster kinetics at the initial adsorption stage; by contrast, RHA due to its larger pore diameter allows for faster pore adsorption and surpasses the initial kinetic rate of BFA. For the same particle size (0.354-0.251mm), the equilibrium capacity of BFA was found to be four times greater than that of RHA; in addition, the surface area of BFA is two times more than that of RHA, suggesting that BFA has more active sites than RHA. It was found that solution pH influences adsorption mechanism of diuron molecule on BMA. The uptake capacity of BFA and RHA is 10 times greater than natural adsorbents such as soil and is comparable with synthetic adsorbents such as activated carbon and multiwalled carbon nanotubes. To our knowledge, removal of diuron using ashes has not been reported previously.

Alternate synthesis of appetite suppressant (R)-2-benzylmorpholine employing Sharpless asymmetric epoxidation strategy - Viswanadh, N.; Mujumdar, P.; Sasikumar, M.; Kunte, S. S.; Muthukrishnan, Murugan (Tetrahedron Letters, 2016)
An alternate synthesis of (R)-2-benzylmorpholine 1, an appetite suppressant agent has been accomplished starting from readily available trans-cinnamyl alcohol employing Sharpless asymmetric epoxidation strategy as a key step, with an overall yield of 24%. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: (R)-2-Benzylmorpholine; Appetite suppressant; Sharpless asymmetric epoxidation

Amelioration of excision wounds by topical application of green synthesized, formulated silver and gold nanoparticles in albino Wistar rats - Naraginti, Saraschandra; Kumari, P. Lakshmi; Das, Raunak Kumar; Sivakumar, A.; Patil, Sagar Hindurao; Andhalkar, Vaibhav Vilas (Materials Science & Engineering C-Materials for Biological Applications, 2016)
Wound healing, a complex biological process, has attained a lot of attention as dermatologists are primarily interested in stimulated wound closure without formation of scar or a faint scar. The recent upsurgence of nanotechnology has provided novel therapeutic materials in the form of silver and gold nanoparticles which accelerate the wound healing process. The effect of formulated nanoparticles using Coleus forskohlii root extract (green synthesized) has been tried out for ameliorating full thickness excision wounds in albino Wistar male rats. The evaluation of in vivo activity of nanoparticles in wound healing was carried out on open wounds made by excision on the dorsal sides of albino Wistar rats under anesthesia, and the healing of the wounds was assessed. Histological aspects of the healing process were studied by a HE (Hematoxylin and Eosin) staining method to assess various degrees of re-epithelialization and the linear alignment of the granulation tissue whereas Van Gieson's histochemical staining was performed to observe collagen fibers. The healing action shown by the formulated nanoparticles was remarkable during the early stages of wound healing, which resulted in the substantial reduction of the whole healing period. Topical application of formulated gold nanoparticles was found to be more effective in suppressing inflammation and stimulating re-epithelialization compared to silver nanoparticles during the healing process. The results throw light on the amelioration of excision wounds using nanoparticles which could be a novel therapeutic way of improving wound healing in clinical practice. The mechanism of advanced healing action of both types of nanoparticles could be due to their antimicrobial, antioxidant and anti-inflammatory properties. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: collagen; Gold; green synthesis; Nanopraticles; wound Healing

Ammonium catalyzed cyclitive additions: evidence for a cation-pi interaction with alkynes - Nagy, Edith; St Germain, Elijah; Cosme, Patrick; Maity, Pradip K.; Terentis, Andrew C.; Lepore, Salvatore D. (Chemical Communications, 2016)
The addition of carbamate nitrogen to a non-conjugated carbon-carbon triple bond is catalyzed by an ammonium salt leading to a cyclic product. Studies in homogeneous systems suggest that the ammonium agent facilitates nitrogen-carbon bond formation through a cation-p interaction with the alkyne unit that, for the first time, is directly observed by Raman spectroscopy.

Angiotensin II analogs comprised of pro-amb (gamma-turn scaffold) as angiotensin II type 2 (AT(2)) receptor agonists - Jedhe, Ganesh S.; Kotmale, Amol S.; Rajamohanan, Pattuparambil R.; Pasha, Santosh; Sanjayan, Gangadhar J. (Chemical Communications, 2016)
We describe herein the design, synthesis and conformational investigation of Pro-Amb (proline-3-amino-2-methoxybenzoic acid) incorporated Angiotensin II and its truncated analogues. Solution-state NMR and CD studies suggest gamma-turn-like conformation in Pro-Amb analogs in aqueous solution. Furthermore, Pro-Amb analogs have been shown to act as AT(2) receptor agonists.

Anti-oxidant properties of ficus religiosa L. Bark extract on human keratinocytes - Dixit, Shailesh S.; Kulkarni, Atul; Seo, Hyo Hyun; Gadgil, Jayant; Dingre, Medini; Umar, Ahmad; Moh, Sang Hyun; Parasharami, Varsha A. (Science of Advanced Materials, 2016)
Ficus religiosa (Sacred Fig) is a medicinally important tree, native to the Indian subcontinent. It has been extensively pharmacologically researched species having wide spectrum of medicinal properties. All parts of F. religiosa tree are known to possess important medicinal properties such as anti-oxidant, anti-inflammatory, wound healing and skin diseases etc. However, effects of F. religiosa on skin cells line HaCaT was not studied for its antioxidant properties. In this report we have investigated F. religiosa bark aqueous extract for its antioxidant properties on human keratinocytes (HaCaT) cell line using DPPH, superoxide dismutase 1, superoxide dismutase 2 and catalase assay. We observed that F. religiosa bark aqueous extract efficiently scavenged (80%) DPPH radicals. Superoxide dismutase1 assay of F. religiosa bark aqueous extract effectively scavenged superoxide radicals (O-2(-)) and showed dose dependent activity. Reactive oxygen species were trapped by superoxide dismutase 2 assay of F. religiosa bark aqueous extract and form hydrogen peroxide. Catalase assay results revelled that hydrogen peroxide was further decomposed to give water and oxygen. Thus various anti-oxidant assays of F. religiosa bark aqueous extract indicate that it efficiently reduced the reactive oxygen species in skin cells.
Keywords: Anti-Oxidant; Catalase Assay; DPPH Assay; Ficus religiosa; Keratinocyte HaCaT Cell Line; Moraceae; SOD Assay

Architecture of 2D MoS2 nanosheets and 3D CdMoS4 marigold flowers: consequence of annealing on field emission performance - Kadam, Sunil R.; Suryawanshi, Sachin R.; Panmand, Rajendra P.; Mate, Vivek R.; More, Mahendra A.; Late, Dattatray J.; Kale, Bharat B. (Microporous and Mesoporous Materials, 2016)
Herein, we report the field electron emission investigations on template free solvothermally synthesized layered MoS2 nanosheets as well as novel phase of CdMoS4 nanoflowers at the base pressure of similar to 1 x 10(-8) mbar. The turn-on field, threshold field and maximum emission current densities for both MoS2 and CdMoS4 are strongly influenced by thermal annealing in inert atmosphere. The turn on field, required to draw emission current density of 1 mu A/cm(2) is found to be 5.8 and 3.2 V/mu m for pristine and annealed MoS2 at 400 degrees C. In case of as prepared and annealed CdMoS4 sample the turn on field values are found to be similar to 6.2 and 5.0 V/mu m, respectively. The emission current versus time (I-t) plot measured at the preset current values of similar to 1 mu A for pristine and annealed sample indicates stable operation of the emitter. The emission current fluctuations for annealed sample are observed to be less as compared with the pristine sample due to conditioning of the emitter, thereby showing highly stable nature of emitter. Thus, the present result demonstrates the potential of annealed MoS2 nanosheets and CdMoS4 nanoflowers as an emerging materials for micro/nanoelectronics and flat panel field emission display applications. (C) 2016 Elsevier Inc. All rights reserved.
Keywords: field emission; MoS2 and CdMoS4; Nanoflowers; nanosheets

Asymmetric transfer hydrogenation of cyclic imines in water with a versatile hydrogen donorformic acid/N-methylpiperidine: rapid access to highly enantioselective amines - Shende, Vaishali S.; Shingote, Savita K.; Deshpande, Sudhindra H.; Kelkar, Ashutosh. A. (Chemistryselect, 2016)
Asymmetric transfer hydrogenation (ATH) of cyclic imines in water has been investigated for the first time by using HCOOH in combination with bases other than triethylamine as H donor. Effect of FA/Base ratio has shown significant impact on activity and enantioselectivity for ATH reaction in water. Use of methanol as a co-solvent improved the reduction performance. FA/N-methylpiperidine was found to be excellent, versatile hydrogen donor for ATH of imine 6,7-dimethoxy-1-methyl-3,4-dihy-droisoquinoline (1a) giving by far the highest noted TOF value of 5940 h(-1). ATH of-different imines derivatives including 3, 4-dihydoisoquinolines, beta-carbolines and cyclic sulfonyl imines have been performed with excellent activity (91-99% yield) and enantioselectivity (88-97%) in very short time (1-2 min). This is very simple protocol for rapid access to enantioselective amines with very new and versatile hydrogen donor 1.1 FA/Nmethylpiperidine.

Au(I)/Ag(I) co-operative catalysis: interception of Ag-bound carbocations with α-gold(I) enals in the imino-alkyne cyclizations with N-allenamides - Bagle, Pradip N.; Mane, Manoj V.; Vanka, Kumar; Shinde, Dinesh R.; Shaikh, Samir R.; Gonnade, Rajesh G.; Patil, Nitin T. (Chemical Communications, 2016)

Balancing omega-6: Omega-3 ratios in oilseeds - Chirmade, T. P.; Sanghi, S.; Rajwade, A .V.; Gupta, V. S.; Kadoo, N. Y. (Omega-3 fatty acids: keys to nutritional health, 2016)
Fats and oils are the essential constituents of human diet, and nearly 80 % of these are obtained from plants. The predominant fatty acids present in plant oils are saturated and unsaturated compounds with straight aliphatic chains of carbon atoms and a single carboxyl group. Depending on the position of the first double bond from the methyl end in the fatty acyl chain, the mono- and polyunsaturated fatty acids can be denoted as -9, -6, or -3. Excess consumption of -6 fatty acids has greatly and unfavorably increased the -6: -3 ratio up to 25:1, which is associated with prevalence of many negative health effects, including cardiovascular diseases, cancer, osteoporosis, and inflammatory and autoimmune diseases. Because the -3 fatty acids (FAs) are the precursors for synthesis of anti-inflammatory eicosanoids, balancing the -6: -3 ratio is vital. The easiest approach to achieve this would be consumption of oils rich in -3 FAs, such as linseed oil. Alternatively, the fatty acid biosynthetic pathway in plants producing high -6 FAs can be altered by biotechnological means, so that they produce higher proportion of -3 FAs. This chapter describes the current knowledge of the fatty acid biosynthesis pathway in plants, including the genes involved, their temporal and spatial expression patterns, and various fluxes that they drive. The choice of oilseeds, genes, and promoters for modulating the fatty acid biosynthesis flux from -6 to -3 fatty acids is also dealt with. The potential hurdles in achieving these and possible solutions have also been described.

Band edge modulated polymer layer to decrease back electron transfer and increase efficiency in sensitized solar cells - Arulkashmir, Arulraj; Sudhakar, Vediappan; Krishnamoorthy, Kothandam (Advanced Energy Materials, 2016)
Recombination of charges residing in the TiO2 and redox electrolyte is one of the factors affecting the efficiency of dye sensitized solar cells (DSSCs). To circumvent this recombination, inorganic oxide barrier layers and organic silanes have been coated on TiO2/dyes. Due to the insulating nature of these layers, the efficiency increase is not very impressive. Conducting polymers with different band edges are used to suppress the charge recombination. Amongst the four polymers that are used as barrier layers, a polymer with a highest occupied molecular orbital energy at -5.8 eV and lowest unoccupied molecular orbital at -3.1 eV is found to increase the electron life time at TiO2 and decrease the charge recombination. The electron life time is found to be 88 ms. In addition to the long electron life time, the recombination resistance of this polymer is also high (91 Omega). This resistance is 18% higher than that measured for DSSCs without polymer barrier layer. These factors impact the efficiency of DSSCs. DSSCs fabricated with this polymer as barrier layer exhibit an efficiency of 9.2%, which is 22% higher than that of DSSCs without polymer barrier layer.

Benz–amidinato stabilized a monomeric calcium Iodide and a lithium calciate(II) cluster featuring group 1 and group 2 elements - Yadav, Sandeep; Swamy, V. S. V. S. N.; Gonnade, Rajesh G.; Sen, Sakya S. (ChemistrySelect, 2016)
Soluble calcium halides reported so far are mostly dimeric in nature. The halides occupy the bridging position and thus provide additional coordination to the metal. We obtained a monomeric calcium iodide [{PhC(NiPr)(2)} CaI(thf)(3)] (1) from the reaction of [PhC(NiPr)(2)] Li with Cal(2) in THF. The compound has been stabilized by electronic donation and steric shielding from the amidinate ligand as well as coordination of three THF molecules. 1 does not show any propensity towards ligand exchange reaction. When the same reaction is carried out in diethyl ether instead of THF, it led to the formation of a Li calciate(II) cluster of composition L2Ca4I8Li4O (L= PhC(NiPr)(2)) (2) with an encapsulated O2+ in the middle of a tetrahedron spanned by four Ca2+ ions. 2 represents a metal-rich halide comprising of both alkali and alkaline earth metals which is quite unprecedented. Another notable aspect is that the amidinate ligand binds to the calcium atom in chelating bidentate mode in 1, whereas in 2 each N atom of the amidinate ligands binds to two Ca atoms leading to bridging bis-chelating coordination mode.

Bicinchoninic acid-based colorimetric chemosensor for detection of low concentrations of cyanide - Biradar, Archana A.; Biradar, Ankush V.; Sun, Tiffany; Chan, Yung; Huang, Xiaoxi; Asefa, Tewodros (Sensors and Actuators B-Chemical, 2016)
Bicinchoninic acid (BCA) is reagent that is widely used to determine the concentration of proteins in solutions through the colored complex it forms with Cu(I) and the proteins. In this report, we present a new use for BCA, where a highly sensitive method for detection of cyanide ions in solutions by using Cu2+-BCA complex as the chemosensing agent is demonstrated. The detection of cyanide ions is achieved by taking advantage of the nucleophilic attack of the Cu2+-BCA complex by cyanide ions. Upon the addition of cyanide ions, the Cu2+-BCA complex undergoes transformations to free BCA via a series of equilibriums and, as a result, forms different Cu(II)-(BCA)(x)(CN)(y) species depending on the concentrations of cyanide ions in the solution. These different Cu(II)-(BCA)(x)(CN)(y) species, in turn, give different metal-to-ligand charge transfer electronic spectra and colors that are easily detectable both with naked eyes and UV-vis spectroscopy. As the cyanide ion concentration increases, the color of the solution containing the complexes changes from green to purple, red, yellow, and finally colorless, giving a corresponding blue shift in the absorption maxima on their UV-vis spectra. Through this process, the complexes enable detection of cyanide ions with a detection level of up to 0.06 ppm in solutions. Thus, this colorimetric technique based on Cu2+-BCA can make low concentrations of cyanide detectable, well before the concentrations possibly reach lethal amounts. Furthermore, the method is shown to give fast detection response with no interference from other anionic and cationic species and has the potential to be adopted for accurate and convenient analysis of cyanide ions in drinking water sources as well as industrial effluents. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: BCA; Bicinchoninic acid; Chemosensor; Colorimetric sensor; Copper; Cyanide

Big Data Deluge in Biology: Challenges and Solutions - Sarkar, Ram Rup (Journal of Informatics and Data Mining, 2016)

Bilayer cryogel wound dressing and skin regeneration grafts for the treatment of acute skinwounds - Priya, S. Geetha; Gupta, Ankur; Jain, Era; Sarkar, Joyita; Damania, Apeksha; Jagdale, Pankaj R.; Chaudhari, Bhushan P.; Gupta, Kailash C.; Kumar, Ashok (ACS Applied Materials & Interfaces, 2016)
In this study, the potential of cryogel bilayer wound dressing and skin regenerating graft for the treatment of surgically created full thickness wounds was evaluated. The top layer was composed of polyvinylpyrrolidone-iodine (PVP-I) and served as the antiseptic layer, while the bottom regenerative layer was made using gelatin cryogel. Both components of the bilayer showed typical features of a cryogel interconnected macropore network, rapid swelling, high water uptake capacity of about 90%. Both PVP and gelatin cryogel showed high tensile strength of 45 and 10 kPa, respectively. Gelatin cryogel sheets were essentially elastic and could be stretched without any visible deformation. The antiseptic PVP-I layer cryogel sheet showed sustained iodine release and suppressed microbial growth when tested with skin pathogens (zone of inhibition cm for sheet of 0.9 cm diameter). The gelatin cryogel sheet degraded in vitro in weeks. The gelatin cryogel sheet supported cell infiltration, attachment, and proliferation of fibroblasts and keratinocytes. Microparticles loaded with bioactive molecules (mannose-6-phosphate and human fibrinogen) were also incorporated in the gelatin cryogel sheets for their role in enhancing skin regeneration and scar free wound healing. In vivo evaluation of healing capacity of the bilayer cryogel was checked in rabbits by creating full thickness wound, defect (diameter 2 cm). Macroscopic and microscopic observation at regular time intervals for 4 weeks demonstrated better and faster skin regeneration in the wound treated with cryogel bilayer as compared to untreated defect and the repair was comparable to commercial skin regeneration scaffold Neuskin-F. Complete skin regeneration was observed after 4 weeks' of implantation with no sign of inflammatory response. Defects implanted with cryogel having mannose-6-phosphate showed no scar formation,, while the wound treated with bilayer incorporated with human fibrinogen microparticles showed early signs of skin regeneration; epidermis formation occurred at 2 weeks after implantation.

Biogenic terbium oxide nanoparticles as the vanguard against osteosarcoma - Iram, Sana; Khan, Salman; Ansary, Abu Ayoobul; Arshad, Mohd; Siddiqui, Sahabjada; Ahmad, Ejaz; Khan, Rizwan H.; Khan, Mohd Sajid (Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 2016)
The synthesis of inner transition metal nanoparticles via an ecofriendly route is quite difficult. This study, for the first time, reports synthesis of terbium oxide nanoparticles using fungus, Fusarium oxysporum. The biocompatible terbium oxide nanoparticles (Tb2O3 NPs) were synthesized by incubating Tb4O7 with the biomass of fungus F. oxysporum. Multiple physical characterization techniques, such as UV-visible and photoluminescence spectroscopy, TEM, SAED, and zeta-potential were used to confirm the synthesis, purity, optical and surface characteristics, crystallinity, size, shape, distribution, and stability of the nanoemulsion of Tb2O3 NPs. The Tb2O3 NPs were found to inhibit the propagation of MG-63 and Saos-2 cell-lines (IC50 value of 0.102 mu g/mL) and remained non-toxic up to a concentration of 0373 gg/mL toward primary osteoblasts. Cell viability decreased in a concentration-dependent manner upon exposure to 10 nmTb(2)O(3) NPs in the concentration range 0.023-0373 mu g/mL Cell toxicity was evaluated by observing changes in cell morphology, cell viability, oxidative stress parameters, and FACS analysis. Morphological examinations of cells revealed cell shrinkage, nuclear condensation, and formation of apoptotic bodies. The level of ROS within the cells an indicator of oxidative stress was significantly increased. The induction of apoptosis at concentrations <= IC50 was corroborated by 4',6-diamidino-2-phenylindole dihydrochloride (DAPI) staining (DNA damage and nuclear fragmentation). Flow-cytometric studies indicated that the response was dose dependent with a threshold effect. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: Biosynthesis; Cytotoxicity; fusarium oxysporum; Osteosarcoma; Tb2O3 nanoparticles

Bioresponsive carbon nano-gated multifunctional mesoporous silica for cancer theranostics - Prasad, Rajendra; Aiyer, Sandhya; Chauhan, Deepak S.; Srivastava, Rohit; Selvaraj, Kaliaperumal (Nanoscale, 2016)
Designing bioresponsive nanocarriers for controlled and efficient intracellular drug release for cancer therapy is a major thrust area in nanomedicine. With recent recognition by the US FDA as a safe material for human trials, mesoporous silica nanoparticles (MSNPs) are being extensively explored as promising theranostic agents. Green fluorescent carbon quantum dots (CQDs), though known as possible alternatives for their more toxic and relatively less efficient predecessors, are less known as gate keepers for drug release control. We report for the first time an efficient bioresponse of CQDs when judiciously designed using glutathione cleavable (redox responsive) disulphide bonds. When the anticancer drug doxorubicin loaded MSNPs are capped with these CQDs, they display promising drug release control on exposure to a mimicked intracellular cancer environment. Their dual functionality is well established with good control on preventing the premature release and exceptional bio-imaging of HeLa cancer cells. Fluorescence images prove selective targeting of HeLa cells by overexpression of folate receptors from the surface functionalised folic acid ligand. Extensive characterisation using XRD, TEM, BET analysis, drug loading tests, drug release kinetics, MTT assay and fluoroscence cell imaging helps in understanding the multi-functionalities of the successful design, extending its scope with exciting prospects towards non-invasive targeted drug delivery and bio-imaging for effective cancer diagnosis and treatment.

Biosurfactant as a promoter of methane hydrate formation: thermodynamic and kinetic studies - Arora, Amit; Cameotra, Swaranjit Singh; Kumar, Rajnish; Balomajumder, Chandrajit; Singh, Anil Kumar; Santhakumari, B.; Kumar, Pushpendra; Laik, Sukumar (Scientific Reports, 2016)
Natural gas hydrates (NGHs) are solid non-stoichiometric compounds often regarded as a next generation energy source. Successful commercialization of NGH is curtailed by lack of efficient and safe technology for generation, dissociation, storage and transportation. The present work studied the influence of environment compatible biosurfactant on gas hydrate formation. Biosurfactant was produced by Pseudomonas aeruginosa strain A11 and was characterized as rhamnolipids. Purified rhamnolipids reduced the surface tension of water from 72 mN/m to 36 mN/m with Critical Micelle Concentration (CMC) of 70 mg/l. Use of 1000 ppm rhamnolipids solution in C type silica gel bed system increased methane hydrate formation rate by 42.97% and reduced the induction time of hydrate formation by 22.63% as compared to water saturated C type silica gel. Presence of rhamnolipids also shifted methane hydrate formation temperature to higher values relative to the system without biosurfactant. Results from thermodynamic and kinetic studies suggest that rhamnolipids can be applied as environment friendly methane hydrate promoter.

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

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

Broad spectrum photon responsive, paramagnetic beta-NaGdF4: Yb3+, Er3+ - mesoporous anatase titania nanocomposite - Padhye, Preeti; Sadhu, Subha; Malik, Monika; Poddar, Pankaj (RSC Advances, 2016)
Herein, we report a novel single multifunctional platform based on broad-spectrum photoactive beta-NaGdF4:18% Yb3+, 2% Er3+ and mesoporous anatase TiO2 for enhanced energy and simultaneous biomedical applications. Currently, the photoactive materials for solar energy harvesting applications have limitations in their efficiency due to their narrow photon absorption spectrum. The upconversion phosphor beta-NaGdF4: 18% Yb3+, 2% Er3+ nanorods collect and harvest the NIR photons (similar to 980 nm) of sunlight and transform them into visible light via anti-Stokes emission (lambda(em) similar to 521 and similar to 540 nm), and the photoactive mesoporous anatase TiO2 (mTiO(2)) utilizes UV and weak visible photons, thus the composite forms a broad spectrum photon-capture system and improved power conversion efficiency for enhanced applications in photocatalysis, and dye sensitized solar cells (DSSCs). The photocatalytic activity of the nanocomposite showed an improvement in comparison to the mTiO(2) for the degradation of various dyes. In addition, the photocurrent density and solar cell efficiency of the nanocomposites showed an improvement by similar to 24% and similar to 17% respectively, over mTiO(2). The beta-NaGdF4: Yb3+, Er3+/mTiO(2) nanocomposite exhibits a strong paramagnetic signal (chi similar to 6.45 x 10(-5) emu g(-1) Oe(-1)). The nuclear magnetic resonance (NMR) measurements showed large longitudinal T1 relaxivity (r(1) = 7.09 s(-1) mM(-1)) and magnetic resonance imaging showed enhanced T-1-weighted MRI images with increased concentrations of beta-NaGdF4: Yb3+, Er3+/mTiO(2) nanocomposite making them suitable for simultaneous magnetoresonance imaging. In addition, this composite system can also be used as a NIR triggered drug delivery system and in biomedical applications. Moreover, mesoporous TiO2 is expected to increase the photocatalytic active sites, dye, and absorption, and drug loading capacity. The as-designed multifunctional beta-NaGdF4:Yb3+, Er3+/mTiO(2) nanocomposite possessed simultaneous multiple discrete functionalities with excellent luminescence properties, intrinsic paramagnetism, biocompatibility, improved photocatalytic activity, and solar cell efficiency. This work provides a promising system to utilize NIR light, which will contribute to efficient photon harvesting and biological applications.

Bromide ion mediated modification to digestive ripening process: preparation of ultra-small Pd, Pt, Rh and Ru nanoparticles - Seth, Jhumur; Bhagavatula L. V. Prasad (Nano Research, 2016)
Nanoparticles of catalytically important transition metals, such as Pd, Pt, Rh, and Ru have been prepared by the well-known “digestive ripening” (DR) and “modified digestive ripening” (mDR) methods. In the traditional DR process, a polydisperse colloidal dispersion is refluxed in the presence of a surface-active molecule, such as alkanethiol. The mDR method involved a small modification in the procedure, wherein refluxing was performed with an alkanethiol and a tetra-alkylammonium bromide surfactant. This minor modification led to a dramatic change in the final particle size distributions, giving access to nanoparticles in the <3 nm size regime; this was not possible with the traditional DR process. Bromide ions, which are present during refluxing, proved to be an important ingredient in the modification process. These bromide ions are revealed to act as etchants, resulting in ultra-small nanoparticles. All transition metal nanoparticles investigated displayed catalytic activity in the reduction reaction of p-nitro phenol. Pd nanoparticles, synthesized by a modified digestive ripening method, exhibited the best catalytic activity among the systems investigated.

Calculation of hyperfine structure constants of small molecules using Z-vector method in the relativistic coupled-cluster framework - Sasmal, Sudip; Talukdar, Kaushik; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Journal of Chemical Sciences, 2016)
The Z-vector method in the relativistic coupled-cluster framework is employed to calculate the parallel and perpendicular components of the magnetic hyperfine structure constant of a few small alkaline earth hydrides (BeH, MgH, and CaH) and fluorides (MgF and CaF). We have compared our Z-vector results with the values calculated by the extended coupled-cluster (ECC) method reported in Phys. Rev. A 91 022512 (2015). All these results are compared with the available experimental values. The Z-vector results are found to be in better agreement with the experimental values than those of the ECC values.

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

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

Catalytic activity of bare and porous palladium nanostructures in the reduction of 4-nitrophenol - Kalekar, Ajit M.; Sharma, Kiran Kumar K.; Luwang, Meitram Niraj; Sharma, Geeta K. (RSC Advances, 2016)
The catalytic activity of bare and porous palladium nanostructures viz. palladium nanoballs (PdNBs) and palladium urchins (Pdurc) synthesized in surfactant based liquid crystalline mesophase have been investigated in the reduction of 4-nitrophenol. The loading of PdNBs and Pdurc nanocatalyst in the reaction are optimized to 1.57 x 10(-4) mol% and 1.57 x 10(-3) mol% respectively. The surface area normalized rate constant obtained at 303 K for PdNBs (0.74 +/- 0.03) s(-1) m(-2) L and Pdurc (0.41 +/- 0.05) s(-1) m(-2) L is the highest, considering the low palladium loading used in the reaction. The specific surface area determined for the PdNBs and Pdurc are 153 m(2) g(-1) and 27 m(2) g(-1) respectively. The high surface area of PdNBs nanostructure is consistent with the highest catalytic activity. The palladium nanostructure catalyzed reaction lacks induction time (t(0)), indicating the influence of porosity in the Langmuir-Hinshelwood mechanism. Besides, PdNBs and Pdurc exhibited thermal stability and structural integrity with good conversion of the substrate (>97%) even up to five consecutive reactions. The mechanistic insight of the bare and porous palladium nanostructures presented in this study is significant for the development of stable and efficient palladium metal based nanocatalyst.

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

Characterizing flow and solid suspension in optimax crystallization workstation - Sardeshpande, M.; Pandit, A.; Vedantam, S.; Ranade, V. V. (North American Mixing Forum 2016 - Core Programming Area at the 2016 AIChE Annual Meeting, 2016)

Characterizing the nanoclay induced constrained amorphous region in model segmented polyurethane-urea/clay nanocomposites and its implications on gas barrier properties - Rath, Sangram K.; Sudarshan, Kathi; Bhavsar, Rupesh S.; Kharul, Ulhas K.; Pujari, Pradeep K.; Patri, Manoranjan; Khakhar, Devang V. (Physical Chemistry Chemical Physics, 2016)
There has been an increasing recognition of the fact that purely geometric factors associated with clay platelet dispersion in a polymer matrix cannot adequately explain the barrier properties of polymer/clay nanocomposites. The objective of the present work is to understand the nanoclay induced structural changes in a polyurethane-urea matrix and clay dispersion at different length scales using segment-specific characterization techniques and implications of the same in gas barrier properties using He, N-2 and CO2 as probe molecules. Wide angle X-ray diffraction (WAXD) and positron annihilation life time spectroscopy (PALS) studies revealed nanoclay induced alterations in the chain packing of the amorphous soft segments of the polyurethane matrix at a molecular scale of a few Angstroms. The hard segment organization and the phase morphology of the nanocomposites, spanning length scales of several nanometers, were investigated by small angle X-ray scattering (SAXS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Furthermore, the presence of a constrained amorphous region surrounding the nanoclay was confirmed from AFM, WAXD and PALS results. Several pertinent structural variables from the gas transport point of view were deduced from these characterization techniques to understand the effect of the barrier properties in tandem with the clay dispersion morphology.

Chitosan-based lead ion-imprinted interpenetrating polymer network by simultaneous polymerization for selective extraction of lead(ii) - Hande, Pankaj E.; Kamble, Sanjay; Samui, Asit B.; Kulkarni, Prashant S. (Industrial & Engineering Chemistry Research, 2016)
In this study, we report the synthesis of a Pb(II) ion-imprinted interpenetrating polymer network (II-IPN) by simultaneous polymerization for selective extraction of Pb(II) from printed-circuit-board (PCB) recycling unit wastewater. Initially, a polymer network was synthesized by polymerization of methacrylic acid (monomer) and ethylene glycol dimethacrylate (cross-linker) and a second polymer network by chitosan (complexing monomer) and tetraethyl orthosilicate (cross-linker). The chemical structure and morphology of the II-IPN were analyzed using Fourier transform infrared, field-emission scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. The interaction of the functionality in the II-IPN with Pb(II) through chelation was studied by X-ray photoelectron spectroscopy analysis. The maximum adsorption capacities for II-IPN and nonimprinted interpenetrating polymer network were 37.5 and 10.3 mg g(-1), respectively. The largest selectivity coefficient for Pb(II) in the presence of W(VI) was 161.58. The developed Pb(II) II-IPN was successfully employed for selective extraction of Pb(II) from PCB recycling unit wastewater.

Cholesterol-dependent conformational plasticity in GPCR dimers - Prasanna, Xavier; Sengupta, Durba; Chattopadhyay, Amitabha (Scientific Reports, 2016)
The organization and function of the serotonin1A receptor, an important member of the GPCR family, have been shown to be cholesterol-dependent, although the molecular mechanism is not clear. We performed a comprehensive structural and dynamic analysis of dimerization of the serotonin1A receptor by coarse-grain molecular dynamics simulations totaling 3.6 ms to explore the molecular details of its cholesterol-dependent association. A major finding is that the plasticity and flexibility of the receptor dimers increase with increased cholesterol concentration. In particular, a dimer interface formed by transmembrane helices I-I was found to be sensitive to cholesterol. The modulation of dimer interface appears to arise from a combination of direct cholesterol occupancy and indirect membrane effects. Interestingly, the presence of cholesterol at the dimer interface is correlated with increased dimer plasticity and flexibility. These results represent an important step in characterizing the molecular interactions in GPCR organization with potential relevance to therapeutic interventions.

Chromium free high temperature water-gas shift catalyst for the production of hydrogen from waste derived synthesis gas - Jha, Ajay; Jeong, Dae-Woon; Lee, Yeol-Lim; Jang, Won-Jun; Shim, Jae-Oh; Jeon, Kyung-Won; Rode, Chandrashekhar V.; Roh, Hyun-Seog (Applied Catalysis A-General, 2016)
A comparative study between monometallic (Me-CeO2, Me =Zn, Cu, Fe and Co) and Ni-doped bimetallic (Me-Ni-CeO2) catalysts has been performed in the high temperature water-gas shift (HT-WGS) reaction using waste derived synthesis gas. Experimental results revealed that Me-Ni-CeO2 exhibited higher catalytic performance than simple Me-CeO2 catalysts. Within the Me-Ni-CeO2 series, Co-Ni-CeO2 exhibited excellent and stable catalytic performance (CO conversion > 90%) at a very high GHSV of 143,000 h(-1). The existence of high" concentration of Ce3+ ions and oxygen vacancies on the catalyst surface were responsible for the increased WGS activity of Co-Ni-CeO2. In addition, Co-Ni-CeO2 maintains a stable performance for 50 h. However, commercial Fe2O3-Cr2O3 catalyst showed a steep decline from their initial CO conversion values 15-10% within 5 h. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: CeO2; Co-Ni-CeO2; Lattice strain; oxygen vacancies; Water-gas shift

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

CO oxidation on large high-index faceted Pd nanostructures - Sreedhala, S.; Sudheeshkumar, V.; Vinod, C. P. (Journal of Catalysis, 2016)
The structure sensitivity of CO oxidation has been investigated on oxide-supported palladium nanoparticles of different morphologies. The reactivity of concave nanocubes and nanoflowers that expose {3 1 0} and {3 1 1} high-index facets showed a lower onset temperature for CO oxidation than Pd nanospheres of size around 6 nm. These concave nanocubes and nanoflowers were also found to catalyze the CO oxidation reaction more efficiently than simple cubes and spheres of similar size that exposed low-index facets. The enhanced activity of these nanoparticles compared with other morphologies are attributed to the presence of sites of under-coordination on the exposed high-index facets. The larger nanoparticles were also found to be more stable in the reaction environment. (C) 2016 Elsevier Inc. All rights reserved.
Keywords: CO oxidation; High-index facets; Pd nanoparticles; structure sensitivity

CO2 Laser direct written MOF-based metal-decorated and heteroatom-doped porous graphene for flexible all-solid-state microsupercapacitor with extremely high cycling stability - Basu, Aniruddha; Roy, Kingshuk; Sharma, Neha; Nandi, Shyamapada; Vaidhyanathan, Ramanathan; Rane, Sunit; Rode, Chandrashekhar V.; Ogale, Satishchandra B. (ACS Applied Materials & Interfaces, 2016)
Over the past decade, flexible and wearable microelectronic devices and systems have gained significant importance. Because portable power source is an essential need of such wearable devices, currently there is considerable research emphasis on the development of planar interdigitated micro energy-torage devices by employing diverse precursor materials to obtain functional materials (functional carbon, oxides, etc.) with the desirable set of properties. Herein we report for the first time the use of metal organic framework (MOF) and zeolitic imidazolate framework (ZIF-67) for high-wavelength photothermal laser direct writing of metal-decorated, heteroatom-doped, porous few-layer graphene electrodes for microsupercapacitor application. We argue that the specific attributes of MOF as a precursor and the high-wavelength laser writing approach (which creates extremely high localized and transient temperature (>2500 degrees C) due to strong absorption by lattice vibrations) are together responsible for the peculiar interesting properties of the carbon material thus synthesized, thereby rendering extremely high cycling stability to the corresponding microsupercapacitor device. Our device exhibits near 100% retention after 200 000 cycles as well as stability under 150 degrees bending.

Cobalt ferrite bearing nitrogen-doped reduced graphene oxide layers spatially separated with microporous carbon as efficient oxygen reduction electrocatalyst - Kashyap, V.; Singh, S. K.; Kurungot, S. (ACS Applied Materials and Interfaces, 2016)
The present work discloses how high-quality dispersion of fine particles of cobalt ferrite (CF) could be attained on nitrogen-doped reduced graphene oxide (CF/N-rGO) and how this material in association with a microporous carbon phase could deliver significantly enhanced activity toward electrochemical oxygen reduction reaction (ORR). Our study indicates that the microporous carbon phase plays a critical role in spatially separating the layers of CF/N-rGO and in creating a favorable atmosphere to ensure the seamless distribution of the reactants to the active sites located on CF/N-rGO. In terms of the ORR current density, the heat-treated hybrid catalyst at 150 °C (CF/N-rGO-150) is found to be clearly outperforming (7.4 ± 0.5 mA/cm 2 ) the state-of-the-art 20 wt % Pt-supported carbon catalyst (PtC) (5.4 ± 0.5 mA/cm 2 ). The mass activity and stability of CF-N-rGO-150 are distinctly superior to PtC even after 5000 electrochemical cycles. As a realistic system level exploration of the catalyst, testing of a primary zinc-air battery could be demonstrated using CF/N-rGO-150 as the cathode catalyst. The battery is giving a galvanostatic discharge time of 15 h at a discharge current density of 20 mA/cm 2 and a specific capacity of ∼630 mAh g -1 in 6 M KOH by using a Zn foil as the anode. Distinctly, the battery performance of this system is found to be superior to that of PtC in less concentrated KOH solution as the electrolyte.

Cobalt-modified covalent organic framework as a robust wateroxidation electrocatalyst - Aiyappa, Harshitha Barike; Thote, Jayshri; Shinde, Digambar Balaji; Banerjee, Rahul; Kurungot, Sreekumar (Chemistry of Materials, 2016)
The development of stable, efficient oxygen evolution reaction (OER) catalyst capable of oxidizing water is one of the premier challenges in the conversion of solar energy to electrical energy, because of its poor kinetics. Herein, a bipyridine-containing covalent organic framework (TpBpy) is utilized as an OER catalyst by way of engineering active Co(II) ions into its porous framework. The as-obtained Co-TpBpy retains a highly accessible surface area (450 m(2)/g) with exceptional stability, even after 1000 cycles and 24 h of OER activity in phosphate buffer under neutral pH conditions with an overpotential of 400 mV at a current density of 1 mA/cm(2). The unusual catalytic stability of Co-TpBpy arises from the synergetic effect of the inherent porosity and presence of coordinating units in the COF skeleton.

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

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

Complexation key to a pH locked redox reaction - Rizvi, Masood Ahmad; Dangat, Yuvraj B.; Shams, Tahir; Khan, Khaliquz Zaman (Journal of Chemical Education, 2016)
An unfavorable pH can block a feasible electron transfer for a pH dependent redox reaction. In this experiment, a series of potentiometric titrations demonstrate the sequential loss in feasibility of iron(II) dichromate redox reaction over a pH range of 0-4. The pH at which this reaction failed to occur was termed as a pH locked reaction. The comparative ability of 10 selected iron binding ligands with varied propensity for the redox potential modification of Fe(III)/Fe(II) redox couple to restore/unlock the pH locked redox reaction is shown using potentiometric titrations. The spectrophotometric speciation analysis of Fe(III) Tiron complexation with pH was carried out to explain the differing ability of EDTA and Tiron to unlock the reaction under different pH Conditions. The experiment illustrates how environmental, biological redox reactions avoid severe laboratory conditions to occur and can be explored in the design of novel redox systems for natural attenuation of environmental toxins to their non- or lesser-toxic forms. The experiment also demonstrates prudent laboratory practice for safe waste disposal.
Keywords: Analytical Chemistry; Aqueous Solution Chemistry; Coordination Compounds; Oxidation/Reduction; pH; Physical Chemistry; Potentiometry; Second-Year Undergraduate; Thermodynamics; Titration/Volumetric Analysis; Upper-Division Undergraduate

Compounds with low-valent p-block elements for small molecule activation and catalysis - Yadav, Sandeep; Saha, Sumana; Sen, Sakya S. (Chemcatchem, 2016)
The past decade has witnessed staggering progress in the chemistry of compounds with low-valent main-group elements. Although these discoveries are mostly fundamental by nature, these compounds show promising reactivity towards small molecule activation. The reactivity of these compounds stems from the modest HOMO-LUMO energy gap; a characteristic known for the transition metals. The journey began in 2005 with the facile activation of dihydrogen by an alkyne analog of germanium [ArGeGeAr; Ar=2,6-Trip(2)-C6H3 (Trip=2,4,6-iPr(3)-C6H2)]. Subsequently, tremendous progress has been achieved in understanding and elucidating the potential of these compounds to activate small molecules as well as to use them in a variety of stoichiometric and catalytic transformations. In this review, we focus on developments in the activation of H-2, NH3, CO, and CO2 by compounds with multiply bound or open shell main-group elements. Emphasis will be given to their catalytic activity.
Keywords: activation; carbenes; main-group elements; silylenes; small molecules

Concise enantioselective synthesis of (+)-L-733,060 and (+)-T-2328 via sequential proline catalysis - Lalwani, Komal G.; Sudalai, Arumugam (Synlett, 2016)
A new, sequential proline-catalyzed approach to the synthesis of (+)-L-733,060 and (+)-T-2328 in high optical purity (93% ee) is described starting from phenyl N-Boc imine. The strategy involves proline-catalyzed Mannich reaction of an arylimine with acetaldehyde followed by -aminoxylation/Wittig olefination in a sequential fashion as the key steps.
Keywords: Aminoxylation; imine; Mannich reaction; olefination; sequential

Concise enantioselective synthesis of (+)-sertraline and (-)-CP-52002 using proline catalysis - Kalshetti, Rupali G.; Venkataramasubramanian, V.; Kamble, Sanjay P.; Sudalai, Arumugam (Tetrahedron Letters, 2016)
A short enantioselective synthesis of (+)-sertraline and its C-4 epimer (-)-CP-52002 with an overall yield of 30%, respectively, as its hydrochloride has been described. The key steps are the proline catalyzed Mannich reaction of acetaldehyde and acid catalyzed intramolecular Friedel-Crafts' alkylation reaction of olefin proceeding with high optical purities. (C) 2016 Elsevier Ltd. All rights reserved.
Keywords: Indatraline; Mannich reaction; Proline catalysis; Sertraline; Tametraline

Conformational dynamics of GPCR dimers is dependent on membrane cholesterol - Sengupta, Durba; Prasanna, Xavier; Chattopadhyay, Amitabha (Biophysical Journal, 2016)

Conformational energy landscape of the ritonavir molecule - Chakraborty, Debayan; Sengupta, Neelanjana; Wales, David J. (Journal of Physical Chemistry B, 2016)
Conformational polymorphism of ritonavir, a well-known pharmaceutical drug, is intricately linked to its efficacy in the treatment of acquired immunodeficiency syndrome (AIDS). Polymorphic transition from the crystalline form I to form II leads to the loss of bioactivity. The constituent ritonavir molecules adopt a trans configuration about the carbamate torsion angle in the form I crystal, and a cis configuration in the form II crystal. Investigating the energetics and mechanistic features of conformational transitions at the single molecule level is a key step toward decoding the complex features of the solid state polymorphism. In this work, we employ the energy landscape framework to investigate the conformational transitions of an isolated ritonavir molecule. The landscape is explored using discrete path sampling (DPS) and visualized in terms of disconnectivity graphs. We identify two distinct funnels corresponding to the two molecular forms that are identified by crystallography. The two regions can be reliably distinguished using the carbamate torsion angle, and the corresponding interconversion rates are predicted to follow Arrhenius behavior. The results provide mechanistic insight into pathways for cis <-> trans interconversion at the molecular level and may also help in elucidating the polymorphic transitions in the crystal state.

Conformational features of the Aβ42 peptide monomer and its interaction with the surrounding solvent - Khatua, Prabir; Jose, Jaya C.; Sengupta, Neelanjana; Bandyopadhyay, Sanjoy (Physical Chemistry Chemical Physics, 2016)

Constructing covalent organic frameworks in water via dynamic covalent bonding - Thote, Jayshri; Aiyappa, Harshitha Barike; Kumar, Raya Rahul; Kandambeth, Sharath; Biswal, Bishnu P.; Shinde, Digambar Balaji; Roy, Neha Chaki; Banerjee, Rahul (Iucrj, 2016)
The formation of keto-enamine based crystalline, porous polymers in water is investigated for the first time. Facile access to the Schiff base reaction in water has been exploited to synthesize stable porous structures using the principles of Dynamic Covalent Chemistry (DCC). Most credibly, the water-based Covalent Organic Frameworks (COFs) possess chemical as well as physical properties such as crystallinity, surface area and porosity, which is comparable to their solvothermal counterparts. The formation of COFs in water is further investigated by understanding the nature of the monomers formed using hydroxy and non-hydroxy analogues of the aldehyde. This synthetic route paves a new way to synthesize COFs using a viable, greener route by utilization of the DCC principles in conjunction with the keto-enol tautomerism to synthesize useful, stable and porous COFs in water.

Controllable synthesis of SnO2 photocatalyst with superior photocatalytic activity for the degradation of methylene blue dye solution - Prakash, K.; Kumar, P. Senthil; Pandiaraj, S.; Saravanakumar, K.; Karuthapandian, S. (Journal of Experimental Nanoscience, 2016)
SnO2 photocatalyst was successfully synthesised by novel chemical route in hydrothermal environment and annealed at two different temperatures viz 550 and 600 degrees C, respectively. The crystal structure, optical properties, surface and bulk morphology have been characterised using various tools like X-ray diffraction (XRD), UV visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscope (TEM) and scanning electron microscope (SEM). Cubic, spheres and porous like morphology of SnO2 photocatalyst was successfully confirmed using SEM micrographs and TEM. In addition to this the photocatalytic activity was evaluated towards the degradation of methylene blue dye solution. SnO2 photocatalyst annealed at 600 degrees C exhibits excellent photocatalytic efficiency which may be attributed to the unique morphology, high crystalline nature and charge separation. The photocatalyst efficiency was further tested towards the concentration of dye, catalyst dosage and pH of the dye. The involvement of center dot OH in the photocatalytic reaction was evidenced using trapping experiment by employing different scavengers. The photocatalyst was moderately active, stable upto its fifth usage and stability of the photocatalyst before and after the photocatalytic reaction was also been studied using XRD and SEM.

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

Copolymers comprising monomers with various dipole and quadrupole as active material in organic field effect transistors - Singh, Saumya; Chithiravel, Sundaresan; Krishnamoorthy, Kothandam (Journal of Physical Chemistry C, 2016)
Copolymers of 4,4-difluoro-4-borata-3a-azonia-4a-aza-s-indacene (BODIPY) and diketopyrrolopyrrole (DPP) were synthesized. The BODIPY has a permanent dipole and the DPP has a quadrupole. The dipole and the quadrupole in the monomers are expected to bring the polymers closer and to improve the charge-transport properties. By judicious choice of these monomers, the electron wave function is evenly distributed through the molecules. However, we notice that the torsional angle at the connecting point of BODIPY and DPP is a function of the methyl moieties at the beta,beta' position of the BODIPY. We found that the polymer comprising DPP and BODIPY without methyl moiety at beta,beta' position showed a torsional angle of 27, the lowest among the three polymers studied in this work. The absorption spectrum of the polymer showed transitions because of vibronic coupling indicating linearity along the polymer backbone. The band gap of the polymer was found to be 1.2 eV. The thermally stable polymer showed an ambipolar charge transport of 0.01 cm(2)/(V s).

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

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

Cu-catalyzed sequential C-N bond formations: expeditious synthesis of tetracyclic indoloindol-3-ones - Kulkarni, Anand M.; Srinivas, Kolluru; Deshpande, Mukund V.; Ramana, Chepuri V. (Organic Chemistry Frontiers, 2016)
The tetracyclic indoloindol-3-one core has been forged from easily accessible 2,2'-bis-bromochalcones employing a reaction cascade comprising Cu-catalyzed SNAr with azide; nitrene C-H insertion and intramolecular Ullmann reaction with all three C-N bond formations in one-go.